A solution study of complex formation between iron(III) and oxalate in dimethylsulphoxide

The complex formation between iron(III) and oxalic acid (ethanedioic acid, H2ox) has been studied by potentiometry in dimethylsulphoxide (dmso) solution. H2ox behaves as a weak diprotic acid in such a solvent, with overall association constants: log βj1=8.551(3) and log βj2=14.242(3) at 25°C and 0.1 Mn-Bu4NClO4. A reliable set of overall stability constants for the iron(III)-oxalato complexes, log β11=13.16(4), log β12=23.66(4) and log β13=30.75(4), have been obtained for the first time under identical conditions. The electrochemical behaviour of such complexes was studied in dmso at a platinum electrode. The coordination ability of oxalate towards iron(III) in dmso and water media is compa…

1D coordination polymer based on copper(II)-containing tetrameric 1,2,3-triazole ligand from click chemistry: Magnetic and catalytic properties

Abstract A novel tetrameric tetra[O-((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)]-pentaerythritol (TBTP) has been synthesized using click chemistry strategy. TBTP was characterized and used as ligand to form new Cu(II) complexes, forming 1-D coordination polymers. Two square planar complexes were characterized by single-crystal X-ray diffraction, presenting formula [Cu(TBTP)][Cu(NO3)4] (1) and [Cu(TBTP)](NO3)2 (2). In both structures, a cationic 1-D coordination polymer (CP) has been formed. The CP contain a 1:1 Cu(II)/TBTP ratio with four neutral triazole groups coordinating the Cu(II) center, forming a Cu N bonds ranging 1.988(2)–2.001(2) A. The study of the magnetic properties of compounds 1…

Unexpected magnetic topology in the heterobimetallic [ReIVBr4(μ-ox)CuII(bpy)2] compound

Abstract A novel oxalato-bridged rhenium(IV)-copper(II) compound, namely [ReIVBr4(μ-ox)CuII(bpy)2] (1), has been obtained by reacting (PPh4)2[ReBr4(ox)] with Cu(CF3SO3)2 and 2,2′-bpy in CH3CN, and its crystal structure determined by single-crystal X-ray diffraction. Intermolecular Br⋯Br interactions and nonbonding Cu⋯Br type contacts between the heterobimetallic dinuclear units lead to a two-dimensional supramolecular structure. Compound 1 behaves magnetically as a [ReIVCuII]2 tetranuclear species with weak antiferromagnetic interactions through the oxalato bridge and intermolecular Br⋯Br contacts.

Magnetic coupling and spin topology in linear oxalato-bridged tetranuclear chromium(III)–copper(II) complexes with aromatic diimine ligands

Abstract A novel heterotetranuclear chromium(III)–copper(II) complex of formula {[CrIII(bpy)(ox)2]2CuII2(bpy)2(ox)}·6H2O (1) has been synthesized by the ligand exchange reaction between Ph4P[CrIII(bpy)(ox)2]·H2O and [CuII(bpy)2(NO3)]NO3·MeOH in methanol (bpy = 2,2′-bipyridine; ox2− = oxalate dianion). The X-ray crystal structure of 1 consists of neutral oxalato-bridged CrIII2Cu2II zigzag entities which are formed by the monodentate coordination of two [CrIII(bpy)(ox)2]− mononuclear anionic units through one of its two oxalato groups toward a [CuII2(bpy)2(ox)]2+ dinuclear cationic moiety featuring relatively long axial bonds at the square pyramidal CuII ions. Variable temperature (2.0–300 K)…

Heterotrimetallic coordination polymers: {Cu(II)Ln(III)Fe(III)} chains and {Ni(II)Ln(III)Fe(III)} layers: synthesis, crystal structures, and magnetic properties.

The use of the [Fe(III) (AA)(CN)4](-) complex anion as metalloligand towards the preformed [Cu(II) (valpn)Ln(III)](3+) or [Ni(II) (valpn)Ln(III) ](3+) heterometallic complex cations (AA=2,2'-bipyridine (bipy) and 1,10-phenathroline (phen); H2 valpn=1,3-propanediyl-bis(2-iminomethylene-6-methoxyphenol)) allowed the preparation of two families of heterotrimetallic complexes: three isostructural 1D coordination polymers of general formula {[Cu(II) (valpn)Ln(III) (H2O)3 (μ-NC)2 Fe(III) (phen)(CN)2 {(μ-NC)Fe(III) (phen)(CN)3}]NO3 ⋅7 H2O}n (Ln=Gd (1), Tb (2), and Dy (3)) and the trinuclear complex [Cu(II) (valpn)La(III) (OH2 )3 (O2 NO)(μ-NC)Fe(III) (phen)(CN)3 ]⋅NO3 ⋅H2O⋅CH3 CN (4) were obtained …

Low-Dimensional 3d–4f Complexes Assembled by Low-Spin [FeIII(phen)(CN)4]− Anions

The synthesis, crystal structure, and magnetic properties of four new mixed 3d-4f complexes with formulas [{FeIII(phen)(CN)4} 4Gd2 III(bpym)(NO3) 2(H2O)4]·2CH3CN· 2H2O}n (1), [{FeIII(phen)(CN)4} 4Tb2 III(bpym)(H2O) 8]·(NO3)2·2CH3CN} n (2), [{FeIII(phen)(CN)4}4Sm III(bpym)(NO3)2(H2O) 5]·2CH3CN}n (3), and [{Fe III(phen)(CN)4}2Pr2 III(bpym)(NO3)4(H2O) 2]n (4) (phen = 1,10-phenanthroline and bpym = 2,2′-bipyrimidine) are discussed here. Compounds 1-3 are isomorphous and their structure consists of neutral ladder-like motifs where the rungs are made up by bpym-bridged dilanthanide(III) cations and the rods are defined by [Fe(phen)(CN)4]- units adopting a bis-monodentate coordination mode through…

Self-assembly of a chiral three-dimensional manganese(II)-copper(II) coordination polymer with a double helical architecture

The use of the anionic dicopper(ii) complex, [CuII(mpba) 2]4- [mpba = N,N′-1,3-phenylenebis(oxamate)], as tetrakis(bidentate) metalloligand toward MnII ions in the presence of oxalate and the chiral (S)-trimethyl-(1-phenylethyl)ammonium cation affords the first example of a mixed oxalato/oxamato-based chiral 3D metal-organic polymer. © 2013 The Royal Society of Chemistry.

All-cis-1,2,3,4,5,6-cyclohexanehexacarboxylate two-dimensional gadolinium(III) complexes: Synthesis, X-ray crystal structure and magnetic properties

Abstract The first gadolinium(III) complexes with the trideprotonated form of the 1,2,3,4,5,6-cyclohexanehexacarboxylic acid (H3clhex3−) of formulae [Gd(H3clhex)(H2O)4]n·3nH2O (1) and [Gd(H3clhex)(H2O)4]n·6nH2O (2) have been prepared through the gel technique and their structures determined by single crystal X-ray diffraction. The structure of 1 is made up of 63 honey-comb layers which are generated by [Gd(H2O)4]3+ cations and H3clhex3− anions acting as three-fold nodes and three-fold connectors, respectively. The structure of 2 consists of a [44,62] two-dimensional network extended in the ac plane where the H3clhex−3 groups act as four-fold connectors and the [Gd(H2O)4]3+ units as four-fol…

Copper(II)-methylmalonate complexes with unidentate N-donor ligands: Syntheses, structural characterization and magnetic properties

Abstract Two new methylmalonate-bridged copper(II) complexes with the formulas [Cu(3-Ipy)(Memal)(H 2 O)] ( 1 ) and [Cu(2,4′-bpy)(Memal)(H 2 O)] · 3H 2 O ( 2 ) [Memal = methylmalonate dianion, 3-Ipy = 3-iodopyridine, 2,4′-bpy = 2,4′-bipyridine] have been synthesized and characterized by X-ray diffraction. Both compounds crystallize in the monoclinic space group P 2 1 / n and Z  = 4, with unit cell parameters a  = 8.5874(13) A, b  = 7.1738(14) A, c  = 19.093(5) A, β  = 99.509(15)° in 1 and a  = 17.375(4) A, b  = 7.3305(14) A, c  = 14.247(3) A, β  = 111.409(15)° in 2 . The structures of 1 and 2 consist of zigzag chains of anti-syn carboxylate-bridged copper(II) ions running along the b directi…

Spin canting in an unprecedented three-dimensional pyrophosphate- and 2,2'-bipyrimidine-bridged cobalt(II) framework.

The three-dimensional cobalt(ii) compound of formula {[Co(2)(P(2)O(7))(bpym)(2)].12H(2)O}(n), where the pyrophosphate and 2,2'-bipyrimidine act as bridging ligands, is a new example of a spin-canted antiferromagnet with T(c) = 19 K.

CuII2, CuII4 and CuII6 complexes with 3-(2-pyridyl)pyrazolate. Structure, magnetism and core interconversion

Abstract Reactions of stoichiometric amounts of L1(−) (HL1 = 3-(2-pyridyl)pyrazole) with [Cu(H2O)6](ClO4)2, with or without PhCO2−, in MeOH or N,N′-dimethylformamide (dmf), led to the isolation of three copper(II) complexes of varying nuclearity, [CuII2(L1)2(ClO4)2(MeOH)2] (1), [CuII4(L1)4(O2CPh)2(MeOH)4](ClO4)2·2H2O (2) and [CuII6(L1)6(O2CPh)2(ClO4)2(dmf)4](ClO4)2·2dmf·2H2O (3). Structural analysis reveals two centrosymmetric four-coordinate {CuII(L1)(ClO4)(MeOH)} units are dipyrazolate-bridged in 1, giving rise to a square-pyramidal (SP; τ = 0.13) coordination to the CuII ion. In 2, two centrosymmetric four-coordinate dipyrazolate-bridged {CuII2(μ-L1)2(MeOH)2}2+ units in two layers are he…

Dimensionally controlled hydrogen-bonded nanostructures: synthesis, structure, thermal and magnetic behaviour of the tris-(chelated)nickel(II) complex [Ni(bipy)3]Cl2·5.5H2O (bipy=2,2′-bipyridyl)

Abstract Single crystals of the compound of formula [Ni(bipy)3]Cl2·5.5H2O (bipy=2,2′-bipyridine) have been prepared and structurally characterised by X-ray diffraction. The structure analysis reveals that the complex has an approximate D3 symmetry. The coordination sphere consists of six nitrogen atoms of the three-bipyridine ligands in an octahedral arrangement about the nickel. One of the chlorine ions is surrounded by twelve CH⋯Cl hydrogen bonds. Three kinds of layers are found in the crystal structure: (i) the Λ-[Ni(bipy)3]2+ cation; (ii) the water/chloride positions (O(1w)/Cl(21) to O(7w)/Cl(27)); (iii) the Δ-[Ni(bipy)3]2+ cation and a chloride ion (Cl(1)). The layers are stacked in t…

Synthesis crystal structure and magnetic properties of [Fe2(bpym)(C5O5)2(H2O)4]·2H2O and two polymorphs of [Fe2(bpym)(C4O4)2(H2O)6]·2H2O (bpym = 2,2′-bipyrimidine)

Abstract Two dinuclear iron(II) complexes of formulae [Fe2(bpym)(C5O5)2(H2O)4]·2H2O (1) and [Fe2(bpym)(C4O4)2(H2O)6]·2H2O (2) (bpym = 2,2-bipyrimidine, C5O52 = dianion of croconic acid (4,5-dihydroxycylopent-4-ene-1,2,3-trione) and C4O42 = dianion of squaric acid (3,4-dihydroxycyclobut-3-ene-1,2-dione)) were prepared and their crystal structures (at 103 K) determined by X-ray diffraction methods. The structure of 1 consists of neutral centrosymmetric [Fe2(bpym)(C5O5)2(H2O)4] units and water molecules of crystallization which are linked by an extensive network of hydrogen bonds. The coordination geometry around each iron atom is that of a compressed octahedron with bpym nitrogen atoms and cr…

[Fe(phen)(CN)4]−: a suitable metalloligand unit to build 3d–4f heterobimetallic complexes with mixed bpym-cyano bridges (phen = 1,10-phenantroline, bpym = 2,2′-bipyrimidine)

The synthesis, crystal structure and magnetic properties of a new series of mixed 3d–4f complexes with the formula [{FeIII(phen)(CN)3(μ-CN)}4Ln2III(NO3)2(H2O)6(μ-bpym)]·nH2O [Ln = Eu (1), Gd (2), Dy (3) and Ho (4); n = 8 (1, 3 and 4) and 11 (2); phen = 1,10-phenantroline; bpym = 2,2′-bipyrimidine] are discussed here. Compounds 1–4 are centrosymmetric hexanuclear species whose structure is made up of two cyano-bridged {Fe2IIILnIII} heterobimetallic moieties which are connected through a bis-bidentate bpym molecule between the two rare-earth centers. The values of the iron–lanthanide distance across the single cyano-bridge are Fe(1)⋯Eu(1) = 5.5587(8) and Fe(2)⋯Eu(1) = 5.4908(8) A (1), Fe(1)⋯G…

Ferromagnetic Coupling through Spin Polarization in a Dinuclear Copper(II) Metallacyclophane.

[DT] Von organischen Radikalen zu Metallkomplexen konnte das bekannte Konzept für Ferroelektrika erfolgreich ausgedehnt werden: Die Abbildung zeigt ein Cyclophan-artiges Molekül mit einem Triplett-Grundzustand, in dem zwei CuII-Zentren von einem doppelten m-Phenylendiamid-Gerüst zusammengehalten werden.

Europium(III), Terbium(III), and Gadolinium(III) Oxamato-Based Coordination Polymers: Visible Luminescence and Slow Magnetic Relaxation

The reaction of aqueous solutions of EuIII, TbIII, and GdIII ions with Na2Hpcpa [H3pcpa = N-(4-carboxyphenyl)oxamic acid] afforded three new isostructural oxamate-containing lanthanide(III) coordination polymers of general formula {LnIII2(Hpcpa)3(H2O)5·H2O}n [Ln = Eu (1),Tb (2), and Gd(3)]. Their structure is made up of neutral zigzag chains running parallel to the [101] direction where double syn-syn carboxylate(oxamate)-bridged dilanthanide(III) pairs (Ln1 and Ln2) are linked by three Hpcpa2- ligands, one of them with the μ-κ2O,O':κO″ coordination mode and the other two with the μ3-κ2O,O':κO″:κO'''. Additionally, two of those chains are interlinked through hydrogen bonding and π-π type in…

Topology and Spin Polarization in Sheetlike Metal(II) Polymers: [ML2X2] (M ˭ Mn, Fe, Co or Ni, L = Pyrimidine or Pyrazine and X = NCS or NCO)

The preparation and the structural and magnetic characterization of a series of sheetlike transition metal polymers of formula [ML2X2] [M ˭ Mn(II), Fe(II), Co(II) and Ni(II): L = pyrazine (pyz) and...

Cobalt(II)-Copper(II) Bimetallic Chains as a New Class of Single-Chain Magnets

Ferromagnetische Kopplung im zweikernigen Bis(μ-end-on-azido)eisen(III)-Komplexanion von [FeII(bpym)3]2[FeIII(N3)10] · 2H2O

Assembling Magnetic Blocks: A Strategy to Control the Nuclearity and Magnetic Properties of Polynuclear Complexes

Synthetic strategies dealing with the polymerization of either di-μ-hydroxocopper(II) complexes or 2,2′-bipyrimidine (bpym)-containing first row transition metal ions allow the preparation of polynuclear compounds whose structures and magnetic properties are presented here. The influence of structural and chemical parameters on the magnitude of the singlet-triplet energy gap (J) in di-μ-hydroxocopper(II) complexes [LCu(OH)2CuL]2+ with L = 2,2′-bipyridine (bpy) and bpym is analyzed and discussed. Special attention is devoted to nature of the counterion which allows the preparation of hydroxo-bridge copper(II) cubane and double cubane type complexes where all the intramolecular magnetic inter…

Discrete and 1D coordination polymeric chloro-bridged copper(II) dimers exhibiting ferro- and antiferromagnetic exchange coupling: Magneto-structural correlations and non-covalent interactions

The synthesis and characterization of two 1D coordination polymers [Cu 2 (MHL)Cl 2 ][ClO 4 ] 2  · CH 3 CN · THF ( 2  · CH 3 CN · THF) and [Cu 2 (MPyPz)Cl 2 ][ClO 4 ] 2  · CH 3 CN ( 3  · CH 3 CN), having repetitive { Cu 2 II ( μ -Cl ) 2 } units, of m -xylyl-based ligands with terminal tridentate (2-pyridyl)alkylamine (MHL = α,α′-bis[ N -(2-pyridylethyl)- N -(2-pyridylmethyl)amino]- m -xylene) and (2-pyridyl)alkylamine/pyrazole (MPyPz = α,α′-bis[ N -(2-pyridylethyl)- N -(pyrazol-1-ylmethyl)amino]- m -xylene) coordination have been accomplished. X-ray crystallographic studies reveal that the copper(II) centers in the recently reported dichloro-bridged discrete { Cu 2 II ( μ -Cl ) 2 } complex […

Crystal growth and structural remarks on malonate-based lanthanide coordination polymers

The synthesis, structural characterization and thermal study of new coordination polymers (CPs) of formula [Ln2(mal)3(H2O)5]·2H2O [Ln = Ho (1·2H2O), Tb (1a), Dy (1b), Er (1c) and Yb (1d); mal = malonate], [Ln2(mal)3(H2O)6] [Ln = Sm (2) and Ce (2a)], [Ce2(mal)3(H2O)6]·2H2O (3·2H2O) and [Ce2(mal)3(H2O)3]·2H2O (4·2H2O) are presented. Complexes 1–4 have been also characterized by single crystal X-ray diffraction. The structure of 2 was previously reported (Elsegood, M. R. J., Husain, S., Private Communication, 2014) and it is very close to that of 3. In the light of these results and those previously reported in the literature for malonate-containing lanthanide(III) complexes, a detailed overvi…

High-dimensional malonate-based materials: Synthesis, crystal structures and magnetic properties of [M2(mal)2(L)(H2O)2]n·n(H2O) M = Zn(ii), Co(ii); H2mal = malonic acid, L = pyrimidine, pyrazine

Four novel coordination polymers [M2(mal)2(pym)(H2O)]n·nH2O, M = Zn (1), Co (2) and [M2(mal)2(pyz)(H2O)]n·nH2O, M = Zn (3), Co (4) (H2mal = malonic acid, pym = pyrimidine, pyz = pyrazine), have been synthesized. Compounds 1 and 2 are isomorphous, as are compounds 3 and 4. X-ray diffraction experiments reveal that 1–4 exhibit an interesting 3D-network, containing malonate and either pyrimidine (1 and 2) and pyrazine (3 and 4) as organic ligands. Variable-temperature magnetic susceptibility measurements indicate the occurrence of weak antiferromagnetic interactions between Co(II) ions in 2 and 4.

Mono-, di- and trinuclear 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz)-containing copper(II) complexes: syntheses, crystal structures and magnetic properties.

Three new copper(ii) complexes of formula [Cu(tppz)(NCO)(2)].0.4H(2)O (1), [Cu(2)(tppz)Br(4)](2) and [Cu(3)(tppz)(C(5)O(5))(3)(H(2)O)(3)].7H(2)O (3)[tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine; C(5)O(5)(2-) = croconate, dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione] have been synthesised and structurally characterized by X-ray diffraction methods. The structure of complex is made up of neutral [Cu(tppz)(NCO)(2)] mononuclear units and uncoordinated water molecules. The mononuclear units are grouped by pairs to give a rather short copper-copper distance of 3.9244(4) angstroms. The structure of complex 1 consists of neutral tppz-bridged [Cu(2)(tppz)Br(4)] dinuclear units, the copper-copp…

Dilution-Triggered SMM Behavior under Zero Field in a Luminescent Zn2Dy2 Tetranuclear Complex Incorporating Carbonato-Bridging Ligands Derived from Atmospheric CO2 Fixation

The synthesis, structure, magnetic, and luminescence properties of the Zn2Dy2 tetranuclear complex of formula {(mu(3)-CO3)2[Zn(mu-L)Dy(NO3)}(2)}center dot 4CH(3)OH (1), where H2L is the compartmental ligand N,N',N"-trimethyl-N,N"-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine, are reported. The carbonate anions that bridge two Zn(mu-L)Dy units come from the atmospheric CO2 fixation in a basic medium. Fast quantum tunneling relaxation of the magnetization (QTM) is very effective in this compound, so that single-molecule magnet (SMM) behavior is only observed in the presence of an applied dc field of 1000 Oe, which is able to partly suppress the QTM relaxation process. At variance,…

Cubane-Type Mo3FeS44+,5+ Complexes Containing Outer Diphosphane Ligands: Ligand Substitution Reactions, Spectroscopic Studies, and Electronic Structure

A general protocol to access Mo(3)FeS(4)(4+) clusters selectively modified at the Fe coordination site is presented starting from the all-chlorine Mo(3)(FeCl)S(4)(dmpe)(3)Cl(3) (1) [dmpe = 1,2-bis(dimethylphosphane-ethane)] cluster and tetrabutylammonium salts (n-Bu(4)NX) (X = CN(-), N(3)(-), and PhS(-)). Clusters Mo(3)(FeX)S(4)(dmpe)(3)Cl(3) [X = CN(-) (2), N(3)(-) (3), and PhS(-) (4)] are prepared in high yield, and comparison of geometric and redox features upon modification of the coordination environment at the Fe site at parity of ligands at the Mo sites is also presented. The existence of the cubane-type Mo(3)FeS(4)(4+,5+) redox couple is demonstrated by cyclic voltammetry and for co…

Towards a better understanding of honeycomb alternating magnetic networks.

Two new two-dimensional homometallic compounds {[M2(bpm)(ox)2]n·5nH2O} with M = Co(II) (1) and Zn(II) (2) and the mononuclear nickel(II) complex [Ni(bpm)2(ox)]·2H2O (3) [bpm = 2,2'-bipyrimidine and ox = oxalate] have been prepared and structurally characterized. 1 and 2 are isostructural compounds whose structures are made up of oxalate-bridged M(II) cations cross-linked by bis-bidentate bpm molecules to afford a honeycomb layered network extending in the crystallographic ab plane. The layers are eclipsed along the crystallographic c axis and show graphitic-like interactions between the bpm rings. The three-dimensional supramolecular network deriving from such interactions is characterized …

[Mnii2(bpym)(H2O)8]4+ and [Miv(CN)8]4– (M = Mo and W) as building blocks in designing bpym- and cyanide-bridged bimetallic three-dimensional networks (bpym = 2,2′-bipyrimidine)Electronic supplementary information (ESI) available: χMT vs. T for 2. See http://www.rsc.org/suppdata/nj/b2/b206124b/

One-pot reaction between the dinuclear [MnII2(bpym)(H2O)8]4+ complex and the mononuclear [MIV(CN)8]4− unit (M = Mo and W; bpym = 2,2′-bipyrimidine) in aqueous solution yields the novel heterobimetallic complexes of formula {(μ-bpym)[Mn(H2O)]2-(μ-NC)6M(CN)2} with M = Mo (1) and W (2). 1 and 2 are isostructural three-dimensional compounds where the manganese atoms are bridged by bisbidentate bpym and hexakismonodentate octacyanometalate units. Variable-temperature magnetic susceptibility data of 1 and 2 show the occurrence of a significant antiferromagnetic coupling between the high spin manganese(II) ions through bridging bpym (Jca. −1.1 cm−1, the exchange Hamiltonian being defined as H = −J…

[CuII{(LISQ)˙−}2] (H2L: thioether-appended o-aminophenol ligand) monocation triggers change in donor site from N2O2 to N2O(2)S and valence-tautomerism

Using a potentially tridentate o-aminophenol-based redox-active ligand H2L1 (2-[2-(benzylthio)phenylamino]-4,6-di-tert-butylphenol) in its deprotonated form, [Cu(L1)2] has been synthesized and crystallized as [CuII(L1)2]·CH2Cl2 (1·CH2Cl2). A cyclic voltammetry experiment (in CH2Cl2; V vs. SCE (saturated calomel electrode)) on 1·CH2Cl2 exhibits two oxidative (E = 0.20 V (peak-to-peak separation, ΔEp = 100 mV) and E = 0.90 V (ΔEp = 140 mV)) and two reductive (E = -0.52 V (ΔEp = 110 mV) and E = -0.92 V (ΔEp = 120 mV)) responses. Upon oxidation using a stoichiometric amount of [FeIII(η5-C5H5)2](PF6), 1·CH2Cl2 yielded [Cu(L1)2](PF6) (2). Structural analysis (100 K) reveals that 1·CH2Cl2 is a fou…

2D and 3D mixed MII/CuIImetal–organic frameworks (M = Ca and Sr) withN,N′-2,6-pyridinebis(oxamate) and oxalate: preparation and magneto-structural study

Three heterobimetallic complexes of formula [Ca2Cu3(mpyba)2(2-apyma)(H2O)7]·8.3H2O (1), [Sr2Cu3(mpyba)2(2-apyma)(H2O)8]·11.6H2O (2) and [Sr4.5Cu4(mpyba)4(ox)(H2O)20]·8.5H2O (3) [H4mpyba = N,N'-2,6-pyridinebis(oxamic acid), 2-apyma = 2-(6-aminopyridinyl)oxamate and ox = oxalate] have been synthesized and structurally characterized. Complexes 1 and 2 are isostructural compounds, with tricopper(ii) units having mpyba and its hydrolytic product (2-apyma) as ligands. They are interlinked through strontium(ii) (1) and calcium(ii) (2) ions to afford neutral two-dimensional networks. Two of the copper(ii) ions are five-coordinate in distorted square pyramidal (Cu3) and trigonal bipyramidal (Cu1) su…

Malonate-based copper(II) coordination compounds: Ferromagnetic coupling controlled by dicarboxylates

Studies on structural and magnetic properties of polynuclear transition metal complexes, aimed at understanding the structural and chemical factors governing electronic exchange coupling mediated by multiatom bridging ligands, are of continuing interest to design new molecular materials exhibiting unusual magnetic, optical and electrical properties, bound to their molecular nature. Looking at potentially flexible bridging ligands, the malonate group seems a suitable candidate. The occurrence of two carboxylate groups in the 1,3 positions allows this ligand to adopt simultaneously chelating bidentate and different carboxylato bridging modes (syn–syn, anti–anti and syn–anti trough one or two …

Synthesis, crystal structure and magnetic properties of an oxalato-bridged Re(IV)Mo(VI) heterobimetallic complex.

The Re(IV)-Mo(VI) compound of formula (PPh(4))(2)[ReCl(4)(μ-ox)MoO(2)Cl(2)] (1) constitutes the first example of a heterodinuclear oxalato-bridged complex in the coordination chemistry of molybdenum.

[Cr(phen)(ox)2]-: a versatile bis-oxalato building block for the design of heteropolymetallic systems. Crystal structures and magnetic properties of AsPh4[Cr(phen)(ox)2]·H2O, [NaCr(phen)(ox)2(H2O)]·2H2O and {[Cr(phen)(ox)2]2[Mn2(bpy)2(H2O)2(ox)]}·6H2O

The new complexes of formula AsPh4[Cr(phen)(ox)2]·H2O (1), [NaCr(phen)(ox)2(H2O)]·2H2O (2) and {[Cr(phen)(ox)2]2[Mn2(bpy)2(H2O)2(ox)]}·6H2O (3) (AsPh4=tetraphenylarsonium cation; phen=1,10-phenanthroline; ox=oxalate dianion; bpy=2,2′-bipyridine) have been prepared and characterized by single-crystal X-ray diffraction. The structure of 1 consists of discrete [Cr(phen)(ox)2]− anions, tetraphenylarsonium cations and uncoordinated water molecules. The chromium environment in 1 is distorted octahedral with Cr–O bond distances between 1.959(3) and 1.947(3) A and Cr–N bonds of 2.083(4) and 2.072(4) A. The angles subtended at the chromium atom by the two oxalates are 83.6(2) and 83.3(1)° whereas th…

Selective Guest Inclusion in Oxalate-Based Iron(III) Magnetic Coordination Polymers

The preparation and structural characterization of four novel oxalate-based iron(III) compounds of formulas {(MeNH3)2[Fe2(ox)2Cl4]·2.5H2O}n (1), K(MeNH3)[Fe(ox)Cl3(H2O)] (2), {MeNH3[Fe2(OH)(ox)2Cl2]·2H2O}n (3), and {(H3O)(MeNH3)[Fe2O(ox)2Cl2]·3H2O}n (4) (MeNH3+ = methylammonium cation and H2ox = oxalic acid) are reported here. 1 is an anionic waving chain of oxalato-bridged iron(III) ions with peripheral chloro ligands, the charge balance being ensured by methylammonium cations. 2 is a mononuclear complex with a bidentate oxalate, three terminal chloro ligands, and a coordinated water molecule achieving the six-coordination around each iron(III) ion. Its negative charge is balanced by potas…

Field-induced slow magnetic relaxation and magnetocaloric effects in an oxalato-bridged gadolinium(iii)-based 2D MOF

The coexistence of field-induced slow magnetic relaxation and moderately large magnetocaloric efficiency in the supra-Kelvin temperature region occurs in the 2D compound [GdIII2(ox)3(H2O)6]n·4nH2O (1), a feature that can be exploited in the proof-of-concept design of a new class of slow-relaxing magnetic materials for cryogenic magnetic refrigeration.

One-dimensional oxalato-bridged copper(II) complexes with 3-hydroxypyridine and 2-amino-4-methylpyridine

Two new one-dimensional oxalato-bridged copper(II) compounds of formula [Cu(ox)L2]n (1) and {[Cu2(ox)2L%3]·L%}n (2) [ox oxalate dianion, L3-hydroxypyridine (pyOH) and L% 2-amino-4-methylpyridine (ampy)] have been synthesized and characterized by FT-IR spectroscopy, variable-temperature magnetic measurements and single-crystal X-ray diffraction. The crystal structure of 1 comprises chains of copper atoms in which cis-[Cu(pyOH)2] 2 units are sequentially bridged by asymmetric bis-bidentate oxalato ligands with an intrachain copper‐copper separation of 5.548(1) A, . Each copper atom is six-coordinated: four oxygen atoms belonging to two bridging oxalato ligands and two nitrogen atoms from two …

Rational design of a new class of heterobimetallic molecule-based magnets: Synthesis, crystal structures, and magnetic properties of oxamato-bridged (M′=LiI and MnII; M=NiII and CoII) open-frameworks with a three-dimensional honeycomb architecture

Abstract Two new series of oxamato-bridged heterobimetallic coordination networks of general formula Li5[Li3M2(mpba)3(H2O)6] · 31H2O [M = NiII (1a) and CoII (1b)] and Li2[Mn3M2(mpba)3(H2O)6] · 22H2O [M = NiII (2a) and CoII (2b)] have been prepared from the metal-mediated self-assembly of the hexakis(bidentate), triple-stranded dinickel(II) and dicobalt(II) complexes [M2(mpba)3]8− [mpba = meta-phenylenebis(oxamato)] with either monovalent lithium(I) or divalent manganese(II) ions respectively, in water. X-ray structural analyses of 1a and 1b show an anionic three-dimensional network formed by an infinite parallel array of oxamato-bridged Li 3 I M 2 II (M = Ni and Co) hexagonal layers, which …

Ferromagnetic Coupling in “Double-Bridged” Dihydrogenpyrophosphate Complexes of Cobalt(II) and Nickel(II)

Three isostructural compounds of the formula {[M(bipy)(H2O)(H2P2O7)]2·2H2O} [bipy = 2,2'-bipyridine; M = Ni (1), Co (2), Mn (3)] have been isolated from aqueous solutions containing the corresponding metal(II) chloride hydrate with a bipy and sodium pyrophosphate solution in a 1:1:2 molar ratio, and their structures were determined by single-crystal X-ray diffraction. The structures of 1-3 consist of neutral aqua(2,2'-bipyridine)metal(II) dinuclear units bridged by two dihydrogenpyrophosphate groups adopting a bidentate/monodentate mode. Each metal ion in 1-3 is six-coordinate in a distorted octahedral geometry, with the reduced value of the angle subtended by the chelating bipy at the meta…

Selective and Efficient Removal of Mercury from Aqueous Media with the Highly Flexible Arms of a BioMOF

A robust and water-stable metal-organic framework (MOF), featuring hexagonal channels decorated with methionine residues (1), selectively captures toxic species such as CH3 Hg(+) and Hg(2+) from water. 1 exhibits the largest Hg(2+) uptake capacity ever reported for a MOF, decreasing the [Hg(2+) ] and [CH3 Hg(+) ] concentrations in potable water from highly hazardous 10 ppm to the much safer values of 6 and 27 ppb, respectively. Just like with biological systems, the high-performance metal capture also involves a molecular recognition process. Both CH3 Hg(+) and Hg(2+) are efficiently immobilized by specific conformations adopted by the flexible thioether "claws" decorating the pores of 1. T…

{[Cu(H2O)3][Cu(phmal)2]}n: a new two-dimensional copper(ii) complex with intralayer ferromagnetic interactions (phmal = phenylmalonate dianion)

The novel sheet-like copper(II) compound of formula {[Cu(H2O)3][Cu(Phmal)2]}n (1) (Phmal = dianion of phenylmalonic acid) has been synthesized and its crystal structure determined by X-ray diffraction. The structure of 1 consists of 21 chains of carboxylate(phenylmalonate)-bridged copper(II) ions which are linked through double μ-oxo(carboxylate) units to afford a two-dimensional network. The interlayer space is filled by the phenyl rings of the phenylmalonate ligands that exhibit offset face-to-face interactions. Variable-temperature magnetic measurements of 1 show the occurrence of significant intralayer ferromagnetic interactions between the copper(II) ions through anti–syn carboxylate- …

Metamorphosis of a butterfly: synthesis, structural, thermal, magnetic and DFT characterisation of a ferromagnetically coupled tetranuclear copper(ii) complex

The reaction in water of Cu(OH)(2) with 2,2'-bipyridine (bipy) and (NH(4))(2)HPO(4) in a 4 : 4 : 2 molar ratio under an inert atmosphere leads to the formation of a tetranuclear copper(II) complex of formula {[(H(2)O)(2)Cu(4)(bipy)(4)(mu(4)-PO(4))(2)(mu(2)-OH)] x 0.5 HPO(4) x 15.5 H(2)O}, 1, with butterfly topology. The structure of the tetranuclear core in 1 consists of four crystallographically unique copper(II) ions in approximate square-pyramidal geometry with each coordinated to a bipy ligand and interacting through two mu(4)-O,O',O''-phosphate bridges. Additional bridging between Cu(3) and Cu(4) is provided by a hydroxide ligand, whereas two water molecules cap the Cu(1) and Cu(2) squ…

Enantioselective self-assembly of antiferromagnetic hexacopper(ii) wheels with chiral amino acid oxamates

The Cu(2+)-mediated self-assembly of oxamato-based ligands derived from either the (S)- or (R)-enantiomers of the amino acid valine leads to the formation of two antiferromagnetically coupled homochiral anionic hexacopper(II) wheels in the presence of templating tetramethylammonium countercations.

Ferromagnetic coupling through the oxalate bridge in heterobimetallic Cr(III)–M(II) (M = Mn and Co) assemblies

Abstract Two novel compounds, {[Cr(pyim)(ox)2]2Mn}n·2nCH3OH (1) and {[Cr(pyim)(ox)2]2Co(H2O)2}·7.5H2O (2) [pyim = 2-(2′-pyridyl)imidazole and H2ox = oxalic acid], were synthesized by using the mononuclear chromium(III) complex PPh4[Cr(pyim)(ox)2]·H2O (PPh4+ = tetraphenylphosphonium) as metalloligand towards the fully solvated manganese(II) (1) and cobalt(II) (2) ions as perchlorate salts. The structure of 1 consists of neutral double chains, with diamond-shaped units sharing the manganese(II) ions with the two other corners being occupied by the chromium(III) ions. The two metal centres in 1 are connected by bis-bidentate oxalate groups, each [CrIII(pyim)(ox)2]− unit being bound to two mang…

A Binuclear MnIII Complex of a Scorpiand-Like Ligand Displaying a Single Unsupported MnIII–O–MnIII Bridge

The crystal structure of a binuclear Mn(III) complex of a scorpiand-like ligand (L) displays an unsupported single oxo bridging ligand with a Mn(III)-O-Mn(III) angle of 174.7°. Magnetic susceptibility measurements indicate strong antiferromagnetic coupling between the two metal centers. DFT calculations have been carried out to understand the magnetic behavior and to analyze the nature of the observed Jahn-Teller distortion. Paramagnetic (1)H NMR has been applied to rationalize the formation and magnetic features of the complexes formed in solution.

Phenylmalonate‐Containing Copper( II ) Complexes: Synthesis, Crystal Structure and Magnetic Properties

Three new copper(II) complexes of formula [Cu(2,2′-bpy)(Phmal)(H2O)]·2H2O (1), [{Cu(2,2′-bpym)(Phmal)}]n (2) and [{Cu(phen)(Phmal)}]n·3nH2O (3) (Phmal = phenylmalonate; 2,2′-bpy = 2,2′-bipyridine; 2,2′-bpym = 2,2′-bipyrimidine; phen = 1,10-phenanthroline) have been prepared and their structures determined by X-ray diffraction techniques. Complex 1 is mononuclear whereas 2 and 3 are uniform chain compounds. The copper atoms in 1−3 are distorted square-pyramidal: two nitrogen atoms from the bidentate nitrogen heterocycle and two carboxylate oxygen atoms from the phenylmalonate ligand build the equatorial plane; the axial position is filled either by a water molecule (1) or a carboxylate oxyge…

Iron(III), chromium(III) and cobalt(II) complexes with squarate: Synthesis, crystal structure and magnetic properties

The preparation and variable temperature-magnetic investigation of three squarate-containing complexes of formula [Fe 2 (OH) 2 (C 4 O 4 ) 2 (H 2 O) 4 ]·2H 2 O ( 1 ) [Cr 2 (OH) 2 (C 4 O 4 ) 2 (H 2 O) 4 ]·2H 2 O ( 2 ) and [Co(C 4 O 4 )(H 2 O) 4 ] n ( 3 ) [H 2 C 4 O 4  = 3.4-dihydroxycyclobutene-1,2-dione (squaric acid)] together with the crystal structures of 1 and 3 are reported. Complex 1 contains discrete centrosymmetric [Fe 2 (OH) 2 (C 4 O 4 ) 2 (H 2 O) 4 ] diiron(II) units where the iron pairs are joined by a di-μ-hydroxo bridge and two squarate ligands acting as bridging groups through adjacent oxygen atoms. Two coordinated water molecules in cis position complete the octahedral environ…

Ligand Effects on the Structure and Magnetic Properties of Alternating Copper(II) Chains with 2,2′-Bipyrimidine- and Polymethyl-Substituted Pyrazolates as Bridging Ligands

A novel series of heteroleptic copper(II) compounds of formulas {[Cu2(μ-H2O)(μ-pz)2(μ-bpm)(ClO4)(H2O)]ClO4·2H2O}n (1), {[Cu2(μ-H2O)(μ-3-Mepz)2(μ-bpm)](ClO4)2·2H2O}n (2), and {[Cu2(μ-OH)(μ-3,5-Me2pz)(μ-bpm)(H-3,5-Me2pz)2](ClO4)2}n (3) [bpm = 2,2'-bipyrimidine, Hpz = pyrazole, H-3-Mepz = 3-methylpyrazole, and H-3,5-Me2pz = 3,5-dimethylpyrazole] have been synthesized and structurally characterized by X-ray diffraction methods. The crystal structures of 1 and 2 consist of copper(II) chains with regular alternating bpm and bis(pyrazolate)(aqua) bridges, whereas that of 3 is made up of copper(II) chains with regular alternating bpm and (pyrazolate)(hydroxo) bridges. The copper centers are six- (1…

{CoIIIMnIII}ncorrugated chains based on heteroleptic cyanido metalloligands

The use of the cyanide-bearing complexes PPh4[CoIII(4,4′-dmbipy)(CN)4] and PPh4[CoII(dmphen)(CN)3] as metalloligands towards [Mn(salen)(H2O)]ClO4 affords one-dimensional coordination polymers with the formulas {[MnIII(salen)(μ-NC)2CoIII(4,4-dmbipy)(CN)2]·H2O}n (1) and {[MnIII(salen)(μ-NC)2CoIII(dmphen)(CN)2]}n (2) [PPh4+ = tetraphenylphosphonium cation, 4,4′-dmbipy = 4,4′-dimethyl-2,2′-bipyridine, dmphen = 2,9-dimethyl-1,10-phenanthroline and H2salen = N,N′-ethylenebis(salicylideneimine)]. Compounds 1 and 2 were structurally characterized. Their structures consist of neutral chains with regular alternating [Mn(salen)]+ and [CoIII(4,4′-dmbipy)(CN)4]− (1)/[CoIII(dmphen)(CN)4]− (2) moieties, t…

A Copper(II)-Cytidine Complex as a Building Unit for the Construction of an Unusual Three-Dimensional Coordination Polymer

The chiral [Cu(cyd) 4 ] 6- anion acts as a multiarmed complex-ligand toward auxiliary copper(II) centers leading to the first example of cytidinate-bridged three-dimensional (3D) coordination polymer of formula [Cu 6 (H 2 O) 7 (ClO 4 ) 3 Cu(cyd) 4 ]-(ClO 4 ) 3 (1). Single crystal X-ray analysis of 1 shows a unique 3D covalent network supported by the exclusive hypercoordination of the cytidinate ligand that bridges four crystallographically independent copper(II) ions via the N3, O2, O2', O3', and O5' set of atoms. Magnetic susceptibility measurements in the temperature range 1.9-295 K reveal the coexistence of ferro- and antiferromagnetic interactions within the hexacopper(II) core of 1, t…

Synthesis, crystal structure and magnetic properties of the complex [ReCl3(tppz)]·MeCN

The reaction of the starting materials [ReIIICl3(MeCN)(PPh3)2] or [ReVOCl3(PPh3)2] with 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) in acetonitrile yielded the Re(III) complex [ReCl3(tppz)]·MeCN (1). This complex crystallizes in the monoclinic space group P21/n and its crystal structure consists of neutral mononuclear entities with meridional geometry of the chloride ligands, and the six-coordination of the Re(III) ion being completed by the tridentate tppz ligand. Each metal centre exhibits a highly distorted octahedral coordination with Re–Cl and Re–Ntppz bond lengths covering the ranges 2.3590(9)–2.3606(8) and 1.971(2)–2.096(2) A, respectively. The magnetic properties of 1 have been inves…

Malonic acid: A multi-modal bridging ligand for new architectures and properties on molecule-based magnets

Abstract In this work, we show how the design of one-, two- and three-dimensional materials can strongly benefit from the use of crystal engineering techniques, which can give rise to structures of different shapes, and how these differences can give rise to different properties. We will focus on the networks constructed by assembling malonate ligands and metal centres. The idea of using malonate (dianion of propanedioic acid, H 2 mal) is that they can give rise to different coordination modes with the metal ions bind. Extended magnetic networks of dimensionalities 1 (1D), 2 (2D) and 3 (3D) can be chemically constructed from malonato-bridged metallic complexes. These coordination polymers b…

Interaction between heterobinuclear molecules and nature of the ground spin state in oximato-bridged [CuIIMII]2 bis-binuclear complexes (M=Cu, Ni, Mn): crystal structure of [Cu(pdmg)Ni(Me3[12]N3)(EtOH)](ClO4)2

[EN] Two new heterobimetallic complexes [Cu(pdmg)Ni(Me-3[12]N-3)(CH3CH2OH)](ClO4)(2)(2) and [Cu(pdmg) Mn(bipy)(2)]-ClO4)(2) . H2O (3) (H(2)pdmg = 3,9-dimethyl-4,8-diazaundeca-3,8-diene-2 10-dione dioxime; Me-3[12]N-3 = 2,4,4-trimethyl-1,5,9-triazacyclododeca-1-ene; bipy = 2,2'-bipyridyl) have been prepared and characterized. The structure of 2 has been determined by single-crystal X-ray diffraction methods. It consists of [Cu(pdmg)Ni(Me-3[12]N-3)(CH3CH2OH)](2+) cations and non-coordinated perchlorate anions. The [Cu(pdmg)(CH3CH2OH)] complex coordinates to the [Ni(Me-3[12]N-3)](2+) fragment to afford the binuclear unit doubly-bridged by oximato groups in cis arrangement. The coordination geo…

Mononuclear and One-Dimensional Cobalt(II) Complexes with the 3,6-Bis(picolylamino)-1,2,4,5-tetrazine Ligand

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[Cr(dpa)(ox)2]–: a new bis-oxalato building block for the design of heteropolymetallic systems. Crystal structures and magnetic properties of PPh4[Cr(dpa)(ox)2], AsPh4[Cr(dpa)(ox)2], Hdpa[Cr(dpa)(ox)2]·4H2O, Rad[Cr(dpa)(ox)2]·H2O and Sr[Cr(dpa)(ox)2]2·8H2O (dpa = 2,2′-dipyridylamine)

[EN] The new complexes of formulae PPh4[Cr(dpa)(ox)(2)] (1), AsPh4[Cr(dpa)(OX)(2)] (2), Hdpa[Cr(dpa)(ox)(2)]-4H(2)O (3), Rad[Cr(dpa)(ox)(2)] . H2O (4) and Sr[Cr(dpa)(ox)(2)](2) . 8H(2)O (5) [PPh4 = tetraphenylphosphonium cation; AsPh4 = tetraphenylarsoniurn cation; dpa = 2,T-dipyridylamine; ox = oxalate dianion; Rad = 2-(4-N-methylpyridinium)4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-a-oxyl-3-N-oxide] have been prepared and characterised by single-crystal X-ray diffraction. The structures of 1-4 consist of discrete [Cr(dpa)(ox)(2)](-) anions, tetraphenylphosphonium. (1), tetraphenylarsonium (2), monoprotonated Hdpa (3) and univalent radical (4) cations and uncoordinated water molecules (2-…

Ligand substitution in hexahalorhenate(IV) complexes: Synthesis, crystal structures and magnetic properties of NBu4[ReX5(DMF)] (X=Cl and Br)

Abstract The preparation, crystal structures, and magnetic properties of two rhenium(IV) mononuclear compounds of formula NBu 4 [ReX 5 (DMF)] ( NBu 4 + = tetrabutylammonium cation and DMF = N , N - dimethylformamide ) with X = Cl ( 1 ) and Br ( 2 ) are reported. 1 and 2 are isostructural complexes which crystallize in the monoclinic system with the space group P 2 1 / n . The rhenium atom is six-coordinated with five X atoms and a DMF molecule forming a somewhat distorted octahedral surrounding [values of Re–X varying in the ranges 2.317(1)–2.358(1) ( 1 ) and 2.495(1)–2.518(1) A ( 2 )]. Magnetic susceptibility measurements on samples of 1 and 2 in the temperature range 1.9–300 K are interpr…

Magnetic phase transition and magnetic bistability in oxamato-based CoIICuII bimetallic MOF thin films

Abstract Thin films of an anionic oxamato-bridged cobalt(II)–copper(II) 3D MOF have been growth at 120 °C in DMSO through a one-pot reaction from Co(NO3)2·6H2O and (Me4N)2[Cu(2,6-Et2pa)2]·6H2O (2,6-Et2pa = N-2,6-diethylphenyloxamate) over Si(111) surfaces functionalized with carboxylic acid terminating groups. These heterobimetallic CoII2CuII3 MOF thin films (2) of about ten nanometers thickness show a ferrimagnetically ordered phase below ca. 10 K with a relatively large magnetic hysteresis similar to that of the bulk material of formula (Me4N)2[Co2Cu3(2,6-Et2pa)6]·5H2O (1).

First Magnetostructural Study on a Heterodinuclear 2,2′-Bipyrimidine-Bridged Complex

The use of the [ReCl(4)(bpym)] precursor as a ligand toward the fully solvated nickel(II) metal ion affords the first example of a 2,2'-bipyrimidine-bridged Re(IV)-Ni(II) complex, [ReCl(4)(μ-bpym)NiBr(2)(H(2)O)(2)] (1), whose intramolecular ferromagnetic coupling has been substantiated from both experimental and theoretical studies.

Intramolecular ferro- and antiferromagnetic interactions in oxo-carboxylate bridged digadolinium(iii) complexes

Two new digadolinium(III) complexes with monocarboxylate ligands, [Gd2(pac)6(H2O)4] (1) and [Gd2(tpac)6(H2O)4] (2) (Hpac = pentanoic acid and Htpac = 3-thiopheneacetic acid), have been prepared and their structures determined by X-ray diffraction on single crystals. Their structures consist of neutral and isolated digadolinium(III) units, containing six monocarboxylate ligands and four coordinated water molecules, the bridging skeleton being built by a muO(1):kappa2O(1)O(2) framework. This structural pattern has already been observed in the parent acetate-containing compound [Gd2(ac)6(H2O)4] x 4 H2O (3) whose structure and magnetic properties were reported elsewhere (L. Cañadillas-Delgado, …

Magneto-structural correlations in asymmetric oxalato-bridged dicopper(II) complexes with polymethyl-substituted pyrazole ligands

Two oxalato-bridged dinuclear copper(II) complexes, [{Cu(Hdmpz)3}2(μ-ox)](ClO4)2·2H2O (1) and [{Cu(Htmpz)3}2(μ-ox)](ClO4)2·2H2O (2) (Hdmpz = 3,5-dimethyl-1H-pyrazole and Htmpz = 3,4,5-trimethyl-1H-pyrazole), have been synthesized and structurally and magnetically characterized. The crystal structures of 1 and 2 consist of asymmetric bis-bidentate μ-oxalatodicopper(II) complex cations with two short [Cu–O = 1.976(2) (1) and 1.973(2) Å (2)] and two long copper–oxygen bonds [Cu–O = 2.122(2) (1) and 2.110(2) Å (2)]. The environment at each CuII ion in 1 and 2 is closer to the trigonal bipyramidal geometry than to the square pyramidal [τ = 0.633 (1) and 0.711 (2)]. The magnetic properties of 1 a…

Ferromagnetic coupling in the malonato-bridged copper(ii) chains [Cu(Im)2(mal)]nand [Cu(2-MeIm)2(mal)]n(H2mal = malonic acid, Im = imidazole and 2-MeIm = 2-methylimidazole)

Two new malonato-bridged copper(II) complexes of formula [Cu(Im)2(mal)]n (1) and [Cu(2-MeIm)2(mal)]n (2) (Im=imidazole, 2-MeIm=2-methylimidazole and mal=malonate dianion) have been prepared and their structures solved by X-ray diffraction methods. The [Cu(Im)2(mal)] and [Cu(2-MeIm)2(mal)] neutral entities act as monodentate ligands towards the adjacent copper(II) units through one of the two carboxylate groups, the OCO bridge exhibiting an anti-anti conformation. The environment of each copper atom in 1 and 2 is distorted square pyramidal: two carboxylate oxygen atoms from a bidentate malonate and two nitrogen atoms from two imidazole (1) or 2-methylimidazole (2) ligands form the equatorial…

Molecular Self-Assembly in a Family of Oxo-Bridged Dinuclear Ruthenium(IV) Systems

A series of six novel RuIV compounds of formula (H2bpy)2[{RuCl5}2(μ-O)] (1), (PPh4)2[{RuCl4(H2O)}2(μ-O)]·4H2O (2), (PPh4)2[{RuCl4(MeCN)}2(μ-O)] (3), (PPh4)2[{RuCl4(dmf)}2(μ-O)] (4), (PPh4)2[{RuCl4(...

Synthesis, Structural, Thermal and Magnetic Characterization of a Pyrophosphato‐Bridged Cobalt(II) Complex

The reaction in water of CoII sulfate heptahydrate with 1,10-phenanthroline (phen) and sodium pyrophosphate (Na4P2O7) in a 2:4:1 stoichiometric ratio resulted in the crystallization of a neutral dinuclear CoII complex, {[Co(phen)2]2(μ-P2O7)}·6MeOH (1), as revealed by a single-crystal X-ray diffraction study. The bridging pyrophosphato ligand between the two [Co(phen)2]2+ units in a bis(bidentate) coordination mode places the adjacent metal centers at 4.857 A distance, and its conformation gives rise to intramolecular π–π stacking interaction between adjacent phen ligands. Indeed, intermolecular π–π stacking interactions between phen ligands from adjacent dinuclear complexes create a supramo…

A step further in the comprehension of the magnetic coupling in gadolinium(III)-based carboxylate complexes

Three new gadolinium(III) complexes of formula [Gd4(bta) 3(H2O)16]n·12nH2O (1), [Gd4(bta)3(H2O)12] n·18nH2O (2) and [Gd2(H 2bta)(bta)(H2O)2]n·4nH 2O (3) (H4bta = 1,2,4,5-benzenetetracarboxylic acid) have been synthesized and their structures determined by X-ray diffraction. 1 and 3 are three-dimensional compounds whereas 2 exhibits a two-dimensional structure. The ability of the bta4- to adopt different coordination modes accounts for these high dimensionalities although it precludes a rational structural design. The structures of 1-3 have in common the double oxo-carboxylate bridge between gadolinium(III) ions (μ-O: κ2O,O′) either as a discrete units (1 and 2) or as a chain (3) and one (3)…

Multiferroics by Rational Design: Implementing Ferroelectricity in Molecule-Based Magnets

Multiferroics (MF) are materials that exhibit simultaneouslyseveral ferroic order parameters. Among the multiferroicmaterials, those combining antiferro- or ferroelectricity (FE)and antiferro-, ferri-, or ferromagnetism (FM) within thesame material are highly desirable: the coexistence of thepolar and magnetic orders paves the way towards four-levelmemories while their interactions through the magnetoelec-tric effect makes it possible to control the magnetization byelectric fields and hence to develop electronically tuneablemagnetic devices, which are an essential feature for spin-tronics.

Structural and Magnetic Characterization of a Novel Heptanuclear Hydroxo-Bridged Copper(II) Cluster of the Corner-Sharing Dicubane Type

New family of thiocyanate-bridged Re(IV)-SCN-M(II) (M = Ni, Co, Fe, and Mn) heterobimetallic compounds: synthesis, crystal structure, and magnetic properties.

The heterobimetallic complexes of formula [(Me(2)phen)(2)M(μ-NCS)Re(NCS)(5)]·CH(3)CN [Me(2)phen = 2,9-dimethyl-1,10-phenanthroline and M = Ni (1), Co (2), Fe (3), and Mn (4)] have been prepared, and their crystal structures have been determined by X-ray diffraction on single crystals. Compounds 1-4 crystallize in the monoclinic C2/c space group, and their structure consists of neutral [(Me(2)phen)(2)M(μ-NCS)Re(NCS)(5)] heterodinuclear units with a Re-SCN-M bridge. Each Re(IV) ion in this series is six-coordinated with one sulfur and five nitrogen atoms from six thiocyanate groups building a somewhat distorted octahedral environment, whereas the M(II) metal ions are five-coordinated with fou…

Chemistry and reactivity of dinuclear iron oxamate complexes: alkane oxidation with hydrogen peroxide catalysed by an oxo-bridged diiron(III) complex with amide and carboxylate ligation

[EN] A new dinuclear iron(III) complex with the tetradentate ligand N,N'-o-phenylenebis(oxamate) (opba) has been synthesised, and structurally, magnetically and electrochemically characterised. It possesses an unprecedented triply bridged Fe-2(mu-O)(mu-RCO2...H2O...O2CR)(2) core, whereby two N-amides from the opba ligand complete the square-pyramidal coordination sphere of the O-carboxylate rich iron site (Fe-N = 2.053 Angstrom and Fe-O = 2.015 Angstrom), The antiferromagnetic exchange interaction between the two high-spin Fe-III ions through the oxo bridge (J = -190 cm(-1); H = -JS(1)(.)S(2)) is weaker than that found in related mu-oxo singly bridged diiron(III) complexes. The lessened ant…

Three different types of bridging ligands in a 3d-3d'-3d'' heterotrimetallic chain.

A one-pot synthesis of a 3d–3d′–3d′′ heterotrimetallic coordination polymer with double diphenoxido, single cyanido and bis-bidentate oxalate as alternating bridges which exhibits an overall antiferromagnetic behaviour has been developed.

Alternierende ferro- und antiferromagnetische Austauschwechselwirkungen in einem kettenförmigen CuII-Koordinationspolymer

Crystal Engineering Applied to Modulate the Structure and Magnetic Properties of Oxamate Complexes Containing the [Cu(bpca)]+ Cation

This work deals with the crystal engineering features of four related copper(II)-based compounds with formulas {[{Cu(bpca)}2(H2ppba)]·1.33DMF·0.66DMSO}n (2), [{Cu(bpca)(H2O)}2(H2ppba)] (3), [{Cu(bpca)}2(H2ppba)]·DMSO (4), and [{Cu(bpca)}2(H2ppba)]·6H2O (5) [H4ppba = N,N′-1,4-phenylenebis(oxamic acid) and Hbpca = bis(2-pyridylcarbonyl)amide] and how their distinct molecular and crystal structures translate into their different magnetic properties. 2 and 3 were obtained through the hydrolytic reaction of the double-stranded oxamato-based dipalladium(II) paracyclophane precursor of formula [{K4(H2O)2}{Pd2(ppba)2}] (1) with the mononuclear copper(II) complex [Cu(bpca)(H2O)2]+, either in a water…

Single-Molecule-Magnet Fe Fe and Antiferromagnetic Fe Coordination Clusters

Supported by endogenous (part of the ligand, in-built) phenoxo bridges provided by the ligand 2,6-bis[{{(5-bromo-2-hydroxybenzyl)}{(2-(pyridylethyl)}amino}methyl]-4-methylphenol) (H3L), in its deprotonated form, exogenous (not part of the ligand, externally added or generated) oxo-/hydroxo- and acetato-bridged [FeII4FeIII2(O)2(O2CMe)4(L)2]·4Et2O (1) and [FeIII4(OH)2(O2CMe)3(L)2](ClO4)·3MeCN·2H2O (2) coordination clusters have been synthesized and structurally characterized. Complexes 1 and 2 have μ4-O and μ3-OH bridges, respectively. Magnetic studies on 1 reveal slow magnetic relaxation below 2 K. Both in-phase ( χ'M) and out-of-phase (χ″M) magnetic susceptibility were found to be frequency…

Squarate and croconate in designing one- and two-dimensional oxamidato-bridged copper(II) complexes: synthesis, crystal structures and magnetic properties of 〚Cu 2 (apox)(C 4 O 4 )(H 2 O) 2 〛 n · n H 2 O and 〚Cu 4 (apox) 2 (C 5 O 5 ) 2 〛·6 H 2 O

Abstract The reaction of squarate (C4O42–, dianion of 3,4-dihydroxycyclobut-3-ene-1,2-dione) and croconate (C5O52–, dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione) with the dinuclear 〚Cu2(apox)〛2+ copper(II) complex 〚H2apox = N,N’-bis(3-aminopropyl)oxamide〛 in aqueous solution affords the compounds of formula 〚Cu2(apox)(C4O4)(H2O)2〛n·n H2O (1) and 〚Cu4(apox)2(C5O5)2〛·6 H2O (2). Crystals of 1 are monoclinic, space group C2/c, with a = 12.5527(9), b = 7.4161(6), c = 18.5198(12) A, β = 100.578(6)° and Z = 4. Crystals of 2 are triclinic, space group P 1 with a = 9.732(5), b = 9.795(2), c = 10.285(3) A, α = 84.95(2), β = 77.30(3), γ = 85.61(3)° and Z = 1. The structure of complex 1 consist…

Crystal structure and magnetic study of the complex salt [RuCp(PTA)2–μ-CN-1κC:2κN–RuCp(PTA)2][Re(NO)Br4(EtOH)0.5(MeOH)0.5]

A new RuII–ReII complex salt, μ-cyanido-κ2 C:N-bis[(η5-cyclopentadienyl)bis(3,5,7-triazaphosphaadamantane-κP)ruthenium(II)] tetrabromido(ethanol/methanol-κO)nitrosylrhenate(II), [Ru(CN)(C5H5)2(C6H12N3P)4][ReBr4(NO)(CH4O)0.5(C2H6O)0.5] or [RuCp(PTA)2–μ-CN–1κC:2κ2 N-RuCp(PTA)2][Re(NO)Br4(EtOH)0.5(MeOH)0.5] (PTA = 3,5,7-triazaphosphaadamantane) was obtained and characterized by single-crystal X-ray diffraction, elemental analysis and infrared spectroscopy. The title salt was obtained by liquid–liquid diffusion of methanol/DMSO solutions of (NBu4)[Re(NO)Br4(EtOH)] and [(PTA)2CpRu–μ-CN–1κC:2κ2 N-RuCp(PTA)2](CF3SO3). The RuII and ReII independent moieties correspond to a binuclear and mononuclear…

Ferromagnetic coupling in a one-dimensional molecular railroad copper(II) azido compound containing a defective double cubane motif.

The compound [Cu2(bpm)2(N3)4]n (bpm = bis(pyrazol-1−yl)methane) shows three unique coordination modes (μ1,1-, μ1,1,1-, μ1,1,3-N3) and ferromagnetic interaction between the copper(II) ions. The structure of the compound exhibits a one-dimensional railroad polymer made up of repeating defective dicubane-type units linked by μ1,1,3-N3 bridges.

On the magneto-structural role of the coordinating anion in oxamato-bridged copper(ii) derivatives

We herein present the synthesis, spectroscopic analysis, description of the crystal structures and magnetic properties of four new complexes of the formula [{Cu(opba)(H2O)1.2}{Cu(dmphen)(SCN)}2]·dmf (1), [{Cu(opba)}2{Cu(dmphen)Cl}4]·1.5dmf·2.5dmso (2), [{Cu(opba)}2{Cu(dmphen)Br}4]·dmf·2.3dmso (3) and [{Cu(opba)}{Cu(dmphen)(dca)}2]n (4) [H4opba = N,N′-1,2-phenylenebis(oxamic acid), dmphen = 2,9-dimethyl-1,10-phenanthroline and dca = dicyanamide anion]. 1 is a neutral tricopper(II) complex where an inner [Cu(opba)]2− fragment adopts a bis-bidentate coordination mode towards two outer [Cu(dmphen)(NCS)]+ units. 2 and 3 are bis-trinuclear species where two oxamato-bridged [Cu(opba){Cu(dmphen)X}2…

[Cr(bpym)(C2O4)2]− in designing heterometallic complexes. Crystal structures and magnetic properties of PPh4[Cr(bpym)(C2O4)2]·H2O and [Ag(bpym)][Cr(C2O4)2](H2O)2]·2H2O (bpym=2,2′-bipyrimidine)

Abstract The preparation, crystal structure and magnetic properties of PPh 4 [Cr(bpym)(C 2 O 4 ) 2 ]·H 2 O ( 1 ) and [Ag(bpym)][Cr(C 2 O 4 ) 2 (H 2 O) 2 ]·2H 2 O ( 2 ) (C 2 O 4  2− =oxalate dianion, bpym=2,2′-bipyrimidine and PPh 4  + =tetraphenylphosphonium cation) are described. The structure of 1 is made up of discrete (2,2′-bipyrimidine)bis(oxalato)chromate(III) anions, teraphenylphosphonium cations and uncoordinated water molecules. The structure of 2 consists chains of univalent silver cations bridged by bis-chelating 2,2′-bypyrimidine, cis -diaquabis(oxalato)chromate(III) anions and crystallisation water molecules. The chromium atom in 1 and 2 has a slightly distorted octahedral geom…

Synthesis, Crystal Structure and Magneto‐Structural Correlation of an Unusual Thiocyanato‐Bridged Nickel( II ) Compound, [Ni(μ‐NCS)(dpt)(NCS)] 2 [Ni(μ‐NCS)(dpt)(NCS)] 4 [dpt = bis(3‐aminopropyl)amine]

Reaction of Ni(ClO4)2·6H2O with bis(3-aminopropyl)amine (dpt) and ammonium thiocyanate produces the novel thiocyanato-bridged nickel(II) compound [Ni(μ-NCS)(dpt)(NCS)]2[Ni(μ-NCS)(dpt)(NCS)]4, which has been structurally characterised. The structure determination reveals that there are two different molecules in the crystal lattice; one is dinuclear and other is tetranuclear. Low-temperature magnetic measurements show that there are ferro- as well as antiferromagnetic interactions. The ferromagnetic interaction arises from the dinuclear part and the doubly bridged part of the tetranuclear unit; the antiferromagnetic interaction occurs between singly bridged nickel centres in the tetranuclear…

Protonated malonate: the influence of the hydrogen bonds on the magnetic behaviour

One hydrogen malonato-bridged complex of formula [Cu(Hmal)2] (1) and two polymorphous malonato-bridged complexes of formula [Cu(H2O)(H2mal)(mal)] (2 and 3), in which the three species of the malonate (H2mal, Hmal−, and mal2−) are present, were synthesised and characterized by X-ray diffraction [H2mal = malonic acid]. Their structures consist of corrugated malonate layers of [Cu(Hmal)2] (1) and [Cu(H2O)(H2mal)(mal)] (2 and 3) units bridged by carboxylate–malonate groups. The layers are linked through hydrogen bonds leading to a three-dimensional network. Variable-temperature (1.9–290 K) magnetic susceptibility measurements indicate the occurrence of weak ferromagnetic interactions between th…

Crystal engineering of 3-D coordination polymers by pillaring ferromagnetic copper(ii)-methylmalonate layers

Three new copper(II) complexes of formula [Cu(Memal)(H2O)]n (1), [Cu2(pyz)(Memal)2] (2) and [Cu2(4,4′-bpy)(Memal)2(H2O)2] (3) (Memal = methylmalonate, pyz = pyrazine and 4,4′-bpy = 4,4′-bipyridine) were obtained and structurally characterized by X-ray diffraction. Complex 1 is a square grid of aquacopper(II) units which are linked by carboxylate-methylmalonate groups in the anti–syn (equatorial–equatorial) coordination mode. The crystal structures of 2 and 3 consist of corrugated layers of copper(II) (2) and aquacopper(II) (3) units with intralayer carboxylate-methylmalonate bridges in the anti–syn (equatorial–apical) coordination mode which are linked through pyrazine (2) and 4,4′-bipyridi…

Prussian Blue Analogues of Reduced Dimensionality

Abstract: Mixed-valence polycyanides (Prussian Blue analogues) possess a rich palette of properties spanning from room-temperature ferromagnetism to zero thermal expansion, which can be tuned by chemical modifications or the application of external stimuli (temperature, pressure, light irradiation). While molecule-based materials can combine physical and chemical properties associated with molecular-scale building blocks, their successful integration into real devices depends primarily on higher-order properties such as crystal size, shape, morphology, and organization. Herein a study of a new reduced-dimensionality system based on Prussian Blue analogues (PBAs) is presented. The system is …

Metamagnetism in hydrophobically induced carboxylate (phenylmalonate)-bridged copper(II) layers

Self-assembly of copper(II) ions, phenylmalonate and pyrimidine yields the layered compound [Cu(pym)(Phmal)]n ( 1) where intralayer ferro- and interlayer antiferromagnetic interactions occur with three-dimensional antiferromagnetic ordering at Tc = 2.15 K Lloret Pastor, Francisco, Francisco.Lloret@uv.es ; Julve Olcina, Miguel, Miguel.Julve@uv.es

A heteropentanuclear oxalato-bridged [ReIV 4GdIII] complex: synthesis, crystal structure and magnetic properties

The compound (NBu 4) 5[Gd III{Re IVBr 4(μ-ox)} 4(H 2O)]·H 2O (1), with intramolecular antiferromagnetic coupling, is the first Re(iv) system incorporating a 4f ion. © 2012 The Royal Society of Chemistry.

Solid‐State Anion–Guest Encapsulation by Metallosupramolecular Capsules Made from Two Tetranuclear Copper(II) Complexes

A new cationic tetranuclear copper(II) complex self-assembles from one 1,3-phenylenebis(oxamato) (mpba) bridging ligand and four CuII ions partially blocked with N,N,N′,N′-tetramethylethylenediamine (tmen) terminal ligands. In the solid state, two of these tetracopper(II) oxamato complexes of bowl-like shape and helical conformation then serve as a building block for the generation of either hetero- (MP) or homochiral (MM/PP) dimeric capsules depending on the nature of the encapsulated anion guest, perchlorate or hexafluorophosphate. The overall magnetic behaviour of these metallosupramolecular capsules does not depend on the nature of the encapsulated anion guest, but it is consistent with…

Enhancing the Magnetic Coupling of Oxalato-Bridged ReIV2MII (M = Mn, Co, Ni, and Cu) Trinuclear Complexes via Peripheral Halide Ligand Effects

Four heterotrinuclear Re(IV)(2)M(II) compounds of general formula (NBu(4))(2)[{Re(IV)Br(4)(μ-ox)}(2)M(II)(Him)(2)] [NBu(4)(+) = tetra-n-butylammonium cation, ox = oxalate, Him = imidazole; M = Mn (1), Co (2), Ni (3), and Cu (4)] have been synthesized by using the novel mononuclear complex [Re(IV)Br(4)(ox)](2-) as a ligand toward divalent first-row transition metal ions in the presence of imidazole. Compounds 1-4 are isostructural complexes whose structure contains discrete trinuclear [{Re(IV)Br(4)(μ-ox)}(2)M(II)(Him)(2)](2-) anions and bulky NBu(4)(+) cations. The Re and M atoms are six-coordinated: four peripheral bromo and two oxalate-oxygens (at Re), and two cis-coordinated imidazole mol…

Ligand Design for Heterobimetallic Single-Chain Magnets: Synthesis, Crystal Structures, and Magnetic Properties of MIICuII (M=Mn, Co) Chains with Sterically Hindered Methyl-Substituted Phenyloxamate Bridging Ligands

Two new series of neutral ox-amato-bridged heterobimetallic chains of general formula [MCu(L x ) 2 ]- m DMSO (m=0-4) (L 1 =N-2-methyl-phenyloxamate, M=Mn (1a) and Co (1 b); L2 = N-2,6-dimethylphenyloxamate, M=Mn (2a) and Co (2b); L 3 = N-2,4,6-trimethylphenyloxamate, M= Mn (3a) and Co (3b)) have been prepared by reaction between the corresponding anionic oxamatocopper(II) complexes [Cu(L x ) 2 ] 2- with Mn 2+ or Co 2+ cations in DMSO. The crystal structures of [CoCu(L 2 ) 2 (H 2 O) 2 ] (2b') and [CoCu(L 3 ) 2 (H 2 O) 2 ]·4H 2 O (3b') have been solved by single-crystal X-ray diffraction methods. Compounds 2b' and 3b' adopt zigzag and linear chain structures, respectively. The intrachain Cu··…

Synthesis, Structure, and Magnetic Properties of a Family of Heterometallic Pentanuclear [Co 4 Ln] (Ln = Gd III , Dy III , Tb III , and Ho III ) Assemblies

The reaction of 6-formyl-2-(hydroxymethyl)-4-methylphenol (LH2) with appropriate lanthanide salts followed by reaction with Co(OAc)2·4H2O afforded the pentanuclear heterobimetalllic compounds [Co4Ln(L)4(OAc)2(S)4](NO3)(S) [LnIII = GdIII, S = MeOH (1); LnIII = DyIII, S = H2O (2); LnIII = TbIII, S = MeOH (3); LnIII = HoIII, S = MeOH (4)] in good yields. All the compounds are stable in solution as confirmed by ESI-MS studies. These complexes contain a distorted Co4 tetrahedral core, which encapsulates a central lanthanide ion. The CoII and LnIII ions are in an all-oxygen environments. All the CoII ions possess a distorted octahedral geometry, and the LnIII ions are in a distorted square-antipr…

Magnetic Molecular Conductors Based on Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and the Tris(chlorocyananilato)ferrate(III) Complex

Electrocrystallization of the bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) organic donor in the presence of the [Fe(ClCNAn)3]3– tris(chlorocyananilato)ferrate(III) paramagnetic anion in different stoichiometric ratios and solvent mixtures afforded two different hybrid systems formulated as [BEDT-TTF]4[Fe(ClCNAn)3]·3H2O (1) and [BEDT-TTF]5[Fe(ClCNAn)3]2·2CH3CN (2) (An = anilato). Compounds 1 and 2 present unusual structures without the typical segregated organic and inorganic layers, where layers of 1 are formed by Λ and Δ enantiomers of the anionic paramagnetic complex together with mixed-valence BEDT-TTF tetramers, while layers of 2 are formed by Λ and Δ enantiomers of the paramagnetic…

Structural and magnetic properties of polynuclear oximate copper complexes with different topologies

Abstract Two new copper(II) complexes containing the methyl(2-pyridyl)ketone oxime ligand (mpkoH) [Cu3(OH)(ClO4)2(mpko)3]·CH3OH (1) and [Cu(ClO4)(mpko)(mpkoH)]n (2) have been prepared from Cu(ClO4)2 and mpkoH in different metal-to-ligand molar ratios. In addition, the compound [Cu{(mpko)2BF2}(H2O)](BF4) (3) [(mpko)2BF2 is the fluoroboration product of the oxime] has been obtained when replacing Cu(ClO4)2 by Cu(BF4)2. Compound 1 is an isolated triangle with a {Cu3(µ3-OH)}5+ core, whereas 2 is a chain of CuII ions linked by anionic mpko− bridges. 1 exhibits strong antiferromagnetic competing interactions, as well as antisymmetric exchange. On the other hand, very weak ferromagnetic interactio…

Cyano-Bridged Bimetallic Assemblies from Hexacyanometalate, [M(CN)6]3- (M = MnIII and FeIII), and [M(N4-macrocycle)]2+ (M = FeIII, NiII and ZnII) Building Blocks. Syntheses, Multidimensional Structures, and Magnetic Properties

Reactions between [M(N4-macrocycle)]2+ (M = ZnII and NiII; macrocycle ligands are either CTH = d,l-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane or cyclam = 1,4, 8, 11-tetrazaazaciclotetradecane) and [M(CN)6]3- (M = FeIII and MnIII) give rise to cyano-bridged assemblies with 1D linear chain and 2D honeycomblike structures. The magnetic measurements on the 1D linear chain complex [Fe(cyclam)][Fe(CN)6]·6H2O 1 points out its metamagnetic behavior, where the ferromagnetic interaction operates within the chain and the antiferromagnetic one between chains. The Neel temperature, TN, is 5.5 K and the critical field at 2 K is 1 T. The unexpected ferromagnetic intrachain interaction can…

Synthesis, crystal structure and magnetic properties of two oxalato-bridged dimetallic trinuclear complexes combined with a polar cation

Two isostructural heterometallic trinuclear oxalato-bridged complexes of formula C(4)[MCr(2)(ox)(6)(H(2)O)(2)]·nH(2)O (C(+) = 4-aminopyridinium; ox(2-) = oxalate dianion; M(2+) = Mn(2+), n = 3, 1; M(2+) = Co(2+), n = 3.25, 2) have been synthesized by using direct self-assembly methods combining C(3)[Cr(ox)(3)] and the chloride salts of the corresponding metal ion. The crystal structures of both compounds have been resolved by single-crystal X-ray diffraction. They crystallize in the C2/c space group [a = 11.5113(15) Å, b = 20.250(3) Å, c = 21.810(4) Å, beta = 100.447(10) degrees, V = 5161.6(3) Å(3), and Z = 4 for 1, and a = 11.4334(16) Å, b = 20.243(2) Å, c = 21.805(3) Å, beta = 101.113(9) …

Ferromagnetic Coupling in the Bis(μ-end-on-azido)iron(III) Dinuclear Complex Anion of[FeII(bpym)3]2[Fe2III(N3)10]·2H2O

Six-coordinate [CoIII(L)2]z (z = 1−, 0, 1+) complexes of an azo-appended o-aminophenolate in amidate(2−) and iminosemiquinonate π-radical (1−) redox-levels: the existence of valence-tautomerism

Aerobic reaction of the ligand H2L1, 2-(2-phenylazo)-anilino-4,6-di-tert-butylphenol, CoCl2·6H2O and Et3N in MeOH under refluxing conditions produces, after work-up and recrystallization, black crystals of [Co(L1)2] (1). When examined by cyclic voltammetry, 1 displays in CH2Cl2 three one-electron redox responses: two oxidative, E11/2 = 0.30 V (peak-to-peak separation, ΔEp = 100 mV) and E21/2 = 1.04 V (ΔEp = 120 mV), and one reductive E1/2 = −0.27 V (ΔEp = 120 mV) vs. SCE. Consequently, 1 is chemically oxidized by 1 equiv. of [FeIII(η5-C5H5)2][PF6], affording the isolation of deep purple crystals of [Co(L1)2][PF6]·2CH2Cl2 (2), and one-electron reduction with [CoII(η5-C5H5)2] yielded bluish-b…

A two-dimensional oxamate- and oxalate-bridged Cu(II)Mn(II) motif: crystal structure and magnetic properties of (Bu4N)2[Mn2{Cu(opba)}2ox].

A new compound of formula (Bu4N)2[Mn2{Cu(opba)}2ox] (1) [Bu4N(+) = tetra-n-butylammonium cation, H4opba = 1,2-phenylenebis(oxamic acid), and H2ox = oxalic acid] has been synthesized and magneto-structurally investigated. The reaction of manganese(II) acetate, [Cu(opba)](2-), and ox(2-) in dimethyl sulfoxide yielded single crystals of 1. The structure of 1 consists of heterobimetallic oxamato-bridged Cu(II)Mn(II) chains which are connected through bis-bidentate oxalate coordinated to the manganese(II) ions to afford anionic heterobimetallic layers of 6(3)-hcb net topology. The layers are interleaved by n-Bu4N(+) counterions. Each copper(II) ion in 1 is four-coordinate in a square planar envi…

Towards oxalate-bridged iron(ii), cobalt(ii), nickel(ii) and zinc(ii) complexes through oxotris(oxalato)niobate(v): an open air non-oxidizing synthetic route

Four compounds with the formula [M2(dmphen)4(μ-C2O4)](ClO4)2·2dmso [M = Fe (1), Co (2) and Zn (4); dmphen = 2,9-dimethyl-1,10-phenanthroline] and [Ni2(dmphen)4(μ-C2O4)]3[NbO(C2O4)3]2·16H2O (3) have been synthesized using the tris(oxalato)oxoniobate(V) complex anion as the oxalate source, and their structures have been determined by single crystal X-ray diffraction. X-ray quality crystals of highly insoluble oxalate-bridged species were obtained by taking advantage of the slow release of oxalate by the tris(oxalato)oxoniobate(V) complex anion. The structures of 1–4 all contain oxalate-bridged dimetal(II) units with didentate dmphen molecules acting as end-cap ligands; electroneutrality is ac…

Neutron diffraction studies of the molecular compound [Co 2(bta)]n (H4bta =1,2,4,5-benzenetetracarboxylic acid): In the quest of canted ferromagnetism

The exchange mechanism and magnetic structure of the organic-inorganic layered molecule-based magnet [Co2(bta)]n (1) (H 4bta =1,2,4,5-benzenetetracarboxylic acid) have been investigated through variable-temperature magnetic susceptibility measurements and supported with a series of neutron diffraction experiments. Cryomagnetic studies have shown an antiferromagnetic ordering at a transition temperature of 16 K that is followed by the appearance of a weak ferromagnetism below 11 K. The weak antiferromagnetic interlayer interaction plays an important role in this system in spite of the long interlayer separation. A ferromagnetic ordering is induced by applied magnetic fields greater than 1800…

Dicopper(II) Metallacyclophanes with Electroswitchable Polymethyl-Substitutedpara-Phenylene Spacers

Double-stranded anionic dinuclear copper(II) metallacyclic complexes of the paracyclophane type [Cu2L2]4- have been prepared by the CuII-mediated self-assembly of different para-phenylenebis(oxamato) bridging ligands with either zero-, one-, or four-electron-donating methyl substituents (L=N,N′-para- phenylenebis(oxamate) (ppba; 1), 2-methyl- N,N′-para-phenylenebis(oxamate) (Meppba; 2), and 2,3,5,6-tetramethyl- N,N′-para-phenylenebis(oxamate) (Me4ppba; 3)). These complexes have been isolated as their tetra-n-butylammonium (1 a-3 a), lithium(I) (1 b-3 b), and tetraphenylphosphonium salts (1 c-3 c). The X-ray crystal structures of 1 a and 3 c show a parallel-displaced π-stacked conformation w…

Dicopper(II) Anthraquinophanes as Multielectron Reservoirs for Oxidation and Reduction: A Joint Experimental and Theoretical Study

Two new dinuclear copper(II) metallacyclophanes with 1,4-disubstituted 9,10-anthraquinonebis(oxamate) bridging ligands are reported that can reversibly take and release electrons at the redox-active ligand and metal sites, respectively, to give the corresponding mono- and bis(semiquinonate and/or catecholate) Cu(II)2 species and mixed-valent Cu(II)/Cu(III) and high-valent Cu(III)2 ones. Density functional calculations allow us to give further insights on the dual ligand- and metal-based character of the redox processes in this novel family of antiferromagnetically coupled di- copper(II) anthraquinophanes. This unique ability for charge storage could be the basis for the development of new k…

Building-block process for the synthesis of new chromium(iii) malonate complexes

We describe the crystal structures of two bimetallic compounds with the malonate and an exo-polydentate N-donor ligand {[Cu(tren)]4[Cr2(mal)4(OH)2]}(ClO4)4·8H2O (3) and [Ni(Htren)2][Cr2(mal)4(OH)2]·8H2O (4) which are prepared from the dinuclear K4[Cr2(mal)4(OH)2]·6H2O precursor (2) [tren = tris(2-aminoethyl)amine and H2mal = malonic acid]. Their crystal packing and supramolecular structures are analyzed in the context of the influence of the dichromium(III) [Cr2(mal)4(OH)2]4− unit, which acts as a building-block. Different supramolecular motifs built up from hydrogen bonds are discussed, and their self-assembly to yield a 3D arrangement is described. The magnetic properties of the compounds…

Synthesis, X‐ray Crystal Structure and Magnetic Properties of Oxalato‐Bridged Copper( II ) Complexes with 2,3‐Bis(2‐pyridyl)pyrazine, 2,3‐Bis(2‐pyridyl)quinoxaline and 2,2′‐Bipyrazine as Peripheral Ligands

Five oxalate-containing copper(II) complexes of formula [Cu(dpq)(H2O)(ox)]·5H2O (1), [Cu(dpp)(H2O)(ox)]·H2O (2), [Cu(bpz)(ox)]n (3), [Cu2(dpp)2(H2O)2(NO3)2(ox)]·4H2O (4) and [Cu2Cl2(bpz)2(H2O)2(ox)][Cu(bpz)(H2O)2(ox)]·2H2O (5) [dpq = 2,3-bis(2-pyridyl)quinoxaline; dpp = 2,3-bis(2-pyridyl)pyrazine; bpz = 2,2′-bipyrazine; ox = oxalate] were prepared and their structures were determined by X-ray diffraction on single crystals. Complexes 1 and 2 are discrete mononuclear complexes with oxalate and dpq (1)/dpp (2) acting as bidentate ligands. Complex 3 is a neutral oxalato-bridged (2,2′-bipyrazine)copper(II) chain where the oxalate adopts a bidentate/monodentate coordination mode, whereas 4 is an…

Mono- and Binuclear Copper(II) and Nickel(II) Complexes with the 3,6-Bis(picolylamino)-1,2,4,5-Tetrazine Ligand

Four new compounds of formulas [Cu(hfac)2(L)] (1), [Ni(hfac)2(L)] (2), [{Cu(hfac)2}2(µ-L)]·2CH3OH (3) and [{Ni(hfac)2}2(µ-L)]·2CH3CN (4) [Hhfac = hexafluoroacetylacetone and L = 3,6-bis(picolylamino)-1,2,4,5-tetrazine] have been prepared and their structures determined by X-ray diffraction on single crystals. Compounds 1 and 2 are isostructural mononuclear complexes where the metal ions [copper(II) (1) and nickel(II) (2)] are six-coordinated in distorted octahedral MN2O4 surroundings which are built by two bidentate hfac ligands plus another bidentate L molecule. This last ligand coordinates to the metal ions through the nitrogen atoms of the picolylamine fragment. Compounds 3 and 4 are cen…

Diphenoxido‐Bridged Co II and Zn II Complexes of Tripodal N 2 O 2 Ligands: Stabilisation of M II ‐Coordinated Phenoxyl Radical Species

Three new tripodal ligands with an N 2 O 2 donor set, namely 2-tert-butyl-6-({(2-hydroxybenzyl)[2-(2-pyridyl)ethyl]amino}-methyl)-4-methylphenol (H 2 L 1 ), 2-tert-butyl-6-({(2-hydroxybenzyl)[2-(2-pyridyl)ethyl]amino}methyl)-4-methoxy-phenol (H 2 L 2 ) and 2-tert-butyl-6-({[2-(dimethylamino)ethyl]-(2-hydroxybenzyl)amino}methyl)-4-methoxyphenol (H 2 L 3 ) have been synthesised. Treatment of the ligands with Co-(CH 3 CO 2 ) 2 ·4H 2 O or [Zn(H 2 O) 6 ][ClO 4 ] 2 in the presence of Et 3 N provides the corresponding Co II and Zn" complexes of composition [M II 2 (L 1 ) 2 ] [M = Co (1) (single-crystals are a solvate with the composition [Co II 2 (L 1 ) 2 ]·2CHCl 3 , i.e. 1·2CHCl 3 ); M = Zn (2)],…

Dimer complexes of 2,4-toluenediamine-N,N,N′,N′-tetraacetic acid (2,4-TDTA) with copper(II), nickel(II), cobalt(II), zinc(II) and manganese(II). Studies in aqueous solution and solid state. X-ray crystal structures of Na4[Ni2(2,4-TDTA)2]·15H2O and Na4[Cu2(2,4-TDTA)2]·20H2O

Abstract Potentiometric investigations in aqueous solution at 25°C and ionic strength 0.1 mol dm−3 KCl show that 2 2,4-toluenediamine-N,N,N′N′-tetraacetic acid (2,4-TDTA) forms with Cu(II), Ni(II), Co(II), Zn(II) and Mn(II) the following complexes (ligand, H4L): monomers [MH2L], [MHL]− and [ML]2−; dimers [M2HL2]3− and [M2L2]4−; with excess of ligand [MH2L2]4−, [MHL2]5− and [ML2]6− (Cu(II), Ni(II) and Zn(II)) and with excess of metal [M2HL]+ (Ni(II), Co(II)and Mn(II) and [M2L] (Cu(II)). The formation constants of the complexes have been determined. The species distribution diagrams indicate that a concentrated solution with a ligand:metal ratio 1:1 at pH 6 is suitable for the synthesis of cr…

Synthesis Crystal Structure and Magnetic Properties of the Trinuclear Nickel(II) Complex Bis[(μ-thiocyanato-N)bis(μ-pyridazine-N1,N2)bis(thiocyanato-N)(pyridazine-N1)nickel(II)- N,N1,N1‘]nickel(II)

Unusual single N-bridging thiocyanato and double pyridazine (pdz) bridges occur in the linear trinuclear nickel(II) complex of formula [Ni3(pdz)6(NCS)6]. The compound exhibits a quasi Curie law behavior, the antiferromagnetic coupling through the double 1,2-diazine links being nearly compensated by the ferromagnetic exchange through the single N-bridging thiocyanato.

Two-Dimensional Assembling of (2,2‘-Bipyrimidine)bis(oxalato)chromate(III) Units through Alkaline Cations

Self-assembling of the tris-chelated [Cr(bpm)(ox)2]- complex with Na+ in aqueous solution leads to the remarkable bimetallic honeycomb layered compound of formula [NaICrIII(bpm)(ox)2]·5H2O (2) (bpm...

[Fe(III)(dmbpy)(CN)4]-: a new building block for designing single-chain magnets.

We herein present the synthesis and magneto-structural study of a new family of heterobimetallic chains of general formula {[Fe(III)(dmbpy)(CN)(4)](2)M(II)(H(2)O)(2)}(n)·pnH(2)O [dmbpy = 4,4'-dimethyl-2,2'-bipyridine; M = Mn (2), Cu (3), Ni (4) and Co (5) with p = 4 (2), 3 (3), 9 (4) and 3.5 (5)] which were prepared by using the mononuclear PPh(4)[Fe(III)(dmbpy)(CN)(4)]·3H(2)O (1) building block (PPh(4)(+) = tetraphenylphosphonium) as a ligand toward fully solvated M(II) ions. The structure of 1 consists of discrete [Fe(III)(dmbpy)(CN)(4)](-) anions, tetraphenylphosphonium cations and noncoordinated water molecules. Complexes 2-5 are isostructural compounds whose structure consists of neutr…

Supramolecular coordination chemistry of aromatic polyoxalamide ligands: A metallosupramolecular approach toward functional magnetic materials

Abstract The impressive potential of the metallosupramolecular approach in designing new functional magnetic materials constitutes a great scientific challenge for the chemical research community that requires an interdisciplinary collaboration. New fundamental concepts and future applications in nanoscience and nanotechnology will emerge from the study of magnetism as a supramolecular function in metallosupramolecular chemistry. Our recent work on the rich supramolecular coordination chemistry of a novel family of aromatic polyoxalamide (APOXA) ligands with first-row transition metal ions has allowed us to move one step further in the rational design of metallosupramolecular assemblies of …

Cobalt(II) and copper(II) assembling through a functionalized oxamate-type ligand

Two new metal complexes of formula {[Co(Hpcpa)(H2O)3]n� 3/2nH2O} (1) and [Cu2(MeHpcpa)4(MeOH)2] � H2O� 3.68 MeOH (2 )[ H 3pcpa = N-(4-carboxyphenyl)oxamic acid and MeH2pcpa = methyl ester derivative of H3pcpa] have been synthesized and their structures determined by X-ray diffraction. 1 is a neutral zigzag chain of cobalt(II) ions bridged by Hpcpa 2� ligands exhibiting the bidentate/monodentate coordination mode. Each cobalt(II) ion is six-coordinate with three mer positioned water molecules, two oxamate-oxygens from a Hpcpa 2� ligand and a carboxylate-oxygen from another Hpcpa 2� group building a somewhat distorted octahedral surrounding. The intrachain cobalt–cobalt separation is 11.326(2…

Dicopper(II) Metallacyclophanes with Oligo(p-phenylene-ethynylene) Spacers: Experimental Foundations and Theoretical Predictions on Potential Molecular Magnetic Wires

Two novel double-stranded dicopper(II) metallacyclophanes of formula (nBu4N)4[Cu2(dpeba)2]·4MeOH·2Et2O (1) and (nBu4N)4[Cu2(tpeba)2]·12H2O (2) have been prepared by the Cu(II)-mediated self-assembly of the rigid ('rod-like') bridging ligands N,N'-4,4'-diphenylethynebis(oxamate) (dpeba) and N,N'-1,4-di(4-phenylethynyl)phenylenebis(oxamate) (tpeba), respectively. Single crystal X-ray diffraction analysis of 1 confirms the presence of a dicopper(II)tetraaza[3.3]4,4'-diphenylethynophane metallacyclic structure featuring a very long intermetallic distance between the two square planar Cu(II) ions [r = 14.95(1) Å]. The overall parallel-displaced π-stacked conformation of the two nearly planar par…

[Cu3(Hmesox)3]3−: a Precursor for the Rational Design of Chiral Molecule-Based Magnets (H4mesox = 2-dihydroxymalonic acid)

Two new compounds K(3)[Cu(3)(Hmesox)(3)(H(2)O)] x 4 H(2)O (1) and {(PPh(4))(2)[CoCu(3)(Hmesox)(3)Cl]} (2) [H(4)mesox = mesoxalic acid (2-dihydroxymalonic acid) and PPh(4)(+) = tetraphenylphosphonium cation] have been prepared and magneto-structurally characterized. Compound 1 contains the [Cu(3)(Hmesox)(3)](3-) entity which can be considered as a new precursor for molecular magnetism. In 1 the triangular arrangement of three copper(II) ions bridged by alkoxo groups are further connected to a symmetry-related tricopper(II) unit through a double oxo(carboxylate) bridge. The resulting hexacopper(II) entities are joined further through anti-syn carboxylate groups into an anionic three-dimension…

A novel class of interpenetrated 3-D network of a dimeric cupric-tetracarboxylate unit

The hydrothermal reaction of Cu(II), fumaric acid and 4,4′-bipyridine (bpy) in equimolar amounts at 160 °C resulted in a new type of two-fold interpenetrating 3-D coordination network composed of tetracarboxylate dicopper(II) units bridged by bipyridine spacers.

Oxalate, squarate and croconate complexes with bis(2-pyrimidylcarbonyl)amidatecopper(II): synthesis, crystal structures and magnetic properties

Abstract The preparation and magnetic properties of three copper(II) compounds of formulae [Cu2(bpcam)2(H2O)2(C2O4)] (1), [Cu2(bpcam)2(H2O)4(C4O4)] · 10 H2O (2) and Cu2(bpcam)2(C5O5)(H2O)3 (3) [bpcam = bis(2-pyrimidyl)amidate, C 2 O 4 2 - = dianion of oxalic acid , C 4 O 4 2 - = dianion of 3 , 4 - dihydroxycyclobut - 3 - ene - 1 , 2 - dione and C 5 O 5 2 - = dianion of 4 , 5 - dihydroxycyclopent - 4 - ene - 1 , 2 , 3 - trione ] are reported. The structures of two of them (1 and 2) have been solved by single crystal X-ray diffraction and consists of centrosymmetric discrete copper(II) dinuclear units bridged by bis-bidentate oxalate (1) and bis-monodentate squarate (2), with the bpcam group …

Copper(II)-phenylmalonate complexes with the bifunctional ligands nicotinamide and isonicotinamide

Abstract The use as coligands of the nicotinamide (nia) and isonicotinamide (inia) molecules in the complex formation between copper(II) and phenylmalonate [Phmal = dianion of phenylmalonic acid] yielded the compounds of formula [Cu(inia)(Phmal)(H2O)] (1) and [Cu(inia)(Phmal)(H2O)]n (2). Although single crystals of 1 of appropriate size were grown, their unresolved twinning and space group ambiguity prevented a satisfactory X-ray structure determination. The crystal structure 2 consists of corrugated layers of copper(II) ions with intralayer carboxylate–phenylmalonate bridges in the anti-syn (equatorial-apical) coordination mode. A water molecule and the isonicotinamide group are coordinate…

Relatively strong intramolecular antiferromagnetic coupling in a neutral Cr(III)2Nb(V)2 heterobimetallic molecular square.

A relatively large antiferromagnetic interaction between the two chromium(III) ions from the molecular square [{Cr(dmso)4}2{Nb(μ-O)2(C2O4)2}2] () (J = -12.0 cm(-1)) is mediated by the diamagnetic oxo-Nb(V)-oxo pathway, its nature and magnitude being substantiated by DFT type theoretical calculations.

Chemistry and reactivity of mononuclear manganese oxamate complexes: Oxidative carbon-carbon bond cleavage of vic-diols by dioxygen and aldehydes catalyzed by a trans-dipyridine manganese(III) complex with a tetradentate o-phenylenedioxamate ligand

[EN] Two new mononuclear octahedral manganese(III) complexes with the tetradentate equatorial ligand o-phenylenebis(oxamate) (opba) and two aquo (1a) or two pyridine (1b) axial ligands have been synthesized and characterized structurally, magnetically, and electrochemically. The cyclovoltammogram of 1a in acetonitrile (25 degrees C, 0.1 M Bu4NPF6) shows an irreversible one-electron oxidation peak at a high anodic potential (E-ap = 1.03 V versus SCE), while that of 1b shows two well-separated one-electron oxidation peaks at moderate to high anodic potentials (E-ap = 0.92 and 1.27 V versus SCE), the first redox-wave being quasireversible in nature. The access to formally high-valent Mn-IV and…

Two copper complexes from two novel naphthalene-sulfonyl-triazole ligands: different nuclearity and different DNA binding and cleavage capabilities.

[EN] Two novel naphthalene-sulfonyl-triazole ligands, 5-amino-N1-(naphthalen-3-ylsulfony1)-1,2,4-triazole (anstrz) and 3,5-diamino-N1-(naphthalen-3-ylsulfony1)-1,2,4-triazole (danstrz), purposely designed to interact with DNA, have been prepared for the first time and then fully characterized by H-1, C-13 NMR and IR spectroscopy, mass spectrometry and elemental analysis. The crystal structures of two copper complexes of these derivatives, i.e. [Cu(anstrz)(4)(NO3)(2)]center dot 4CH(3)OH (1), mononuclear, and [Cu(danstrz)(mu-OAc)(2)](2)center dot 2(danstrz) (OAc = acetato) (2), dinuclear, have been determined by single-crystal X-ray diffraction. In both cases the ligand coordinates in a monod…

Spin control in oxamato-based manganese(II)-copper(II) coordination polymers with brick-wall layer architectures.

Two new heterobimetallic manganese(II)-copper(II) coordination polymers of formulas [Mn(2)Cu(2)(Me(3)mpba)(2)(H(2)O)(6)]·8H(2)O (1) and [Mn(2)Cu(2)(Me(4)ppba)(2)(H(2)O)(6)]·8H(2)O (2) [Me(3)mpba = 2,4,6-trimethyl-N,N'-1,3-phenylenebis(oxamate) and Me(4)ppba = 2,3,5,6-tetramethyl-N,N'-1,4-phenylenebis(oxamate)] have been synthesized following a molecular-programmed self-assembly method from the corresponding dicopper(II) complexes acting as metalloligands toward Mn(II) ions. 1 and 2 consist of neutral Mn(II)(2)Cu(II)(2) layers with a brick-wall structure made up of oxamato-bridged Mn(II)Cu(II) chains connected through double meta- (1) and para-substituted (2) permethylated phenylene spacers.…

Cyanido‐Bearing Cobalt(II/III) Metalloligands – Synthesis, Crystal Structure, and Magnetic Properties

New examples of cyanido-bearing cobalt(III/II) complexes have been obtained by treatment of CoCl2·6H2O with bidentate nitrogen donors and potassium cyanide in a methanol/water mixture. Depending on the chelating ligand, the cobalt(III) complexes PPh4[Co(en)(CN)4] (1, en = ethylenediamine), PPh4[Co(ampy)(CN)4]·1.5H2O [2, ampy = 2-(aminomethyl)pyridine], and PPh4[Co(phen)(CN)4]·CH3OH·0.25H2O (3, phen = 1,10-phenanthroline) and the cobalt(II) complex PPh4[Co(dmphen)(CN)3]·3H2O (4, dmphen = 2,9-dimethyl-1,10-phenanthroline) were obtained. The complexes were characterized by single-crystal X-ray diffraction and variable-temperature magnetic measurements. They are all mononuclear species with six…

A heterobimetallic [MnII5CuII5] nanowheel modulated by a flexible bis-oxamate type ligand

The synthesis, crystal structure and preliminary magnetic characterization of a new heterobimetallic [MnII5CuII5] wheel containing a flexible bis-oxamate type ligand are described. This decanuclear compound exhibits a relatively strong intra-wheel antiferromagnetic interaction leading to a ground spin state S = 10.

Well-resolved unusual alternating cyclic water tetramers embedded in a crystal host

Infinite network involving two hydrogen-bonded tetrameric water rings (S4 and D2h) in a (4,4)-square grid crystal host

Magneto-structural correlations in Ni(ii) [2 × 2] metallogrids featuring a variable number of μ-aquo or μ-hydroxo extra bridges

Four new [2 × 2] grid-type metallosupramolecular species have been obtained by using the ditopic 3,6-bis(2′-pyridyl)pyridazine ligand (dppn) and nickel(II) salts containing poorly coordinating anions. Three of them have the formula [Ni4(μ-dppn)4(μ-OH)2(μ-H2O)2]X6·nH2O [with X = ClO4− (1), NO3− (2) and CF3SO3− (3), and n = 6.5 (1), 14 (2) and 4 (3)]. Their crystal structure shows the same tetranuclear core, constituted by four six-coordinate metal ions and four dppn molecules. Two hydroxo groups and two water molecules efficiently interact forming two hydrated hydroxide (H3O2−) supramolecular bridging anions, further stabilizing the grid. The other compound, [Ni4(μ-dppn)4(μ-OH)3(μ-H2O)](ClO4…

Thermodynamics of the two-dimensional Heisenberg classical honeycomb lattice

In this article we adapt a previous work concerning the two-dimensional (2D) Heisenberg classical square lattice [Physica B 245, 263 (1998)] to the case of a honeycomb lattice. Closed-form expressions of the main thermodynamic functions of interest are derived in the zero-field limit. Notably, near absolute zero (i.e., the critical temperature), we derive the values of the critical exponents $\ensuremath{\alpha}=0,\ensuremath{\eta}=\ensuremath{-}1,\ensuremath{\gamma}=3,$ and $\ensuremath{\nu}=1,$ as for the square lattice, thus proving their universal character. A very simple model allows one to give a good description of the low-temperature behaviors of the product $\ensuremath{\chi}T.$ Fo…

Ferromagnetic coupling and spin canting behaviour in heterobimetallic ReIVMII/III(M = CoII/III, NiII) species

Three novel heterobimetallic Re(IV) compounds of formulae [ReBr(4)(μ-ox)M(4,7-Cl(2)phen)(2)]·CH(3)CN·CH(3)NO(2) [M = Co(II) (1) and Ni(II) (2)] and [ReBr(4)(ox)](3)[Co(III)(5,6-dmphen)(3)](2)·CH(3)CN·2CH(3)NO(2)·4H(2)O (3) [ox = oxalate, 4,7-Cl(2)phen = 4,7-dichloro-1,10-phenanthroline and 5,6-dmphen = 5,6-dimethyl-1,10-phenanthroline] have been synthesised and the structures of 1 and 3 determined by single crystal X-ray diffraction. Compound 1 is an oxalato-bridged Re(IV)Co(II) heterodinuclear complex where the [ReBr(4)(ox)](2-) unit acts as a bidentate ligand towards the [Co(4,7-Cl(2)phen)(2)](2+) entity, the separation between Re(IV) and Co(II) across the oxalate being 5.482(1) Å. Compou…

Study of the influence of the bridge on the magnetic coupling in cobalt(II) complexes.

Two new cobalt(II) complexes of formula [Co(2)(bta)(H(2)O)(6)](n) x 2nH(2)O (1) and [Co(phda)(H(2)O)](n) x nH(2)O (2) [H(4)bta = 1,2,4,5-benzenetetracarboxylic acid, H(2)phda = 1,4-phenylenediacetic acid] have been characterized by single crystal X-ray diffraction. Compound 1 is a one-dimensional compound where the bta(4-) ligand acts as 2-fold connector between the cobalt(II) ions through two carboxylate groups in para-conformation. Triply bridged dicobalt(II) units occur within each chain, a water molecule, a carboxylate group in the syn-syn conformation, and an oxo-carboxylate with the mu(2)O(1);kappa(2)O(1),O(2) coordination mode acting as bridges. Compound 2 is a three-dimensional comp…

Oligo-m-phenyleneoxalamide Copper(II) Mesocates as Electro-Switchable Ferromagnetic Metal–Organic Wires

Double-stranded copper(II) string complexes of varying nuclearity, from di- to tetranuclear species, have been prepared by the CuII-mediated self-assembly of a novel family of linear homo- and heteropolytopic ligands that contain two outer oxamato and either zero (1 b), one (2 b), or two (3 b) inner oxamidato donor groups separated by rigid 2-methyl-1,3-phenylene spacers. The X-ray crystal structures of these CuIIn complexes (n=2 (1 d), 3 (2 d), and 4 (3 d)) show a linear array of metal atoms with an overall twisted coordination geometry for both the outer CuN2O2 and inner CuN4 chromophores. Two such nonplanar all-syn bridging ligands 1 b–3 b in an anti arrangement clamp around the metal ce…

The Role of Order-Disorder Transitions in the Quest for Molecular Multiferroics: Structural and Magnetic Neutron Studies of a Mixed Valence Iron (II)-Iron (III) Formate Framework

Neutron diffraction studies have been carried out to shed light on the unprecedented order-disorder phase transition (ca. 155 K) observed in the mixed-valence iron(II)-iron(III) formate framework compound [NH 2(CH3)2]n[FeIIIFe II(HCOO)6]n. The crystal structure at 220 K was first determined from Laue diffraction data, then a second refinement at 175 K and the crystal structure determination in the low temperature phase at 45 K were done with data from the monochromatic high resolution single crystal diffractometer D19. The 45 K nuclear structure reveals that the phase transition is associated with the order-disorder of the dimethylammonium counterion that is weakly anchored in the cavities …

Oxalate and 2,2′-bipyrimidine as bis-chelating ligands in the honeycomb layered compound {[Fe2(bpym)(ox)2]·5H2O}n

The novel two-dimensional iron(II) compound of formula {[Fe2(bpym)(ox)2]·5H2O}n (1) [bpym = 2,2′-bipyrimidine and ox = oxalate dianion] is obtained by reaction of oxalic acid, iron(II) chloride and 2,2′-bipyrimidine in aqueous solution. The structure of 1 is made up of oxalato-bridged iron(II) chains cross-linked by bischelating bpym affording a honeycomb lattice. Variable-temperature magnetic susceptibility data of 1 show the occurrence of relatively large antiferromagnetic interactions between the high spin iron(II) ions separated by more than 5.5 A through bridging bpym [Jbpym = −4.0(2) cm−1] and ox [Jox = ca. −7.8(2) cm−1] ligands. These values compare well with those obtained in the ir…

Coordination chemistry of N,N′-bis(coordinating group substituted)oxamides: a rational design of nuclearity tailored polynuclear complexes

Abstract The coordinating properties of N , N ′-bis(coordinating group substituted)oxamides have been thoroughly investigated both in aqueous solution and in the solid state. The easy cis – trans isomerization equilibria that they exhibit together with the great variety of N , N ′-substituents which can be used to play on the overall charge, complexing ability and polarity, make them very suitable ligands in designing homo- and heterometallic species. The knowledge of their complex formation in aqueous solution by potentiometry and using the hydrogen ion concentration as a probe, allowed us to settle the basis of a rational design of oxamidate-containing polynuclear species whose nuclearity…

A new mixed-valence hexanuclear cobalt complex, [Co4IICo2III(dea)2(Hdea)4)(piv)4](ClO4)2·H2O: Synthesis, crystal structure and magnetic properties

A new Co II /Co III hexanuclear complex, [Co 4 II Co 2 III (dea) 2 (Hdea) 4 )(piv) 4 ](ClO 4 ) 2 ·H 2 O 1 , has been obtained by reacting cobalt(II) perchlorate, diethanolamine, and pivalic acid (H 2 dea = diethanolamine and piv = pivalato anion). The cobalt ions are held together by four μ 3 and four μ 2 alkoxo bridges as well as by four syn – syn carboxylato groups. The hexanuclear motif contains four Co(II) and two Co(III) ions. The {Co II 4 Co III 2 (μ 2 -O) 4 (μ 3 -O) 4 } core can be described as a four face-sharing monovacant and bivacant distorted heterocubane units. The cobalt(III) ions are hexacoordinated. Two of the cobalt(II) are hexacoordinated, while the two others are pentacoo…

Coordination versatility of 1,3-bis[3-(2-pyridyl)pyrazol-1-yl]propane: Co(II) and Ni(II) complexes

Abstract The ligand 1,3-bis[3-(2-pyridyl)pyrazol-1-yl]propane (L8) has afforded six-coordinate monomeric and dimeric complexes [(L8)CoII(H2O)2][ClO4]2 (1), [(L8)NiII(MeCN)2][BPh4]2 (2), [(L8)NiII(O2CMe)][BPh4] (3), and [ ( L 8 ) 2 Co 2 II ( μ - O 2 CMe ) 2 ] [ BPh 4 ] 2 ( 4 ) . The crystal structures of 1, 2 · MeCN, 3, and 4 revealed that the ligand L8 is flexible enough to expand its coordinating ability by fine-tuning the angle between the chelating fragments and hence folds around cobalt(II)/nickel(II) centers to act as a tetradentate chelate, allowing additional coordination by two trans-H2O, cis-MeCN, and a bidentate acetate affording examples of distorted octahedral Co II N 2 ( pyridy…

Synthesis, crystal structure and magnetic properties of a novel heterobimetallic rhenium(IV)-dysprosium(III) chain.

The use of the mononuclear rhenium(IV) precursor [ReBr5 (H2 pydc)](-) (H2 pydc=3,5-pyridinedicarboxylic acid) as a metalloligand towards dysprosium(III) afforded the first heterobimetallic Re(IV) -Dy(III) complex. Crystal structures and static and dynamic magnetic properties of both rhenium-containing species are reported herein. The 5d-4f compound shows an extended 1D structure and the AC magnetic measurements reveal frequency dependence at low temperature suggesting slow relaxation of the magnetization.

Magnetostructural relationships in polymorphic ethylmalonate-containing copper(ii) coordination polymers

Three ethylmalonate-containing copper(II) chiral complexes of the formula {[Cu(H2O)4][Cu(Etmal)2(H2O)]}n (1), [Cu(Etmal)(H2O)]n (2) and {[Cu(Etmal)(H2O)]·H2O}n (3) (H2Etmal = ethylmalonic acid) were obtained by reacting copper(II) nitrate trihydrate, ethylmalonic acid and sodium carbonate in water. Compound 1 is a chiral zigzag chain with regular alternation of [Cu(Etmal)2(H2O)]2− and [Cu(H2O)4]2+ units, the former acting as bis-monodentate ligands toward the latter ones through the two carboxylate groups. The chirality of 1 is a result of the [Cu(Etmal)2(H2O)]2− fragment whose five-coordinate copper(II) surrounding exhibits the Δ or Λ conformation within the Δ or Λ-crystals. The structure …

Metal-organic coordination frameworks based on mixed methylmalonate and 4,4′-bipiridine ligands: synthesis, crystal structure and magnetic properties

Five new complexes of formulae [M2(4,4′-bpy)(Memal)2X2]n [M = Fe(III) (2), Mn(II) (3), Co(II) (4), Ni(II) (5) and Zn(II) (6), and X = Cl−/OH− (2) and H2O (3–6); 4,4′-bpy = 4,4′-bipyridine and Memal = methylmalonate dianion] have been synthesized by following the previously reported procedure for [Cu2(4,4′-bpy)(Memal)2(H2O)2]n (1). Moreover, two new phases of the Cu(II)/Memal/4,4′-bpy system, namely {[Cu(4,4′-bpy)2][Cu(4,4′-bpy)2(Memal)(NO3)(H2O)]}n·nNO3·3.5nH2O (7) and [Cu(4,4′-bpy)2(Memal)(H2O)]n·nH2O (8), were obtained by varying the synthetic conditions. They were all structurally characterized by single crystal X-ray diffraction, and the magnetic properties of 2–5, 7 and 8 were investig…

Slow magnetic relaxation in a hydrogen-bonded 2D array of mononuclear dysprosium(III) oxamates.

The reaction of N-(2,6-dimethylphenyl)oxamic acid with dysprosium(III) ions in a controlled basic media afforded the first example of a mononuclear lanthanide oxamate complex exhibiting a field-induced slow magnetic relaxation behavior typical of single-ion magnets (SIMs). The hydrogen-bond-mediated self-assembly of this new bifunctional dysprosium(III) SIM in the solid state provides a unique example of 2D hydrogen-bonded polymer with a herringbone net topology.

Slow relaxation of the magnetization in a 4,2-wavelike Fe(III)2Co(II) heterobimetallic chain.

The reaction of the low-spin iron(III) complex [Fe(dmbpy)(CN)(4)](-) (1) with fully solvated cobalt(II) ions affords the cyanide-bridged heterobimetallic chain {[Fe(III)(dmbpy)(CN)(4)](2)Co(II)(H(2)O)(2)}(n) · 4nH(2)O (2), which exhibits intrachain ferromagnetic coupling and double slow relaxation of the magnetization.

Reversible solvatomagnetic switching in a single-ion magnet from an entatic state

We have developed a new strategy for the design and synthesis of multifunctional molecular materials showing reversible magnetic and optical switching.

Alternating cationic–anionic layers in the [Mii(H2O)6][Cuii(mal)2(H2O)] complexes linked through hydrogen bonds (M = Mn, Co, Ni, Cu and Zn; H2mal = malonic acid)

The compounds of formula [MII(H2O)6][CuII(mal)2(H2O)2] [M = Mn (1), Co (2), Ni (3), Cu (4), Zn (5) and H2mal = malonic acid] have been prepared and structurally characterised. Each compound adopts a structure where the layers of [Cu(mal)2(H2O)2]2− anions alternate with layers of [M(H2O)6]2+ cations. The layers are linked to each other through hydrogen bonds affording a three-dimensional network. A quasi-Curie law behaviour is observed for the complexes 1–5 in the temperature range 2.0–298 K.

Modeling Tyrosinase and Catecholase Activity Using New m-Xylyl-Based Ligands with Bidentate Alkylamine Terminal Coordination

Chemical model systems possessing the reactivity aspects of both tyrosinase and catechol oxidase are presented. Using two m-xylyl-based ligands providing bidentate alkylamine terminal coordination, 1,3-bis[(N,N-dimethylaminoethyl)aminomethyl]benzene (L(H,H)) and 1,3-bis[(N,N,N'-trimethylaminoethyl)aminomethyl]benzene (L(Me,Me)), four new dicopper(I) complexes, [Cu(I)(2)(L(H,H))(MeCN)(4)][ClO(4)](2) (1), [Cu(I)(2)(L(H,H))(PPh(3))(2)(MeCN)(2)][ClO(4)](2) (2), [Cu(I)(2)(L(Me,Me))(MeCN)(2)][ClO(4)](2) (3), and [Cu(I)(2)(L(Me,Me))(PPh(3))(2)][ClO(4)](2) (4), have been synthesized and characterized. Complex 2 has been structurally characterized. Reaction of the dicopper(I) complex 3(2+) with diox…

Field-induced slow relaxation of magnetisation in two one-dimensional homometallic dysprosium(iii) complexes based on alpha- and beta-amino acids.

Two one-dimensional dysprosium(III) complexes based on α-glycine (gly) and β-alanine (β-ala) amino acids, with the formula {[Dy2(gly)6(H2O)4](ClO4)6·5H2O}n (1) and {[Dy2(β-ala)6(H2O)4](ClO4)6·H2O}n (2), have been synthesised and characterised structurally and magnetically. Both compounds crystallise in the triclinic system with the space group P. In 1, two DyIII ions are eight-coordinate and bound to six oxygen atoms from six gly ligands and two oxygen atoms from two water molecules, showing different geometries (bicapped trigonal prism and square antiprism). In 2, two DyIII ions are nine-coordinate and bound to seven oxygen atoms from six β-ala ligands and two oxygen atoms from two water m…

Synthesis, crystal structure and magnetic properties of the helical oxalate-bridged copper(II) chain {[(CH3)4N]2[Cu(C2O4)2] · H2O}n

Abstract The preparation, crystal structure and magnetic properties of a new oxalate-containing copper(II) chain of formula {[(CH3)4N]2[Cu(C2O4)2] · H2O}n (1) [(CH3)4N+ = tetramethylammonium cation] are reported. The structure of 1 consists of anionic oxalate-bridged copper(II) chains, tetramethylammoniun cations and crystallization water molecules. Each copper(II) ion in 1 is surrounded by three oxalate ligands, one being bidentate and the other two exhibiting bis-bidenate coordination modes. Although all the tris-chelated copper(II) units from a given chain exhibit the same helicity, adjacent chains have opposite helicities and then an achiral structure results. Variable-temperature magne…

Titelbild: Cyanide-Bridged Iron(III)–Cobalt(II) Double Zigzag Ferromagnetic Chains: Two New Molecular Magnetic Nanowires (Angew. Chem. 13/2003)

Nuclearity controlled cyanide-bridged bimetallic CrIII-MnII compounds: synthesis, crystal structures, magnetic properties and theoretical calculations.

The preparation, X-ray crystallography and magnetic investigation of the compounds PPh4[Cr(bipy)(CN)4].2 CH3CN.H2O (1) (mononuclear), [[Cr(bipy)(CN)4]2Mn-(H2O)4].4H2O (2) (trinuclear), [[Cr(bipy)(CN)4]2Mn(H2O)2] (3) (chain) and [[Cr(bipy)(CN)4]2Mn(H2O)].H2O.CH3CN (4) (double chain) [bipy=2,2'-bipyridine; PPh4 (+)=tetraphenylphosphonium] are described herein. The [Cr(bipy)(CN)4]- unit act either as a monodentate (2) or bis-monodentate (3) ligand toward the manganese atom through one (2) or two (3) of its four cyanide groups. The manganese atom is six-coordinate with two (2) or four (3) cyanide nitrogens and four (2) or two (3) water molecules building a distorted octahedral environment. In 4…

From Mononuclear Compounds to [2 × 2] Metallogrids: Ferromagnetically Coupled Systems Built by Nickel(II) and 3,6-Bis(2′-pyridyl)pyridazine (dppn)

Mono-, di-, tri-, and tetranuclear compounds of nickel(II) of formula [Ni(dppn)3](NCS)2·0.5dppn (1), [{Ni(dppn)(NCS)}2(μ-dppn)(μ-NCS)]NCS (2), [Ni3(dppn)2(N3)2(μ-dppn)2(μ-N3)2](ClO4)2·CH3CH2OH·2H2O...

Ligand effects on the structures and magnetic properties of tricyanomethanide-containing copper(II) complexes.

The preparation, crystal structure and magnetic properties of four heteroleptic copper(II) complexes with the tricyanomethanide (tcm(-)) and the heterocyclic nitrogen donors 3,6-bis(2-pyridyl)pyridazine (dppn), 2,5-bis(2-pyridyl)pyrazine (2,5-dpp), 2,3-bis(2-pyridyl)pyrazine (2,3-dpp) and 2,3-bis(2-pyridyl)quinoxaline (2,3-dpq) are reported, {[Cu(2)(dppn)(OH)(tcm)(2)] x tcm}(n) (1), {[Cu(2,5-dpp)(tcm)] x tcm}(n) (2), {[Cu(2)(2,3-dpp)(2)(tcm)(3)(H(2)O)(0.5)] x tcm x 0.5H(2)O}(n) (3) and [Cu(2,3-dpq)(tcm)(2)](n) (4). 1 has a ladder-like structure with single mu-1,5-tcm ligands forming the sides and a bis-bidentate dppn and a single mu-hydroxo providing the rung. Each copper atom in 1 exhibits…

Field-Induced Hysteresis and Quantum Tunneling of the Magnetization in a Mononuclear Manganese(III) Complex

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[Ni(cyclam)(μ1,3-dca)2Cu(μ1,5-dca)2]:  A Genuine 3D Bimetallic Coordination Polymer Containing Both μ1,3- and μ1,5-Bidentate Dicyanamide Bridges and a Ferromagnetic Interaction between Copper(II) and Nickel(II) Ions

The structure of [Ni(cyclam)(μ 1 , 3 -dca) 2 Cu(μ 1 , 5 -dca) 2 ], a genuine 3D dicyanamide-bridged bimetallic coordination polymer, is made up of 2D [Cu(μ- 1 , 5 dca) 2 ] n layers connected by [Ni(cyclam)(μ 1 , 3 -dca) 2 ] bridging moieties; it exhibits a ferromagnetic exchange interaction between copper(ll) and nickel(ll) ions through the μ 1 , 3 -bidentate dicyanamide bridges.

Synthesis, crystal structure and magnetic properties of [Cu(bipy)2(CH3COO)][Cu(bipy)2(Cr(C2O4)3)]·∼10.5H2O, the first compound containing the [Cr(C2O4)3]3− building block acting as a monodentate ligand

Abstract The reaction between copper(II) acetate with 2,2′-bipyridine and K3[Cr(C2O4)3] leads to the novel salt [Cu(bipy)2(CH3COO)][Cu(bipy)2(Cr(C2O4)3)]·∼10.5H2O, 1 (bipy=2,2′-bipyridine). The crystal structure of 1 consists of mononuclear cationic species [Cu(bipy)2(CH3COO)]+ and heterobinuclear anionic units, [Cu(bipy)2(Cr(C2O4)3)]−. The tris-oxalato-chromium entity behaves as a monodentate ligand toward the copper(II) ion within the complex anion. The distance between Cr(III) and Cu(II) across the bridging oxalato group is 5.056(2) A. The copper(II) ions exhibit a distorted trigonal bipyramidal surrounding in both cationic and anionic species. The π–π stacking interaction between bipy l…

Variation of the ground spin state in homo- and hetero-octanuclear copper(II) and nickel(II) double-star complexes with a meso-helicate-type metallacryptand core.

Homo- and heterometallic octanuclear complexes of formula Na₂{[Cu₂(mpba)₃][Cu(Me₅dien)]₆}-(ClO₄)₆·12H₂O (1), Na₂{[Cu₂(Mempba)₃][Cu(Me₅dien)]₆}(ClO₄)₆·12H₂O (2), Na₂{[Ni₂(mpba)₃]-[Cu(Me₅dien)]₆}(ClO₄)₆·12H₂O (3), Na₂{[Ni₂(Mempba)₃][Cu(Me₅dien)]₆}(ClO₄)₆·9H₂O (4), {[Ni₂(mpba)₃][Ni(dipn)(H₂O)]₆}(ClO₄)₄·12.5H₂O (5), and {[Ni₂(Mempba)₃][Ni(dipn)-(H₂O)]₆}(ClO₄)₄·12H₂O (6) [mpba = 1,3-phenylenebis(oxamate), Mempba = 4-methyl-1,3-phenylenebis(oxamate), Me₅dien = N,N,N',N'',N''-pentamethyldiethylenetriamine, and dipn = dipropylenetriamine] have been synthesized through the "complex-as-ligand/complex-as-metal" strategy. Single-crystal X-ray diffraction analyses of 1, 3, and 5 show cationic M(II)₂M'(I…

A phenoxo-bridged dicopper(ii) complex as a model for phosphatase activity: mechanistic insights from a combined experimental and computational study

A μ-phenoxo-bis(μ2-1,3-acetato)-bridged dicopper(II) complex [CuII2(L1)(μ-O2CMe)2][NO3] (1) has been synthesized from the perspective of modeling phosphodiesterase activity. Structural characterization was done initially with 1·3Et2O (vapour diffusion of Et2O into MeOH solution of 1; poor crystal quality) and finally with its perchlorate salt [CuII2(L1)(μ-O2CMe)2][ClO4]·1.375MeCN·0.25H2O, crystallized from vapour diffusion of n-pentane into a MeCN–MeOH mixture (comparatively better crystal quality). An asymmetric unit of such a crystal contains two independent molecules of compositions [CuII2(L1)(μ-O2CMe)2][ClO4] and [CuII2(L1)(μ-O2CMe)2(MeCN)][ClO4] (coordinated MeCN with 0.75 occupancy), …

Metamagnetic Behavior in [M (tvp) (NCS)2] Coordination Polymers (M = Fe(II) and Co(II); tvp = 1,2-di-(4-pyridyl)-ethylene)

Abstract We report the synthesis and magnetic properties of two new coordination polymers of formula [M(tvp)(NCS)2] (M = Fe(II) and Co(II)). The magnetic data reveal the occurrence of metamagnetic behavior. Switching from bulk antiferromagnetic to ferromagnetic behavior occurs for magnetic fields greater than 1300 G (Fe(II)) and 450 G (Co(II)) at temperatures lower than 4 K. Both compounds are isomorphous. A molecular structure is suggested in the light of the magnetic properties and precedent data on related systems.

Synthesis, crystal structures and magnetic properties of single and double cyanide-bridged bimetallic Fe2(III)Cu(II) zigzag chains.

The bimetallic complexes [[Fe(III)(phen)(CN)4]2Cu(II)(H2O)2].4H2O (1), [[Fe(III)(phen)(CN)4]2Cu(II)].H2O (2) and [[Fe(III)(bipy)(CN)4]2Cu(II)].2H2O (3) and [[Fe(III)(bipy)(CN)4]2Cu(II)(H2O)2].4H2O (4) (phen = 1,10-phenanthroline and bipy = 2,2'-bipyridine) have been prepared and the structures of 1-3 determined by X-ray diffraction. The structure of 1 is made up of neutral cyanide-bridged Fe(III)-Cu(II) zigzag chains of formula [[Fe(III)(phen)(CN)4]2Cu(II)(H2O)2] and uncoordinated water molecules with the [Fe(phen)(CN)4]- entity acting as a bis-monodentate bridging ligand toward two trans-diaquacopper(II) units through two of its four cyanide groups in cis positions. The structure of 2 can …

Heteropolymetallic Supramolecular Solid-State Architectures Constructed from [Cr(AA)(C2O4)2]- Tectons, and Sustained by Coordinative, Hydrogen Bond and π−π Stacking Interactions (AA = 2,2‘-Bipyridine; 1,10-Phenanthroline)

The paper reports on four novel solid-state architectures constructed by using tectons having the general formula:  [Cr(AA)(C2O4)2]- [AA = 2,2‘-bipyridine (bipy) and 1,10-phenanthroline (phen)]. These building blocks are involved in various intermolecular interactions:  coordinative, hydrogen bonds, and π−π contacts. Two new crystallohydrates in the Ba[Cr(AA)(C2O4)2]2·nH2O family have been characterized:  [BaCr2(bipy)2(C2O4)4(H2O)2]·4H2O (1) and [BaCr2(phen)2(C2O4)4(H2O)2] (2). Because of the different numbers of water molecules, their crystal structures are completely different from those of two others previously reported, [BaCr2(bipy)2(C2O4)4(H2O)]·H2O and [BaCr2(phen)2(C2O4)4(H2O)2]·4H2O…

Reversible Solvatomagnetic Switching in a Spongelike Manganese(II)-Copper(II) 3D Open Framework with a Pillared Square/Octagonal Layer Architecture

The concept of "molecular magnetic sponges" was introduced for the first time in 1999 by the creative imagination of the late Olivier Kahn. It refers to the exotic spongelike behavior of certain molecule-based materials that undergo a dramatic change of their magnetic properties upon reversible dehydration/rehydration processes. Here we report a unique example of a manganese(II)-copper(II) mixed-metal-organic framework of formula [Na(H(2)O)(4)](4)[Mn(4){Cu(2)(mpba)(2)(H(2)O)(4)}(3)]·56.5H(2)O (1) (mpba=N,N'-1,3-phenylenebis(oxamate)). Compound 1 possesses a 3D Mn(II)(4)Cu(II)(6) pillared layer structure with mixed square and octagonal pores of approximate dimensions 1.2×1.2 nm and 2.1×3.0 n…

Syntheses, crystal structures and magnetic properties of tricyanomethanide-containing bis(2-pyrimidylcarbonyl)amidate copper(II) complexes

Abstract Three new copper(II) complexes of formulae [Cu(bpcam)(tcm)(H2O)] · 2H2O (1), [Cu(bpcam)(tcm)(H2O)] (2) and [Cu(bpcam)(tcm)]n (3) [bpcam = bis(2-pyrimidylcarbonyl)amidate and tcm = tricyanomethanide] have been prepared and their structures determined by single crystal X-ray diffraction. Complexes 1 and 2 are mononuclear species where each copper atom is five-coordinated in a somewhat distorted square pyramidal environment with a tridentate bpcam ligand and a terminally bound tcm group building the basal plane and a water molecule in the apical position. Compound 3 is a uniform copper(II) chain where the [Cu(bpcam)]+ units are connected through single μ-1,5-tcm bridges which link one…

From Paramagnetic to Single‐Molecule Magnet Behaviour in Heterobimetallic Compounds Containing the Tetrakis(thiocyanato‐ κN )cobaltate(II) Anion

Syntheses, crystal structures and magnetic properties of copper(II) polynuclear and dinuclear compounds with 2,3-bis(2-pyridyl)pyrazine (dpp) and pseudohalide as ligands

Abstract The preparation, crystal structures and magnetic properties of four heteroleptic copper(II) complexes with 2,3-bis(2-pyridyl)pyrazine (dpp) and azide, cyanate or thiocyanate as ligands are reported, [Cu(dpp)(N3)2]n (1), [Cu(dpp)(NCO)2]n (2), [Cu(dpp)(NCS)2]2 (3) and [Cu(H2O)(dpp)(NCS)2]2·2H2O (4). Compounds 1 and 2 are isomorphous, triclinic, space group P1, and consist of mononuclear building blocks featuring copper atoms with close to square planar coordination geometries. The mononuclear units are, however, associated into chains through weak axial Cu–N bonds formed by end-on asymmetrically bridging azido/cyanato groups and by pyridyl nitrogen atoms. Taking these contacts into a…

Single chain magnet behaviour in an enantiopure chiral cobalt(II)–copper(II) one-dimensional compound

The self-assembly of an enantiomerically pure, chiral dianionic oxamatocopper(II) complex with cobalt(II) ions leads to neutral oxamato-bridged heterobimetallic chains that combine chirality and slow magnetic relaxation, providing thus the first example of ‘‘chiral single chain magnets (CSCMs). Ruiz Garcia, Rafael, Rafael.Ruiz@uv.es ; Lloret Pastor, Francisco, Francisco.Lloret@uv.es

Pyrophosphate-mediated magnetic interactions in Cu(II) coordination complexes.

The reaction in water of Cu(NO(3))(2)·2.5H(2)O with 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), or 1,10-phenanthroline-5-amine (phenam), and sodium pyrophosphate (Na(4)P(2)O(7)), at various pHs, afforded three new copper(II)-pyrophosphate complexes, namely, {[Cu(bipy)(cis-H(2)P(2)O(7))](2)}·3H(2)O (1a), {[Cu(phen)(H(2)O)](4)(HP(2)O(7))(2)}(ClO(4))(2)·4H(2)O (2), and {[Cu(2)(phenam)(2)(P(2)O(7))](2)·25H(2)O}(n) (3). A solvent free crystalline phase of 1a was also isolated with formula {[Cu(bipy)(trans-H(2)P(2)O(7))](2)} (1b), which can be regarded as a pseudo-polymorph of 1a. Single crystal X-ray analyses revealed these compounds to have uncommon molecular architectures, with 3 being…

A self-assembled tetrameric water cluster stabilized by the hexachlororhenate(IV) anion and diprotonated 2,2′-biimidazole: X-ray structure and magnetic properties

A self-assembled tetrameric water cluster stabilized by [ReCl6]2− anions and [H4biim]2+ cations occurs in the new compound [H4biim][ReCl6]·4H2O, which exhibits a weak ferromagnetic coupling between the Re(IV) centers through an unusual ReIV–Cl⋯(H2O)⋯Cl–ReIV pathway.

Mixed Valence Materials: Prussian Blue Analogues of Reduced Dimensionality (Small 16/2012)

Molecular-Programmed Self-Assembly of Homo- and Heterometallic Tetranuclear Coordination Compounds: Synthesis, Crystal Structures, and Magnetic Properties of Rack-Type CuII2MII2 Complexes (M = Cu and Ni) with Tetranucleating Phenylenedioxamato Bridging Ligands

New homo- and heterobimetallic tetranuclear complexes of formula [Cu4(mpba)(Me4en)4(H2O)4](ClO4)4·3H2O (1), [Cu4(mpba)(Me4en)4(H2O)4](PF6)4·2H2O (2), [Cu4(ppba)(Me4en)4(H2O)4](ClO4)4·2H2O (3), [Cu4(mpba)(dipn)4](ClO4)4·3H2O (4), [Cu4(ppba)(dipn)4](ClO4)4·2H2O (5), and [Cu2Ni2(ppba)(dipn)4(H2O)2](PF6)4 (6) [mpba = N,N′-1,3-phenylenebis(oxamate), ppba = N,N′-1,4-phenylenebis(oxamate), Me4en = N,N,N′,N′-tetramethylethylenediamine, and dipn = dipropylenetriamine] have been synthesized and structurally and magnetically characterized. Complexes 1−6 have been prepared following a molecular-programmed self-assembly method, where a heteropolytopic tetranucleating phenylenedioxamato bridging ligand (…

Trans-dicyanobis(acetylacetonato)ruthenate(III) as a precursor to build novel cyanide-bridged RuIII–MII bimetallic compounds [M=Co and Ni]

Abstract The use of the mononuclear complex trans-[Ru(acac)2(CN)2]− as a ligand towards the preformed species [Ni2L(H2O)2Cl2], [Co(dmphen)](NO3)2, [Ni(dmphen)](NO3)2 and [Co(H2O)6](NO3)2 afforded the novel cyanide-bridged bimetallic compounds of formula [{Ru(acac)2(CN)2}{Ni2(L)(H2O)2}]{Ru(acac)2(CN)2}·2H2O (1), [{Ru(acac)2(CN)2}{Co(dmphen)(NO3)}]·H2O (2) and [{Ru(acac)2(CN)2}{Ni(dmphen)(NO3)}]·H2O (3) and [{Ru(acac)2(CN)2}2Co] (4) [Hacac = acetylacetone, dmphen = 2,9-dimethylphenanthroline and H2L = 11,23-dimethyl-3,7,15,19-tetrazatricyclo[19.3.1.19,13]hexacosa-2,7,9,11,13(26),14,19,21(25),22,24-decaene-25,26-diol]. Their syntheses, X-ray crystal structures and magnetic properties are repor…

Magnetic behavior control in niccolite structural metal formate frameworks [NH2(CH3)2][Fe(III)M(II)(HCOO)6] (M = Fe, Mn, and Co) by varying the divalent metal ions.

By changing template cation but introducing trivalent iron ions in the known niccolite structural metal formate frameworks, three complexes formulated [NH(2)(CH(3))(2)][Fe(III)M(II)(HCOO)(6)] (M = Fe for 1, Mn for 2, and Co for 3) were synthesized and magnetically characterized. The variation in the compositions of the complexes leads to three different complexes: mixed-valent complex 1, heterometallic but with the same spin state complex 2, and heterometallic heterospin complex 3. The magnetic behaviors are closely related to the divalent metal ions used. Complex 1 exhibits negative magnetization assigned as Neel N-Type ferrimagnet, with an asymmetric magnetization reversal in the hysteres…

Rational enantioselective design of chiral heterobimetallic single-chain magnets: synthesis, crystal structures and magnetic properties of oxamato-bridged M(II)Cu(II) chains (M=Mn, Co).

A new series of neutral oxamato-bridged M(II)Cu(II) chiral chains of general formula [MCuL(x)(S)(m)(H(2)O)(n)]·aS·bH(2)O [L(1)=(M)-1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (1a) and Co (1b); L(2)=(P)-1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (2a) and Co (2b)] and the analogous racemic chains of formula [MCuL(3)(S)(m)(H(2)O)(n)]·aS·bH(2)O [L(3)=1,1'-binaphthalene-2,2'-bis(oxamate) with M=Mn (3a) and Co (3b)] have been prepared by reaction of the corresponding dianionic oxamatocopper(II) complex [Cu(L(x))](2-) with Mn(2+) or Co(2+) cations in either dimethylformamide (DMF) or dimethyl sulfoxide (DMSO). Solid circular dichroism (CD) spectra of the bimetallic chain compounds were reco…

Ferromagnetic coupling through a carbonate bridge in the copper (II) chain [Cu(CO3)(4-apy)2] · H2O (4-apy = 4-aminopyridine)

Abstract Atmospheric CO2 fixation by aqueous solutions containing copper(II) bromide and 4-aminopyridine (4-apy) yields the first carbonatobridged copper(II) chain of formula [Cu(CO3)(4-apy)2] · H2O that exhibits an intrachain ferromagnetic coupling.

Novel Three-Dimensional Cage Assembly of amgr;(4)-Carbonato-Bridged Cobalt(II) Compound [Co(2)(bpm)(H(2)O)(2)(CO(3))(OH)]NO(3).4H(2)O.

The new three-dimensional cobalt(II) complex of formula [Co2(bpm)(H2O)2(CO3)(OH)]NO3·4H2O (1) is obtained from aqueous solutions containing cobalt(II) nitrate hexahydrate, 2,2‘-bipyrimidine (bpm), ...

Synthesis, crystal structure and magnetic properties of the first structurally characterized 1,2-dithiocroconato-containing Cu(II) complex, [Cu(bpca)(H2O)]2[Cu(1,2-dtcr)2]·2H2O

Abstract The first crystal and molecular structure of a transition metal complex containing 1,2-dithiocroconate (1,2-dtcr, dianion of 1,2-dimercaptocylopent-1-ene-3,4,5-trione), [Cu(bpca)(H2O)]2[Cu(1,2-dtcr)2]·2H2O (where bpca is the bis(2-pyrdidylcarbonyl)amide anion), has been determined by single crystal X-ray diffraction methods. The compound crystallizesin the monoclinic syste, space group P21/c, with a = 11.661(3), b = 20.255(6), c = 8.265(3) A , s = 107.26(2)° and Z = 2. The structure is formally built of [Cu(1,2-dtcr)2]2− and [Cu(bpca)(H2O)]+ ions and water of hydration. The copper atom of the anion is situated at a crystallographic inversion centre, bonded to four sulfur atoms in a…

The influence of pseudohalide ligands on the SIM behaviour of four-coordinate benzylimidazole-containing cobalt(ii) complexes.

Three, mononuclear complexes of the formula [Co(bmim)2(SCN)2] (1), [Co(bmim)2(NCO)2] (2) and [Co(bmim)2(N3)2] (3) [bmim = 1-benzyl-2-methylimidazole] were prepared and structurally analyzed by single-crystal X-ray crystallography. The cobalt(ii) ions in 1-3 are tetrahedrally coordinated with two bmim molecules and two pseudohalide anions. The angular distortion parameter δ was calculated and the SHAPE program (based on the CShM concept) was used for 1-3 to estimate the angular distortion from an ideal tetrahedron. The molecules of 1-3 are effectively separated, and the values of the shortest distance of cobalt-cobalt are 8.442(6) and 6.774(8) A for 1, 10.349(8) and 10.716(8) A for 2 and 6.7…

Synthesis, Structure, and Magnetic Properties of Regular Alternating μ-bpm/di-μ-X Copper(II) Chains (bpm = 2,2′-bipyrimidine; X = OH, F)

The preparation and X-ray crystal structure of four 2,2'-bipyrimidine (bpm)-containing copper(II) complexes of formula {[Cu(2)(μ-bpm)(H(2)O)(4)(μ-OH)(2)][Mn(H(2)O)(6)](SO(4))(2)}(n) (1), {[Cu(2)(μ-bpm)(H(2)O)(4)(μ-OH)(2)]SiF(6)}(n) (2), {Cu(2)(μ-bpm)(H(2)O)(2)(μ-F)(2)F(2)}(n) (3), and [Cu(bpm)(H(2)O)(2)F(NO(3))][Cu(bpm)(H(2)O)(3)F]NO(3)·2H(2)O (4) are reported. The structures of 1-3 consist of chains of copper(II) ions with regular alternation of bis-bidentate bpm and di-μ-hydroxo (1 and 2) or di-μ-fluoro (3) groups, the electroneutrality being achieved by either hexaaqua manganese(II) cations plus uncoordinated sulfate anions (1), uncoordinated hexafluorosilicate anions (2), or terminally …

Crystal Structure and Magnetic Properties of 3,5-Pyridinedicarboxylate-Bridged Re(Ii)M(Ii) Heterodinuclear Complexes (M = Cu, Ni and Co)

Abstract The use of the mononuclear rhenium(II) precursor NBu4[Re(NO)Br4(H2pydc)]·i-PrOH (1) (H2pydc = 3,5-pyridinedicarboxylic acid) as a metalloligand towards Cu(II), Ni(II) and Co(II) afforded three new heterobimetallic complexes [Re(NO)Br4(μ-Hpydc)Cu(4,4′-dmbipy)2]·(CH3)2CO·0.25MeCN (2), [Re(NO)Br4(μ-Hpydc)Ni(dmphen)2]·MeCN (3) and [Re(NO)Br4(μ-Hpydc)Co(dmphen)2]·2H2O (4), respectively [4,4′-dmbipy = 4,4′-dimethyl-2,2′-bipyridine, dmphen = 2,9-dimethyl-1,10-phenanthroline and Bu4N+ = tetra-n-butylammonium]. The crystal structures of 1 and 2 are reported herein together with the cryomagnetic investigation of 1–4 in the temperature range of 2.0–300 K. 1 is a mononuclear compound whose str…

Ferromagnetic coupling and magnetic anisotropy in oxalato-bridged trinuclear chromium(iii)-cobalt(ii) complexes with aromatic diimine ligands

Two novel heterotrinuclear chromium(III)-cobalt(II) complexes of formula {[Cr(III)(bpy)(ox)(2)](2)Co(II)(Me(2)bpy)}.2H(2)O (1) and {[Cr(III)(phen)(ox)(2)](2)Co(II)(Me(2)bpy)}.1.5H(2)O (2) [ox = oxalato, bpy = 2,2'-bipyridine, Me(2)bpy = 6,6'-dimethyl-2,2'-bipyridine, and phen = 1,10-phenanthroline] have been synthesized using the "complex-as-ligand/complex-as-metal" strategy. The X-ray crystal structure of 2 consists of neutral oxalato-bridged Cr(III)(2)Co(II) bent entities formed by the coordination of two anionic [Cr(III)(phen)(ox)(2)](-) complexes through one of their oxalato groups toward a cationic cis-[Co(II)(Me(2)bpy)](2+) complex. The three tris(chelated), six-coordinated metal atom…

Metallosupramolecular compounds based on Cu(ii)/oxalate/twisted NSSN ligands showing a new in situ S–C bond cleavage

Four new complexes, [Cu2(C2O4) 2(SCS)]·3H2O (1), [Cu2(C 2O4)3(SCSH)2]·H2O (2), [Cu(C2O4)(SS)2]·3H2O (3) and [Cu(C2O4)(SS)]·6H2O (4) [where SCS = bis(4-pyridylthio)methane and SS = 4,4′-dipyridyldisulfide], have been synthesized by the reaction of the SS and SCS ligands with the corresponding copper(ii) oxalate salt. The different synthetic conditions allowed control of the preparation of a 3D open metal-organic framework in 1, a dinuclear zwitterionic molecular compound in 2 and one- and two-dimensional (1D and 2D) coordination polymers in 3 and 4, respectively. Compound 4 was also obtained by in situ transformation of the dithioether ligand (SCS) to the disulfide ligand (SS) under hydrothe…

A study of the exchange interaction through phenolato, oximato and oxamidato bridges in MnIICuII dimers. Crystal structure of [Cu(salen)Mn(hfa)2]

Abstract Three new heterodinuclear CuIIMnII complexes of formula [Cu(salen)Mn(hfa)2] (1), [Cu(pdmg)Mn(phen)2](ClO4)2·2.5H2O (2) and [Cu(apox)Mn(bpy)2](ClO4]2·0.5H2O (3) (salen=N,N′-ethylenebis(salicylideneiminate), hfa=hexafluoroacetylacetonate, pdmg=3,9-dimethyl-4,8-diazaundeca-3,8-diene-2,10-dione dioximate, phen=1,10- phenanthroline, apox=N,N′-bis(3-aminopropyl)oxamidate and bipy=2,2′-bipyridyl) have been synthesized. The crystal and molecular structure of 1 has been determined by X-ray diffraction methods. It crystallizes in the triclinic system, space group P 1 with cell constants a=15.584(4), b=12.039(3), c=9.470(2) A, α=113.83(2), β=107.17(3), γ=84.28(3)°; V=1552(1) A3, D (calc., Z=2…

2,3,5,6-Tetrakis(2-pyridyl)pyrazine (tppz)-containing iron(II) complexes: Syntheses and crystal structures

Abstract The preparation and crystal structure of two iron(II) complexes of formula PPh4-mer-[Fe(tppz)(CN)3] · 7H2O (1) and [Fe(tppz)2][Fe(NCS)4] (2) [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine; PPh 4 + = tetraphenylphosphonium cation ] are reported here. The structure of 1 consists of mononuclear mer-tricyano[2,3,5,6-tetrakis(2-pyridyl)pyrazine]ferrate(II) anions, tetraphenylphosphonium cations and crystallization water molecules. Three carbon atoms from three cyanide groups in a mer arrangement and three nitrogen atoms from a tridentate tppz ligand build a somewhat distorted octahedral surrounding around the iron atom in 1. The values of the Fe–C [1.925(6)–1.947(5) A] and Fe–N [1.870(4)–1…

A two-dimensional coordination polymer constructed from binuclear copper(II) metalloligands and manganese(II) ions: Synthesis, crystal structure and magnetic properties

Abstract The self-assembly process between the binuclear [Cu2(HL)(L)]− complex and the manganese(II) ion affords a two-dimensional coordination polymer of formula [Mn{Cu2(HL)(L)}2(H2O)2]n (1) (H3L = 3-hydroxyiminomethylsalicylic acid) where parallel ladder-like motifs of defective double cubanes of bis(phenoxo)dicopper(II) units as rods and anti-syn carboxylato bridges as rungs act as ligands towards tetraaqua-manganese(II) entities through the deprotonated oxime groups. The topology of 1 is compared with the one of another compound, [Mn{Cu2(HL)(L)}2(H2O)4]·4H2O·2DMF (1′) which was obtained in different conditions by Okawa et al. (J. Chem. Soc., Dalton Trans. (2001) 3119). Magnetic suscepti…

Topological control of the spin coupling in dinuclear copper(II) complexes with meta- and para-phenylenediamine bridging ligands

Abstract A novel series of copper(II) complexes of formula [Cu(tren)(mpda)](ClO4)2 · 1/2H2O (1), [Cu2(tren)2(mpda)](ClO4)4 · 2H2O (2), and [Cu2(tren)2(ppda)](ClO4)4 · 2H2O (3) containing the tetradentate tris(2-aminoethyl)amine (tren) terminal ligand and the potentially bridging 1,n-phenylenediamine [n = 3 (mpda) and 4 (ppda)] ligand have been prepared and spectroscopically characterized. X-ray diffraction on single crystals of 1 and 3 show the presence of mono- (1) and dinuclear (3) copper(II) units where the mpda (1) and ppda (3) ligands adopt terminal monodentate (1) and bridging bis(monodentate) (3) coordination modes toward [Cu(tren)]2+ cations with an overall non-planar, orthogonal di…

Self-assembly, metal binding ability, and magnetic properties of dinickel(II) and dicobalt(II) triple mesocates

Two metallacyclic complexes of general formula Na-8[(M2L3)-L-II]center dot xH(2)O [M = Ni (4) and Co (5) with x = 15 (4) and 17 (5)] have been self-assembled in aqueous solution from N,N'-1,3-phenylenebis(oxamic acid) (H4L) and M2+ ions in a ligand/metal molar ratio of 3 : 2 in the presence of NaOH acting as base. X-Ray structural analyses of 4 and 5 show triple-stranded, dinuclear anions of the meso-helicate-type (so-called mesocates) with C-3h molecular symmetry. The two octahedral metal-tris(oxamate) moieties of opposite chiralities (Delta, Lambda form) are connected by three m-phenylene spacers at intermetallic distances of 6.822(2) (4) and 6.868(2) angstrom (5) to give a metallacryptan…

Synthesis, crystal structures and magnetic properties of tricyanomethanide-containing copper(II) complexes

The preparation, crystal structures and magnetic properties of the copper(II) complexes of formula [Cu(pyim)(tcm)(2)](n) (1), [Cu(bpy)(tcm)(2)](n) (2), [Cu(4)(bpz)(4)(tcm)(8)] (3), {[Cu(terpy)(tcm)].tcm}(n) (4) and {[Cu(2)(tppz)(tcm)(4)].3/2H(2)O}(n) (5) [pyim = 2-(2-pyridyl)imidazole, tcm = tricyanomethanide, bpy = 2,2'-bipyridine, bpz = 2,2'-bipyrazine, terpy = 2,2':6',2''-terpyridine and tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine] are reported. Complexes, 1, 2 and 4 are uniform copper(II) chains with single- (1 and 4) and double-(2) micro-1,5-tcm bridges with values of the intrachain copper-copper separation of 7.489(1) (1), 7.520(1) and 7.758(1) (2) and 7.469(1) A (4). Each copper atom …

Very Long-Distance Magnetic Coupling in a Dicopper(II) Metallacyclophane with Extended π-Conjugated Diphenylethyne Bridges

Self-assembly of the rigid rodlike ligand N,N'-4,4'-diphenylethynebis(oxamate) (dpeba) and Cu(2+) ions affords a novel dinuclear copper(II) metallacyclophane (nBu(4)N)(4)[Cu(2)(dpeba)(2)]·4MeOH·2Et(2)O (1) featuring a very long intermetallic distance (r = 15.0 Å). Magnetic susceptibility measurements for 1 reveal a moderately weak but nonnegligible intramolecular antiferromagnetic coupling between the two metal centers across the double para-substituted diphenylethynediamidate bridge (J = -3.9 cm(-1); H = -JS(1)S(2), where S(1) = S(2) = S(Cu) = (1)/(2)). Density functional electronic structure calculations on 1 support the occurrence of a spin polarization mechanism.

Synthesis, crystal structure and magnetic properties of the Re(II) complexes NBu4[Re(NO)Br4(L)] (L = pyridine and diazine type ligands).

Four novel Re(II) complexes of formula NBu4[Re(NO)Br4(L)] [NBu4(+) = tetra-n-butylammonium cation and L = pyridine (1), pyrazine (2), pyrimidine (3), pyridazine (4)] have been prepared by a substitution reaction involving NBu4[Re(NO)Br4(EtOH)] and L. Their crystal structures have been determined by single crystal X-ray diffraction. They are all mononuclear complexes whose structure is made up of [Re(NO)Br4L](-) anions and NBu4(+) cations. Each Re(II) ion is six-coordinate with four bromide ligands, a linear nitrosyl group and one monodentate nitrogen donor L building a tetragonally distorted octahedral surrounding. The Re-Br bond distances cover a narrow range [2.5048(8)-2.5333(5) Å] and th…

Synthesis, crystal structure and magnetic properties of [Co(bpcam)2]ClO4·dmso·H2O, [Co(bpcam)2]2[Co(NCS)4]·dmso·H2O and [Ni(bpcam)2]·H2O [Hbpcam = bis(2-pyrimidylcarbonyl)amide]

The preparation, spectroscopic characterization, structural study and magnetic investigation of three new complexes of formula [Co(bpcam)2]ClO4·dmso·H2O (1), [Co(bpcam)2]2[Co(NCS)4]·dmso·H2O (2) and [Ni(bpcam)2]·H2O (3) [Hbpcam = bis(2-pyrimidylcarbonyl)amide] are reported. Each bpcam group in 1–3 acts as a tridentate ligand being coordinated to the cobalt(III) (1 and 2)/nickel(II) (3) ions through three nitrogen atoms in a mer-arrangement. Six-coordinate cobalt(III) and nickel(II) occur in 1 and 3 respectively, whereas six-coordinate cobalt(III) and four-coordinate cobalt(II) coexist in 2. Cyclic voltammetry of 1 in acetonitrile shows the occurrence of one quasi reversible CoIII ↔ CoII pro…

Coexistence of ferro- and antiferromagnetic interactions in a metal-organic radical-based (6,3)-helical network with large channels.

A metal–organic open-framework with an unprecedented (6,3)-helical topology, large channels and mixed ferro- and antiferromagnetic interactions has been synthesized using a three-connecting tricarboxylic polychlorotriphenylmethyl radical and Co(II) ions. Lloret Pastor, Francisco, Francisco.Lloret@uv.es

Synthesis, crystal structure, electrochemical and magnetic properties of (NBu4)[ReCl5(L)] with L=pyrimidine and pyridazine

Abstract Two novel rhenium(IV) compounds, namely (NBu4)[ReCl5(pym)] (1) and (NBu4)[ReCl5(pyd)] (2) (pym = pyrimidine, pyd = pyridazine and NBu4 = n-tetrabutylammonium cation), have been obtained by reaction of [ReCl6]2− and the diazine in dmf, and their crystal structures determined by single-crystal X-ray diffraction. The structures of 1 and 2 consist of [ReCl5(pym)]− or [ReCl5(pyd)]− anions and NBu 4 + cations held together by electrostatic forces and van der Waals interactions. Stacking interactions are present only in 1. The coordination sphere of the ReIV ion is defined by five chloride anions and one nitrogen atom of a monodentate diazine, resulting in a distorted octahedral environme…

Dinuclear and two- and three-dimensional gadolinium(III) complexes with mono- and dicarboxylate ligands: synthesis, structure and magnetic properties

Three new gadolinium(III) complexes with carboxylate ligands of formula [Gd2(ac)6(H2O)4]·2H2O (1), [Gd2(ac)2(fum)2(H2O)4]n (2) and [Gd2(ox)(fum)2(H2O)4]n·4nH2O (3) (ac = acetate, fum = fumarate and ox = oxalate) have been prepared and their structures determined by X-ray diffraction on single crystals. The structure of 1 is made up of discrete centrosymmetric di-µ-oxo(carboxylate acetate)digadolinium(III) units with an intramolecular Gd⋯Gd separation of 4.1589(3) A. Each gadolinium atom in 1 is nine-coordinated with two water molecules and seven carboxylate-oxygen atoms from four acetate ligands building a monocapped square antiprism environment. Compound 2 exhibits a sheet-like structure, …

Synthesis, crystal structure and magnetic properties of the dinuclear manganese(II) complexes [Mn2(bpym)3(NCX)4] (bpym = 2,2′-bipyrimidine; X = S, Se)

Abstract The dinuclear manganese(II) compounds of formula [Mn2(bpym)3(NCX)4], where bpym = 2,2′-bipyrimidine and X = S(1) and Se(2), have been prepared and their crystal structures determined by X-ray diffraction methods. 1 and 2 are isostructural. They crystallize in the triclinic P 1 space group with Z = 1, γ ( Mo K α ) = 0.71073 A , T = 295 K and a = 9.141(2), b = 9.248(2), c = 11.733(2) A , α = 74.88(2), β = 80.29(2), γ = 61.03(2)°, V = 836.7(3) A 3 , D c = 1.621 g cm −3 , M r = 316.7, F(000) = 412, and μ( Mo K α) = 10.54 cm −1 for 1 and a = 9.244(2), b = 9.278(2) A , c = 11.887(2) A , α = 75.19(2), β = 80.83(2), γ = 61.54(2)°, V = 865.7(3) A 3 , D c = 1.926 g cm −3 , M r = 1004.3, F(00…

A Mixed-Valence Mixed-Spin Prussian-Blue-Like Heptanuclear Complex

Highly Anisotropic Rhenium(IV) Complexes: New Examples of Mononuclear Single-Molecule Magnets

The rhenium(IV) complex (NBu4)2[ReBr4(ox)] (1) (ox = oxalate and NBu4(+) = tetra-n-butylammonium cation) has been prepared and its crystal structure determined by X-ray diffraction. The structure is made up of discrete [ReBr4(ox)](2-) anions and bulky NBu4(+) cations. Each [ReBr4(ox)](2-) anion is surrounded by six NBu4(+) cations, which preclude any significant intermolecular contact between the anionic entities, the shortest rhenium···rhenium distance being 9.373(1) Å. Variable temperature dc and ac magnetic susceptibility measurements and field-dependent magnetization experiments on polycrystalline samples of 1 reveal the occurrence of highly anisotropic magnetically isolated Re(IV) cent…

Synthesis, characterization and magnetic properties of mixed-valence iron complexes with 2-pyridyl oximes

Two new mixed-valence iron complexes with 2-pyridyl oximes, [Fe(mpko)3Fe(H2O)2(NO3)](NO3)·2H2O (1) (mpko− = methyl(2-pyridyl)ketone oximate) and [{Fe(dpko)3}2Fe](ClO4)·4H2O (2) (dpko− = bis(2-pyridyl)ketone oximate), have been prepared by reaction of FeIII with mpkoH in methanol (1) and FeII with dpkoH in methanol/water (2). Dinuclear FeII(low-spin)FeIII(high-spin) and trinuclear FeII(low-spin)FeIII(high-spin)FeII(low-spin) cations are present in the crystal structure of 1 and 2, respectively. Intermolecular hydrogen bonds in 1 lead to weak antiferromagnetic interactions between pairs of neighboring FeIII centers, which allows observation of single-ion zero-field splitting effects.

4,2-Ribbon like ferromagnetic cyano-bridged FeIII2NiII chains: a magneto-structural study

The low-spin iron(III) complex AsPh(4)[Fe(III)(bpy)(CN)(4)].CH(3)CN (1) [AsPh(4) = tetraphenylarsonium cation] and the heterobimetallic chains [{Fe(III)(L)(CN)(4)}(2)Ni(II)(H(2)O)(2)].4H(2)O with L = bpy (2) and phen (3) [bpy = 2,2'-bipyridine and phen = 1,10-phenanthroline] have been prepared and their structures determined by X-ray diffraction methods. The structure of 1 consists of mononuclear [Fe(bpy)(CN)(4)](-) anions, tetraphenylarsonium cations and acetonitrile molecules of crystallization. The iron(III) is hexacoordinated with two nitrogen atoms of the bidentate bpy and four carbon atoms of four terminal cyanide groups building a distorted octahedral surrounding around the metal ato…

A methylenediphosphonate bridged copper(II) tetramer: Synthesis, structural, thermal, and magnetic characterization of [Cu4(H2O)2(phen)4(μ-P2O6CH2)2]·21H2O

Abstract A novel tetracopper(II) complex namely, [Cu4(H2O)2(phen)4(μ-P2O6CH2)2]·21H2O (1) was synthesized by using copper(II) chloride, 1,10-phenanthroline (phen), and methylene diphosphonic acid (MDP). The structure of 1 was characterized by single crystal X-ray diffraction and spectroscopy. Compound 1 crystallizes in the triclinic system, P 1 ¯ space group and its crystal structure consists of neutral centrosymmetric tetranuclear copper(II)-methylene diphosphonate units where each peripheral {Cu(phen)(P2O6CH2)}2− fragment adopts the bidentate(Oeq-P-Oeq)/monodentate (Oax) bridging mode towards each of the two inner {Cu(phen)}2+ entities resulting in a “clamshell”-like orientation. The two …

Crystal Structure and Magnetic Properties of an Oxamato‐Bridged Heterobimetallic Tetranuclear [Ni II Cu II ] 2 Complex of the Rack Type

Exchange coupling in a thiocyanato-bridged copper(II) chain: Computational approach to magnetostructural correlations

Abstract In this article we report the synthesis and magneto-structural characterization of two new copper(II) compounds with thiocyanato and methyl(2-pyridil) ketone oxime (mpkOH), namely [Cu(NCS)(mpkO)(mpkOH)] (1) and [Cu(µ-NCS)(NCS)(mpkOH)]n (2). Compound 1 is a mononuclear complex that crystallizes as discrete units. Conversely, compound 2 is a single equatorial-axial end-to-end thiocyanato bridged polymeric chain of Cu(II) with the oxime as a co-ligand. The coordination geometry around the Cu(II) centers is distorted square pyramidal for 1 and 2. The magnetic susceptibility data for 2 reveal weak intrachain antiferromagnetic coupling, with J value −0.74(3) cm−1 and g  = 2.10(1). The ap…

Nickel(II) Complex of a Hexadentate Ligand with Two o-Iminosemiquinonato(1-) π-Radical Units and Its Monocation and Dication.

Aerobic reaction of a hexadentate redox-active o-aminophenol-based ligand, H4L(3) = N,N'-bis(2-hydroxy-3,5-di-tert-butylphenyl)-2,2'-diamino(diphenyldithio)-ethane, in CH3OH with Ni(II)(O2CCH3)2·4H2O and Et3N afforded isolation of a reddish-brown crystalline solid [Ni(L(3))] 1. Cyclic voltammetry (CV) experiment exhibits two oxidative responses at E1/2 = 0.09 and 0.53 V vs SCE (saturated calomel electrode). Chemical oxidation of 1 in air by [Fe(III)(η(5)-C5H5)2][PF6] and AgBF4 in CH2Cl2 led to the isolation of one-electron oxidized species [1](1+) as purple [1][PF6]·CH2Cl2 and two-electron oxidized species [1](2+) as dark purple [1][BF4]2·CH2Cl2, respectively. X-ray crystallographic analysi…

Magnetic properties of six-coordinated high-spin cobalt(II) complexes: Theoretical background and its application

Abstract In this contribution we study and analyse the influence of the different parameters involved in the magnetic susceptibility of six-coordinated high-spin Co(II) complexes. We propose an empirical expression to fit the magnetic susceptibility of polycrystalline samples of mononuclear Co(II) complexes with an axial distortion, the variable parameters being Δ (axial distortion), α (orbital reduction factor) and λ (spin–orbit coupling). This expression avoids solving the 12 × 12 matrix associated to the distortion of the 4 T 1g term. In order to take into account the magnetic coupling ( J ) in the polynuclear Co(II) complexes, a perturbational approach is proposed to describe their magn…

Solid-State Aggregation of Metallacyclophane-Based MnIICuII One-Dimensional Ladders

Two distinct one-dimensional (1) and two-dimensional (2) mixed-metal-organic polymers have been synthesized by using the "complex-as-ligand" strategy. The structure of 1 consists of isolated ladderlike Mn(II)(2)Cu(II)(2) chains separated from each other by neutral Mn(II)(2) dimers, whereas 2 possesses an overall corrugated layer structure built from additional coordinative interactions between adjacent Mn(II)(2)Cu(II)(2) ladders. Interestingly, 1 and 2 show overall ferri- and antiferromagnetic behavior, respectively, as a result of their distinct crystalline aggregation in the solid state.

Synthesis, structural, thermal, and magnetic investigations of Co(II), Ni(II), and Mn(II) pyrophosphate chains

The reaction in water of cobalt(II), nickel(II) or manganese(II) chloride with 1,10-phenanthroline (phen) and sodium pyrophosphate (Na 4 P 2 O 7 ) at low pH (∼2) afforded three isostructural pyrophosphate complexes of an unprecedented one-dimensional typology, namely, {[M(phen)(H 2 O)(H 2 P 2 O 7 )]·H 2 O} n with M = Co( 1 ), Ni( 2 ) and Mn( 3 ). The di-hydrogen-pyrophosphate anion featured in these complexes adopts a rare bidentate/monodentate bridging mode leading to chain propagation. This unusual bridging pathway produces a metal–metal intra-chain separation of about 6.6–6.7 A for 1 – 3 , values much larger than the metal–metal distance across the classic bis-bidentate PPi in the parent…

A Metalloligand Approach for the Self-Assembly of a Magnetic Two-Dimensional Grid-of-Grids

The efficient organization of discrete functional molecules into extended frameworks, while retaining their physical properties, is a mandatory requisite to move toward applications. Here we descri...

Synthesis, crystal structure, and magnetic characterization of the three-dimensional compound [Co2(cbut)(H2O) 3]n (H4cbut = 1,2,3,4- cyclobutanetetracarboxylic acid)

A novel cobalt(II) complex of formula [Co2(cbut)(H 2O)3]n (1) (H4cbut = 1,2,3,4-cyclobutanetetracarboxylic acid) has been synthesized under hydrothermal conditions and its crystal structure has been determined by means of synchrotron radiation and neutron powder diffraction. The crystal structure of 1 consists of layers of cobalt(II) ions extending in the bc-plane which are pillared along the crystallographic a-axis through the skeleton of the cbut 4- ligand. Three crystallographically independent cobalt(II) ions [Co(1), Co(2), and Co(3)] occur in 1. They are all six-coordinate with four carboxylate-oxygens [Co(1)-Co(3)] and two cis-[Co(1)] or trans-water molecules [Co(2) and Co(3)] buildin…

Crystal structure and magnetic properties of the single-μ-chloro copper(II) chain [Cu(bipy)Cl2] (bipy = 2,2′-bipyridine)

Abstract The crystal and molecular structure of the copper(II) chain [Cu(bipy)Cl2] (1) (bipy = 2,2′-bipyridine) has been determined by X-ray diffraction methods. The crystal structure of 1 consists of neutral single chloro-bridged copper(II) chains with alternating short and long Cu–Cl distances through a screw axis parallel to a. The copper surrounding is best described as distorted square pyramidal, the equatorial plane being built by the two nitrogen atoms of the chelating bipy and two chlorine atoms (one terminal and the other bridging), whereas the apical position is filled by the bridging chlorine atom from the symmetry-related adjacent unit. The equatorial Cu–Cl bonds (2.291(3) and 2…

Generation of lanthanide coordination polymers with dicarboxylate ligands: synthesis, structure, thermal decomposition and magnetic properties of the two-dimensional triaquatris(malonato)dipraseodymium(III) dihydrate {[Pr2(C3H2O4)3(H2O)3]·2H2O}

The malonate complex of formula [Pr2(C3H2O4)3(H2O)3]·2H2O (1) was prepared and his crystal structure determined by X-ray diffraction methods. 1 crystallizes in the monoclinic space group P21, Z = 4, with unit cell parameters a = 7.631(2), b = 12.899(4), c = 8.923(2) A and β = 101.11(3)°. 1 is a polymer which grows in the (110) plane. The hydrogen bond stabilizes the crystal structure forming a three-dimensional network. The two non-equivalent praseodymium(III) ions have different environments. Finally, the thermal behaviour and magnetic properties were investigated.

Heterobimetallic Oxalate‐Bridged M II Re IV (M = Zn, Cu, Ni, Co and Mn) Complexes Incorporating Bis(3,5‐dimethylpyrazol‐1‐yl)methane: Synthesis and Magneto‐Structural Studies

Five oxalato-bridged heterobimetallic compounds of general formula [ReCl4(ox)M(bdmpzm)2].2MeCN [ox = oxalate, bdmpzm = bis(3,5-dimethylpyrazol-1-yl)methane and M = Zn (1),Cu (2), Ni (3), Co (4) and Mn (5)] have been successfully synthesized in self-assembly reactions of the [ReCl4(ox)]2- metalloligand with the coordinatively unsaturated [M(bdmpzm)2]2+ complex generated in situ by the reaction of the suitable metal(II) salt with the bdmpzm ligand. 1-5 are isostructural compounds whose crystal structures consist of neutral heterodinuclear [ReCl4(ox)M(bdmpzm)2] units and free acetonitrile molecules. The magnetic properties of 1-5 were investigated in the temperature range 2.0-300 K. The nature…

Synthesis, crystal structure and magnetic properties of the three-dimensional compound [Na2Ni(mal)2(H2O)6]n (H2mal=malonic acid)

Abstract A new three-dimensional nickel–sodium compound of formula [Na 2 Ni(mal) 2 (H 2 O) 6 ] n (H 2 mal=malonic acid) was prepared and its structure was determined by X-ray diffraction methods. Four malonate–oxygen atoms and two trans -(Ni) or cis -(Na) coordinated water molecules build distorted octahedral surroundings around the metal atoms. The malonate group exhibits bidentate (Ni) and tetrakis-monodentate (Na) coordination modes. The structure can be described as corrugated sheets of malonato-containing Ni(II) and Na(I) cations which grow in the (101) plane, each sheet being linked to the adjacent one in the [101] direction through bis(μ-aqua)disodium(I) units. Within each corrugated…

Dinuclear, tetranuclear and one-dimensional pyrazine-based copper(II) complexes: preparation, X-ray structure and magnetic properties.

The preparation, crystal structures and magnetic properties of the copper(II) complexes of formula [Cu(2)(tppz)(H(2)O)(2)(CF(3)SO(3))(4)] (1), [Cu(tppz)(CrO(4))](n) x 3nH(2)O (2) and [Cu(4)(tppz)(4)(H(2)O)(4)(MoO(4))(2)](CF(3)SO(3))(4) x 7 H(2)O (3) [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine] are reported. Complex 1 is a dinuclear species where tppz adopts a bis-tridentate bridging mode with an intramolecular copper-copper separation of 6.5221(6) A. Each copper(II) ion in 1 has an elongated octahedral geometry with three tppz nitrogen atoms and a water molecule in the equatorial positions and two triflate oxygen atoms occupying the axial sites. Complex 2 is a uniform copper(II) chain where…

New Magnetic Thin Film Hybrid Materials Built by the Incorporation of Octanickel(II)-oxamato Clusters Between Clay Mineral Platelets

We report on a new method based on the combination of Langmuir-Schaefer deposition with self-assembly to insert highly anisotropic Ni(8) molecules in a hybrid organic-inorganic nanostructure. Spectroscopic, crystallographic, and magnetic data prove the successful insertion of the guest cationic molecule between templating clay platelets. These results open a new route toward the highly controlled fabrication of tailored functional organic-inorganic nanomaterials.

Synthesis, crystal structures and magnetic properties of cyanide- and phenolate-bridged [MIIINiII]2tetranuclear complexes (M = Fe and Cr)

The binuclear complex NiII2L(H2O)2(ClO4)2 (1) and the neutral tetranuclear bimetallic compounds [{MIII(phen)(CN)4}2{NiII2L(H2O)2}]·2CH3CN with M = Fe (2) and Cr (3) [H2L = 11,23-dimethyl-3,7,15,19-tetraazatricyclo[19.3.1.19,13]hexacosa-2,7,9,11,13(26),14,19,21(25),22,24-decaene-25,26-diol] have been synthesized and the structures of 2 and 3 determined by single crystal X-ray diffraction. 2 and 3 are isostructural compounds whose structure is made up of centrosymmetric binuclear cations [Ni2(L)(H2O)2]2+ and two peripheral [M(phen)(CN)4]− anions [M = Fe (2) and Cr (3)] acting as monodentate ligands towards the nickel atoms through one of their four cyanide nitrogen atoms. The environment of t…

High proton conduction in a chiral ferromagnetic metal-organic quartz-like framework.

A complex-as-ligand strategy to get a multifunctional molecular material led to a metal-organic framework with the formula (NH(4))(4)[MnCr(2)(ox)(6)]·4H(2)O. Single-crystal X-ray diffraction revealed that the anionic bimetallic coordination network adopts a chiral three-dimensional quartz-like architecture. It hosts ammonium cations and water molecules in functionalized channels. In addition to ferromagnetic ordering below T(C) = 3.0 K related to the host network, the material exhibits a very high proton conductivity of 1.1 × 10(-3) S cm(-1) at room temperature due to the guest molecules.

Spin-crossover complex encapsulation within a magnetic metal-organic framework.

The solid-state incorporation of a mononuclear iron(III) complex within the pores of a magnetic 3D metal–organic framework (MOF) in a single crystal to single crystal process leads to the formation of a new hybrid material showing both a guest-dependent long-range magnetic ordering and a spin-crossover (SCO) behaviour.

One-dimensional oxalato-bridged heterobimetallic coordination polymers by using [the [Cr(pyim)(C2O4)2]− complex as metalloligand [pyim = 2-(2′-pyridyl)imidazole]

Abstract Four new coordination polymers based on the use of the [Cr(pyim)(C2O4)2]− species as a metalloligand, namely [LiCr(pyim)(C2O4)2(MeOH)]n (1), {[CaCr2(pyim)2(C2O4)4]·2MeOH}n (2), {[SrCr2(pyim)2(C2O4)4(H2O)]·0.45MeOH·4.55H2O}n (3) and {[CdCr2(pyim)2(C2O4)4]·MeOH}n (4) [pyim = 2-(2′-pyridyl)imidazole] have been synthesized and characterized by elemental analyses, IR spectra and X-ray diffraction on single crystals. Complex 1 is a neutral heterobimetallic chain where the tris(chelated) chromium(III) unit acts as a bis-bidentate ligand towards {Li(MeOH)}+ fragments through its two oxalate ligands, each lithium ion being five-coordinate in a intermediate surrounding between square pyramid…

Synthesis, Crystal Structure and Magnetic Properties of Heteropolynuclear Re IV M II Complexes Based on the Robust [ReCl 5 (pyzCOO)] 2– Unit (pyzCOO = 2‐pyrazinecarboxylate)

The syntheses, crystal structures and magnetic properties of four rhenium(IV) compounds of formulae NBu4[ReCl5(pyzCOOH)]·H2O (1), [ReCl5(µ-pyzCOO)M(dmphen)2]·2CH3CN [M = Ni (2) and Co (3)] and {[ReCl5(µ3-pyzCOO)]2Mn2(dmphen)3}n (4) (NBu4 = tetra-n-butylammonium cation, pyzCOOH = 2-pyrazinecarboxylic acid, dmphen = 2,9-dimethyl-1,10-phenanthroline) are reported herein. Compound 1 was obtained by the reaction of NBu4[ReCl5(dmf)] (dmf = dimethylformamide) with pyzCOOH in acetone, whereas the other complexes were obtained by the reaction of 1 with M(ClO4)2·6H2O [M = Ni (2), Co (3), Mn (4)] and dmphen in acetonitrile. Complex 1 is a mononuclear compound, 2 and 3 are neutral heterodinuclear compl…

Azido- und 2,2′-Bipyrimidin-Liganden als nützliche Werkzeuge zur Synthese zwei- und dreidimensionaler Mangan(II)-Netzwerke

Syntheses, crystal structures and magnetic properties of one- and two-dimensional pap-containing copper(II) complexes (pap = pyrazino[2,3-  f  ][4,7]phenanthroline)

Three polynuclear complexes containing copper(II) and pyrazino[2,3-f][4,7]phenanthroline (pap) as the basic building blocks have been prepared [Cu2(pap)(H2O)2(NO3)3]n[NO3]n1, [Cu4(pap)4Cl7]nCln·15nH2O 2, and [Cu4(pap)4(H2O)4(C4O4)2]n[C4O4]n[NO3]2n·12nH2O 3, and their crystal structures and variable-temperature magnetic susceptibilities determined. Compound 1 is a single stranded zigzag chain where pap and nitrate alternate as bridges between the copper atoms. The copper coordination geometry is to a first approximation distorted square pyramidal, but with an additional semi-coordinated oxygen from non-bridging nitrate groups. The bridging nitrate coordinates in the apical position to both c…

Design of single chain magnets through cyanide-bearing six-coordinate complexes

Abstract The design and preparation of stable cyanide-bearing six-coordinate complexes of formula [MIII(L)(CN)x](x + l − m)− (M = trivalent transition metal ion and L = polydentate blocking ligand) are summarized here. Their use as ligands towards either fully hydrated metal ions or coordinatively unsaturated preformed species, to afford a wide variety of low-dimensional metal assemblies whose nuclearity, dimensionality and magnetic properties can be tuned, is also reviewed. Special emphasis is put on the appropriate choice of the end-cap ligand L whose denticity determines the number of coordinated cyanide groups in the mononuclear precursors. Among the different new spin topologies obtain…

Co-existence of ferro- and antiferromagnetic interactions in a hexanuclear mixed-valence CoIII2MnII2MnIV2 cluster sustained by a multidentate Schiff base ligand

The successful utilization of the “direct synthesis” approach yielded the unprecedented hexanuclear complex of formula [Co2MnII2MnIV2(L1)4Cl2(μ3-O)2(dmf)4]·2dmf (1) (H3L is the Schiff base derived from the condensation of salicylaldehyde and 3-aminopropane-1,2-diol). Single crystal X-ray analysis revealed that 1 crystallizes in the monoclinic system P21/c and it contains a rare mixed-valence {CoIII2MnII2MnIV2(μ2-O)8(μ3-O)2} core where all metal ions are linked through the phenolato and alkoxo groups of the L3− ligand. Besides the charge balance resulting from the X-ray structure, the oxidation state of the metal ions has been confirmed by XPS spectroscopy. Cryomagnetic studies indicate the …

Guanine-containing copper(ii) complexes: synthesis, X-ray structures and magnetic properties

Three new compounds of formula {[Cu(gua)(H(2)O)(3)](BF(4))(SiF(6))(1/2)}(n) (1), {[Cu(gua)(H(2)O)(3)](CF(3)SO(3))(2).H(2)O}(n) (2) and [Cu(gua)(2)(H(2)O)(HCOO)]ClO(4).H(2)O.1/2HCOOH] (3) [gua = 2-amino-1H-purin-6(9H)-one] showing the unprecedented coordination of neutral guanine, have been synthesised and structurally characterized. The structures of the compounds 1 and 2 contain uniform copper(II) chains of formula [Cu(gua)(H(2)O)(3)](n)(2n+), where the copper atoms are bridged by guanine ligands coordinated via N(3) and N(7). The electroneutrality is achieved by uncoordinated tetrafluoroborate and hexafluorosilicate (1) and triflate (2). Each copper atom in 1 and 2 is five-coordinated in …

Slow magnetic relaxation in carbonato-bridged dinuclear lanthanide(iii) complexes with 2,3-quinoxalinediolate ligands

The coordination chemistry of the 2,3-quinoxalinediolate ligand with different lanthanide(iii) ions in basic media in air affords a new family of carbonato-bridged M 2 III compounds (M = Pr, Gd and Dy), the Dy 2 III analogue exhibiting slow magnetic relaxation behaviour typical of single-molecule magnets. This journal is © 2012 The Royal Society of Chemistry.

New 3d–4f supramolecular systems constructed by [Fe(bipy)(CN)4]− and partially blocked lanthanide cations

Abstract The reaction of acetonitrile (1–5) and mixed acetonitrile/water 1:1 (6–9) solutions containing the cyanide-bearing [Fe(bipy)(CN)4]− building block (bipy = 2,2′-bipyridine) and the partially blocked [Ln(bpym)]3+ cation (Ln = lanthanide trivalent cation and bpym = 2,2′-bipyrimidine) has afforded two new families of 3d–4f supramolecular assemblies of formula [Ln(bpym)(NO3)2(H2O)3][Fe(bipy)(CN)4] · H2O · CH3CN [Ln = Sm (1), Gd (2), Tb (3), Dy (4) and Ho (5)] and [Ln(bpym)(NO3)2(H2O)4][Fe(bipy)(CN)4] [Ln = Pr (6), Nd (7), Sm (8), Gd (9)]. They crystallize in the P21/c (1–5) and P2/c (6–9) space groups and their structures are made up of [Fe(bipy)(CN)4]− anions (1–9) and [Ln(bpym)(NO3)2(…

Enantiopure Conducting Salts of Dimethylbis(ethylenedithio)tetrathiafulvalene (DM‐BEDT‐TTF) with the Hexachlororhenate(IV) Anion

Invited for the cover of this issue is the group of Narcis Avarvari (CIMI team) at the Laboratory MOLTECH-Anjou, UMR 6200 CNRS – Universite d'Angers, France. The cover image shows the enantiopure tetrathiafulvalene precursors used for the preparation of chiral radical cation conducting salts, together with an artwork of their packing diagrams and the suggested mirror image relationship between them.

Heterometallic CoII-CoIII-MII alkoxido-bridged heptanuclear motifs (M = Cu, Zn). Syntheses, crystal structures and magnetic properties

Two new alkoxido-bridged heterometallic complexes of formula [CoIICoIII 3CuII 3(dea)6(CH3COO)3](ClO4)0.75(CH3COO)1.25 (1) and [CoII 2CoIII 2ZnII 3(tea)2(piv)6(CH3O)2(OH)2(CH3OH)2]·H2O 2 (H2dea=diethanolamine, H3tea=triethanolamine and Hpiv=pivalic acid) have been assembled using aminoalcohol ligands. The cationic core in 1 possesses a threefold crystallographic axis, and it exhibits a set of three copper(II), one cobalt(II) and three cobalt(III) ions arranged as a hexagon of alternating copper(II) and cobalt(III) ions around the central cobalt(II) ion. Each edge of the hexagon is defined by a double alkoxido bridge, the outer one being bis-monodentate with copper(II)-cobalt(III) pair wherea…

[Mn2(bipym)(H2O)8]4+and [Fe(bipy)(CN)4]−as building blocks in designing novel bipym- and cyanide-bridged heterobimetallic complexes (bipym = 2,2′-bipyrimidine and bipy = 2,2′-bipyridine)

Two new cyano complexes, K[Fe(bipy)(CN)4]·H2O (1) and (μ-bipym)[Mn(H2O)3{Fe(bipy)(CN)4}]2[Fe(bipy)(CN)4]2·12H2O (2), have been synthesised and their structures determined by single-crystal X-ray diffraction. Complex 1 is made up of mononuclear [Fe(bipy)(CN)4]− anions, potassium cations and water molecules of crystallization. The iron(III) is six-coordinated, being surrounded by two nitrogen atoms of a chelating bipy and four carbon atoms of four cyanide groups [Fe–N and Fe–C 1.991(3)–1.990(3) and 1.958(5)–1.914(5) A, respectively]. Complex 2 consists of centrosymmetric tetranuclear (μ-bipym)[Fe(H2O)3{Fe(bipy)(CN)4}]22+ cations, [Fe(bipy)(CN)4]− anions and water molecules of crystallization.…

Enantiopure Conducting Salts of Dimethylbis(ethylenedithio)tetrathiafulvalene (DM‐BEDT‐TTF) with the Hexachlororhenate(IV) Anion (Eur. J. Inorg. Chem. 24/2014)

A dihydrogen arsenate-mediated supramolecular network: crystal structure and magnetic properties of {[(bipy)Cu(μ-H2AsO4)(H2AsO4)]2}n

Treatment of an aqueous suspension of Cu(OH)2 and 2,2′-bipyridine (bipy) with either Na2HAsO4·7H2O (1∶1∶2) or As2O5 (1∶1∶1) yields single crystals of {[(bipy)Cu(μ-H2AsO4)(H2AsO4)]2}n, 1, on standing. The solid-state structure of 1 consists of a three dimensional supramolecular network, supported by a combination of coordination covalent, hydrogen bonding and face-to-face π–π interactions. Variable temperature magnetic susceptibility measurements reveal very weak antiferromagnetic coupling between Cu(II) centres across the dihydrogen arsenate bridges (J = −0.58 cm−1).

Polymorphic Derivatives of NiII and CoII Mesocates with 3D Networks and “Brick and Mortar” Structures: Preparation, Structural Characterization, and Cryomagnetic Investigation of New Single-Molecule Magnets

In this work we describe the preparation, spectroscopic, thermal and structural characterization, and cryomagnetic investigation of four new polymorphic derivatives of the [M2(H2mpba)3]2– mesocate ...

Six-coordinate CoIII and four-coordinate MII (M = Co, Zn) mixed-valence dimers supported by a deprotonated pyridine amide ligand: magnetism of a CoIIICoII complex and C–H⋯O/Cl/Br interactions

Using a pyridine amide ligand 4-methyl-2-{N-(2-pyridyl)carbamoyl}pyridine (HL), in its deprotonated form, binuclear mixed-valence homonuclear bimetallic complexes [CoIII,II2(L)3(X)]X·S [X = Cl (1); X = Br, S = CH3OH (2)] and heteronuclear bimetallic complex [CoIIIZnII(L)3(Cl)]Cl·CH3OH·5H2O (3) have been synthesized. Structural analysis revealed that trivalent cobalt is in distorted octahedral and bivalent cobalt/zinc is in distorted tetrahedral environment. Three L(−) ligands provide six-coordination by utilizing three pyridine amide units (pyridine N and amide N donor set) in a facial mode, which in turn places three 4-methylpyridine nitrogens to coordinate to another metal center, which c…

2,2′-Oxydiacetato-bridged complexes containing Sm(III) and bivalent cations. Synthesis, structure, magnetic properties and chemical speciation

Abstract Heterometallic compounds containing Sm(III), bivalent cations M (M = Cu, Ni, Co, Mn, Ca, Mg), and 2′,2′-oxydiacetate (oda) as connecting ligand have been prepared and characterized. The complexes can be formulated as [Sm 2 M 3 (oda) 6 ] · xH 2 O. The structure of [Sm 2 Cu 3 (oda) 6 (H 2 O) 6 ] shows the presence of the Sm(III) coordinated by six carboxy and three ether oxygen atoms, and the Cu(II) cation bonded to four carboxy oxygens and two molecules of water. An open 3D framework is observed, containing large hexagonal channels. At room temperature, the polynuclear complexes behave as built by magnetically isolated paramagnetic ions, but at low temperatures, very weak antiferrom…

Structural versatility in cobalt(ii) complexes with 1,2,4,5-benzenetetracarboxylic acid (H4bta) and 4,4′-bipyridine-N,N′-dioxide (dpo)

Four new high-spin cobalt(II) complexes of formula [Co(H2O)6](H2bta)·dpo·4H2O (1), [{Co(H2O)4(dpo)}2(bta)]·4H2O·(2), [Co(H2O)2)(dpo)2(H2bta)]n (3) and [Co(H2O)3(dpo)(bta)1/2]n (4) (H4bta = 1,2,4,5-benzenetetracarboxylic acid and dpo = 4,4′-bipyridine-N,N′-dioxide) have been synthesized and their structures solved by single crystal X-ray diffraction methods. Compound 1 is an ionic salt whose structure is made up of [Co(H2O)6]2+ cations, H2bta2− anions, uncoordinated dpo groups and crystallization water molecules, which are linked by extensive hydrogen bonds to afford a three-dimensional network. The structure of 2 consists of bta-bridged dinuclear cobalt(II) complexes where four coordinated …

A Three-Dimensional Homometallic Molecular Ferrimagnet

A novel two-dimensional honeycomb-like bimetallic iron(iii)–nickel(ii) cyanide-bridged magnetic material [Ni(cyclam)]3[Fe(CN)6]2·nH2O (cyclam = 1,4,8,11-tetraazacyclodecane)

The 2D honeycomb-like layered iron(iii)–nickel(ii) cyanidebridged complex [Ni(cyclam)]3[Fe(CN)6]2·nH2O exhibits ferromagnetic intralayer and antiferromagnetic interlayer interactions; above 3 K the magnetic properties are typical of a metamagnet with Hc = 5000 G, whereas below 3 K a canted structure is formed, leading to a long range ferromagnetic ordering. Lloret Pastor, Francisco, Francisco.Lloret@uv.es

A three-dimensional copper(ii) 12-metallacrown-4 complex with malonomonohydroxamic acid (H3mmh) as a ligand

Slow diffusion of an ethanolic solution of copper(ii) into an aqueous solution of partially deprotonated malonodihydroxamic acid (H4mdh) affords the pentanuclear complex of formula {[K(H2O) 2]2[Cu5(mmh)4]}n (1) (H3mmh = malonomonohydroxamic acid) which is formed by 12-MC-4 metallacrown units with the fifth copper(ii) ion being placed at the center of the square metallacrown unit. The dianionic pentacopper(ii) planar entity interacts with diaquapotassium(i) counterions through the carboxylate-oxygen atoms resulting in a neutral three-dimensional structure. Magnetic susceptibility measurements in the temperature range 1.9-300 K for 1 show the occurrence of relatively strong antiferromagnetic …

Synthesis, Structural, Magnetic and Thermal Characterization of {[Cu(bipy)] 2 (μ‐HP 2 O 7 )(μ‐Cl)}·H 2 O

Copper(II) hydroxide reacts with 2,2′-bipyridine (bipy) and sodium pyrophosphate in a 2:2:1 stoichiometric ratio under ambient conditions at pH 1.6 in water. The resulting neutral dinuclear CuII complex features a bridging set containing bridging monoprotonated pyrophosphate and a monoatomic chloro bridge (making this the first pyrophosphate bridged coordination complex containing an alternate, additional halide bridge between the metal centers). Single-crystal X-ray diffraction studies revealed the complex to be {[Cu(bipy)]2(μ-HP2O7)(μ-Cl)}·H2O. The structure consists of a dimeric copper(II) system with each metal ion in a square pyramidal geometry. The asymmetric [Cu(bipy)]2+ units are br…

Structure and magnetic properties of a linear oximato-bridged tetranuclear copper(II) complex

Abstract The tetranuclear copper(II) complex of formula [Cu2(dmg)(Hdmg)(terpy)]2(ClO4)2 (1) (H2dmg = dimethylglyoxime and terpy = 2,2′:6′,2″-terpyridine) has been synthesized and its crystal structure determined by X-ray diffraction methods. It crystallizes in the triclinic system, space group P(−1), with a = 14.382(3), b = 13.728(3), c = 8.979(2) A, α = 96.99(2), β = 111.85(2), γ = 111.22(3)°, V = 1465.0(9) A3, Z = 1, Dc = 1.607 g cm−3, Mr = 1418.0, F(000) = 719, λ(Mo Kα) = 0.71073 A, μ(Mo Kα) = 16.61 cm−1 and T = 298 K. A total of 4891 reflections were measured over the range 2 ≤ θ ≤ 25° and 4393 of them were unique (I > 2.5σ(I) and used in the structural analysis. The structure of 1 may …

One-dimensional iron(III) and two-dimensional iron(III)nickel(II) cyanide-bridged ferromagnetic arrays from hexacyanoferrate(III) and [Ni(cyclam)]2+ building blocks: Synthesis, crystal structure and magnetic properties

Abstract The X-ray structures and magnetic properties of a iron(III) linear chain and a honeycomb-like layered iron(III)-nickel(II) cyanide-bridged compound are reported. The former contains alternating iron sites and unexpected ferromagnetic behaviour, justified on the basis of the axial distortion from regular octahedral geometry of one of the iron ions. The latter is metamagnetic with ferromagnetic intralayers and antiferromagnetic interlayers interactions with a Neel temperature, TN= 7.7 K. The field-induced transition from an antiferro- to a ferromagnetic state takes place at Hc= 5000 G. The antiferromagnetic ordered phase exhibits spin-canting and long range ferromagnetic ordering at …

Copper(II) assembling with bis(2-pyridylcarbonyl)amidate and N,N'-2,2-phenylenebis(oxamate).

We herein present the synthesis and X-ray structures of five copper(II) complexes of formulae [Cu(bpca)(CF3SO3)(H2O)]·H2O (1), [Cu(bpca)(Phpr)(H2O)]·3/2H2O (2), {[Cu(bpca)]2[Cu(opba)(H2O)]}·H2O (3), {[Cu(bpca)]2(H2opba)}2·6H2O (4) and [Cu(bpca)(EtH2opba)]n (5), where bpca = bis(2-pyridylcarbonyl)amidate, Phpr = 3-phenylpropionate, CF3SO3(−) = triflate (anion of the trifluoromethanesulphonic acid), H4opba = N,N′-1,2-phenylenebis(oxamic acid), and EtH3opba = monoethyl ester derivative of the H4opba. 1 and 2 are mononuclear copper(II) complexes where the copper atom is five-coordinate in distorted square pyramidal surroundings with a tridentate bpca and a water molecule (1)/carboxylate oxygen …

Syntheses, crystal structures and magnetic properties of polynuclear 1,4,5,8,9,12-hexaazatriphenylene (hat)-bridged copper(II) complexes

Three polynuclear compounds containing copper(II) and 1,4,5,8,9,12-hexaazatriphenylene (hat) as the basic building blocks have been prepared, [Cu4(hat)2Cl8]n·6nH2O 1, [Cu(hat)(H2O)2]n[NO3]2n2, and [Cu2(hat)(H2O)6]n[SO4]2n·2nH2O 3, their crystal structures determined and variable-temperature magnetic susceptibility data measured. The basic building block in 1 is the dinuclear [Cu2(hat)Cl4] entity, two such units being connected to tetranuclear units through relatively strong axial Cu–Cl bonds (out-of-plane di-μ-chloro bridges). Weaker axial Cu⋯Cl interactions link the units into a sheet structure. In 2 and 3 hat-bridged copper(II) chains extending along glide planes are present. hat serves a…

Ferromagnetic Coupling between Low- and High-Spin Iron(III) Ions in the Tetranuclear Complex fac-{[FeIII{HB(pz)3}(CN)2(μ-CN)]3FeIII(H2O)3}· 6H2O ([HB(pz)3]- = Hydrotris(1-pyrazolyl)borate)

The novel mononuclear PPh4-fac-[FeIII{HB(pz)3}(CN)3]·H2O (1) [PPh4+= tetraphenylphosphonium cation; (HB(pz)3)- = hydrotris(1-pyrazolyl)borate] and tetranuclear fac-{[FeIII{HB(pz)3}(CN)2(μ-CN)]3FeIII(H2O)3}·6H2O (2) have been prepared and characterized by X-ray diffraction analysis. Crystal data for compound 1:  monoclinic, space group P21/c, a = 9.575(3) A, b = 21.984(4) A, c = 16.863(3) A, β = 100.34(2)°, U = 3486(1) A3, Z = 4. Crystal data for compound 2:  orthorhombic, space group Pnam, a = 14.084(3) A, b = 14.799(4) A, c = 25.725(5) A, U = 5362(2) A3, Z = 4. Compound 1 is a low-spin iron(III) compound with three cyanide ligands in fac arrangement and a tridentate pyrazolylborate ligand …

Geometric isomeric pairs: synthesis, structure, thermal decomposition and magnetic properties of cis- and trans-[Cr(mal)(bpy)(H2O)2][NO3]·xH2O (H2mal=malonic acid, bpy=2,2′-bipyridine)

Abstract Procedures are given for the preparation and isolation of cis-[Cr(mal)(bpy)(H2O)2][NO3]·3H2O (I) and trans-[Cr(mal)(bpy)(H2O)2][NO3]·H2O (II) (H2mal=malonic acid, bpy=2,2′-bipyridine). The single crystals X-ray structure of cis-compound reveals that the cations and anions as well as cations between cations are linked into hydrogen-bonded chains. Unfortunately, little structural information is available for the trans compound II (only isotropic cation refinement), nevertheless, from this result is observed that there also exists a hydrogen-bonded network between anion units. Thermal analysis and magnetic behaviour for both compounds were studied.

Bis(oxalato)chromium(III) complexes: Versatile tectons in designing heterometallic coordination compounds

Abstract The mononuclear oxalato-containing chromium(III) complexes of general formula [Cr(AA)(C2O4)2]− (AA = α-diimine type ligand) are able to produce a large variety of heterometallic complexes by acting as ligands towards either fully solvated metal ions or preformed cationic complexes with available coordination sites. This review focuses on the structural diversity of the polynuclear complexes (oligonuclear and coordination polymers) which are generated by the bis(oxalato)chromate(III) species, with a special emphasis to their magnetic properties.

New cyanide-bridged Mn(III)-M(III) heterometallic dinuclear complexes constructed from [M(III)(AA)(CN)4]- building blocks (M = Cr and Fe): synthesis, crystal structures and magnetic properties.

Three Mn(III)-M(III) (M = Cr and Fe) dinuclear complexes have been obtained by assembling [Mn(III)(SB)(H(2)O)](+) and [M(III)(AA)(CN)(4)](-) ions, where SB is the dianion of the Schiff-base resulting from the condensation of 3-methoxysalicylaldehyde with ethylenediamine (3-MeOsalen(2-)) or 1,2-cyclohexanediamine (3-MeOsalcyen(2-)): [Mn(3-MeOsalen)(H(2)O)(µ-NC)Cr(bipy)(CN)(3)]·2H(2)O (1), [Mn(3-MeOsalen)(H(2)O)(µ-NC)Cr(ampy)(CN)(3)][Mn(3-MeOsalen)(H(2)O)(2)]ClO(4)·2H(2)O (2) and [Mn(3-MeOsalcyen)(H(2)O)(µ-NC)Fe(bpym)(CN)(3)]·3H(2)O (3) (bipy = 2,2'-bipyridine, ampy = 2-aminomethylpyridine and bpym = 2,2'-bipyrimidine). The [M(AA)(CN)(4)](-) unit in 1-3 acts as a monodentate ligand towards th…

Highly selective chemical sensing in a luminescent nanoporous magnet.

Among the wide variety of properties of interest that a given material can exhibit, luminescence is attracting an increasing attention due to its potential application in optical devices for lighting equipment and optical storage, [ 1a − c] optical switching, [ 1d ,e] and sensing. [ 1f − i ] At this respect, many scientists, working in the multidisciplinary fi eld of the materials science, have directed their efforts to the obtention of luminescent materials with potential sensing applications. For instance, sensitive and selective detection of gas and vapor phase analytes can result specially interesting because of the variety of applications that can be found in many different fi elds. A …

Photoswitching of the antiferromagnetic coupling in an oxamato-based dicopper(ii) anthracenophane

Thermally reversible photomagnetic (ON/OFF) switching behavior has been observed in a dinuclear oxamatocopper(ii) anthracenophane upon UV light irradiation and heating; the two CuII ions (SCu = 1/2) that are antiferromagnetically coupled in the dicopper(ii) metallacyclic precursor (ON state) become uncoupled in the corresponding [4+4] photocycloaddition product (OFF state), as substantiated from both experimental and theoretical studies. © 2011 The Royal Society of Chemistry.

Syntheses, Structures, and Magnetic Properties of Copper( II ) Complexes with 1,3‐[Bis(2‐pyridylmethyl)amino]benzene (1,3‐tpbd) as Ligand

The dinuclear copper(II) complexes {[Cu2(1,3-tpbd)(H2O)(OAc)2](ClO4)2}0.23{[Cu2(1,3-tpbd)(H2O)2(OAc)](ClO4)3}0.77·0.77H2O (1), [Cu2(1,3-tpbd)(H2O)2(OAc)2](ClO4)2·2H2O (2), and the tetranuclear copper(II) complex [Cu4(1,3-tpbd)2(H2O)2(SO4)4]·8H2O (3) {1,3-tpbd = 1,3-bis[bis(2-pyridylmethyl)amino]benzene} were synthesised and structurally characterised by X-ray diffraction. Variable-temperature (2.0−290 K) magnetic susceptibility measurements on these complexes as well as on the dinuclear copper(II) complex [Cu2(1,3-tpbd)(H2O)2(ClO4)3]ClO4 (4) (whose structure was published earlier) were performed. In contrast to 2 and 3, significant ferromagnetic coupling with J = +9.3 cm−1 was observed for …

Cobalt(II) Sheet-Like Systems Based on Diacetic Ligands: from Subtle Structural Variances to Different Magnetic Behaviors

The preparation, X-ray crystallography, and magnetic investigation of the compounds [Co(H(2)O)(2)(phda)](n) (1), [Co(phda)](n) (2), and [Co(chda)](n) (3) [H(2)phda = 1,4-phenylenediacetic acid and H(2)chda = 1,1-cyclohexanediacetic acid] are described herein. The cobalt atoms in this series are six- (1) and four-coordinated (2 and 3) in distorted octahedral (CoO(6)) and tetrahedral (CoO(4)) environments. The structures of 1-3 consists of rectangular-grids which are built up by sheets of cobalt atoms linked through anti-syn carboxylate bridges, giving rise to either a three-dimensional structure across the phenyl ring (1 and 2) or to regularly stacked layers with the cyclohexyl groups acting…

Synthesis, X‐ray Structure, Thermal and Magnetic Behavior of [(bipy) 2 Ni 2 (μ‐Cl) 2 Cl 2 (H 2 O) 2 ]: The First Neutral Ferromagnetically Coupled Six‐Coordinate Dichlorido‐Bridged Nickel(II) Dimer

NiCl2·6H2O and 2,2′-bipyridine (bipy) (1:1) were allowed to react under ambient conditions in dimethyl sulfoxide in the presence of acetylacetone (Hacac). The resulting green solution was concentrated in vacuo, and a green solid was isolated by precipitation with cold acetone. X-ray quality crystals of [(bipy)2Ni2(μ-Cl)2(Cl)2(H2O)2] (1) were grown by subsequent vapor/liquid diffusion of acetonitrile into a methanolic solution for one week. The structure of 1 consists of a dimeric nickel system with each metal atom in an octahedral geometry. Both equatorial bridging and axial chlorine atoms are present in this neutral species. The nickel–nickel distance (3.441 A) is the shortest reported to …

New hexanuclear FeIII clusters with the gem-diol hydrated form of di(2-pyridyl)ketone and carboxylato ligands: Crystal structures and magnetic properties

Abstract The hexanuclear compounds [Fe6O2Cl2{(py)2CO2}2(pyOH)2(pyCOO)2(ButCOO)6] (1) and [Fe6O2{(py)2CO2}2(pyCOO)4(ButCOO)6] (2) were obtained by condensation of the trinuclear μ3-oxo-centered iron(III) pivalate [Fe3O(ButCOO)6(H2O)3]+ in the presence of di(2-pyridyl)ketone [(py)2CO] in MeCN at ambient temperature. Both complexes contain an analogous core which can be described as two {Fe3O}7+ units joined by gem-diolato (py)2CO22− bridges. Variable-temperature magnetic susceptibility measurements in polycrystalline samples of 1 and 2 reveal strong antiferromagnetic couplings between the iron(III) ions leading to S = 0 ground states.

Dimensionality Switching Through a Thermally Induced Reversible Single-Crystal-to-Single-Crystal Phase Transition in a Cyanide Complex

International audience; The heterometallic hexanuclear cyanide-bridged complex {[Mn(bpym)(H(2)O)](2)[Fe(HB(pz)(3))(CN)(3)](4)} (1), its C(15)N and D(2)O enriched forms {[Mn(bpym)(H(2)O)](2)[Fe(HB(pz)(3))(C(15)N)(3)](4)} (2) and {[Mn(bpym)(D(2)O)](2)[Fe(HB(pz)(3))(CN)(3)](4)} (3), and the hexanuclear derivative complex {[Mn(bpym)(H(2)O)](2)[Fe(B(pz)(4))(CN)(3)](4)}*4H(2)O (4) [bpym = 2,2'-bipyrimidine, HB(pz)(3)(-) = hydrotris(1-pyrazolyl)borate, B(pz)(4)(-) = tetra(1-pyrazolyl)borate] have been synthesized. Their structures have been determined through single-crystal X-ray crystallography at different temperatures. Whereas 3 and 4 maintain a discrete hexanuclear motif during the entire temp…

Hexacyanocobaltate(III) Anions as Precursors of Co(II)−Ni(II) Cyano-Bridged Multidimensional Assemblies:  Hydrothermal Syntheses, Crystal and Powder X-ray Structures, and Magnetic Properties

Three novel cyanide-bridged heterobimetallic coordination polymers have been synthesized by hydrothermal routes, in superheated water solutions, by using K3[Co(CN)6], NiCl2.6H2O, and alpha-diimine ligands: [Ni(CN)4Co(phen)] (1; phen = 1,10-phenanthroline), [Ni(CN)4Co(2,2'-bipy)] (2; 2,2'-bipy = 2,2'-bipyiridine), and [Ni(CN)4Co(2,2'-bipy)2] (3). The isostructural compounds 1 and 2 contain a two-dimensional network with Co(II) centers octahedrally coordinated by one chelating 2,2'-bipy ligand and four cyanide groups of four distinct [Ni(CN)4]2-, through crystallographically equivalent, bridging units. Compound 3 contains one-dimensional zigzag chains in which the Co(II) ion is coordinated by…

Syntheses, crystal structures and magnetic properties of five new manganese(ii) complexes: Influence of the conformation of different alkyl/aryl substituted malonate ligands on the crystal packing

et al.

Cover Picture: Solid-State Molecular Nanomagnet Inclusion into a Magnetic Metal-Organic Framework: Interplay of the Magnetic Properties (Chem. Eur. J. 2/2016)

Single ion magnet behaviour in a two-dimensional network of dicyanamide-bridged cobalt(II) ions

A novel two-dimensional coordination polymer of the formula [Co(dca)2(atz)2]n (1) resulted from assembling trans-bis(2-amino-1,3,5-triazine)cobalt(II) motifs by dicyanamide spacers. Variable-temperature dc and ac magnetic susceptibility measurements of 1 show that the high-spin cobalt(II) ions act as single ion magnets (SIMs).

Crystal structures and magnetic properties of the squarate-O1,On-bridged dinuclear copper(II) complexes [Cu2(phen)4(C4O4)](CF3SO3)2 · 3H2O (n=2) and [Cu2(bipy)4(C4O4)](CF3SO3)2 · 6H2O (n=3)

Abstract Two dinuclear copper(II) complexes of the formula [Cu2(phen)4(C4O4)](CF3SO3)2 · 3H2O (1) and [Cu2(bipy)4(C4O4)](CF3SO3)2 · 6H2O (2) [phen=1,10-phenanthroline, bipy=2,2′-bipyridine and C4O4 2−=dianion of 3,4-dihydroxy-3-cyclobuten-1,2-dione (squaric acid)] have been synthesized and characterized by single-crystal X-ray diffraction. Their structures consist of [Cu2(phen)4(C4O4)]2+ (1) and [Cu2(bipy)4(C4O4)]2+ (2) dinuclear copper(II) cations, uncoordinated CF3SO3 − anions and crystallization water molecules. The copper is in a distorted square pyramidal environment: one squarate-oxygen atom and three phen- (1) or bipy- (2) nitrogen atoms of two phen (1) or bipy (2) terminal ligands f…

Solid state polymerization causing transition to a ferromagnetic state. Crystal structures and magnetic properties of [Cu2(dpp)(H2O)(dmso)Cl4]·dmso and [Cu2(dpp)Cl4]n (dpp = 2,3-bis(2-pyridyl)pyrazine)

The preparation, crystal structures and variable-temperature magnetic susceptibility data for [Cu2(dpp)(H2O)(dmso)Cl4]·dmso (1a) and [Cu2(dpp)Cl4]n (2) (dpp = 2,3-bis(2-pyridyl)pyrazine, dmso = dimethyl sulfoxide) are reported. 1a consists of dinuclear dpp-bridged molecules with chlorine, water and dmso serving as terminal ligands. The two copper atoms are crystallographically independent, with distorted square pyramidal and trigonal bipyramidal coordination geometries, respectively. In a first approximation 2 may be described as a chain compound with out-of-plane mono-μ-chloro bridges (Cu–Cl–Cu–Cl). Only one of the crystallographically independent copper atoms participates in this chain fo…

Novel chiral three-dimensional iron(III) compound exhibiting magnetic ordering at T(c) = 40 K.

The preparation and crystal structure determination of the iron(III) compound of formula [(NH(4))(2)[Fe(2)O(ox)(2)Cl(2)].2H(2)O](n) (1) (ox = oxalate dianion) are reported here. Complex 1 crystallizes in the orthorhombic system, space group Fdd2, with a = 14.956(7) A, b = 23.671(9) A, c = 9.026(4) A, and Z = 8. The structure of complex 1 consists of the chiral anionic three-dimensional network [Fe(2)O(ox)(2)Cl(2)](2-) where the iron(III) ions are connected by single oxo and bisbidentate oxalato groups. The metal-metal separations through these bridging ligands are 3.384(2) and 5.496(2) A, respectively. Ammonium cations and crystallization water molecules are located in the helical pseudohex…

Two Novel Ternary Dicopper(II) μ-Guanazole Complexes with Aromatic Amines Strongly Activated by Quantum Dots for DNA Cleavage

Two novel (μ-guanazole)-bridged binuclear copper(II) complexes with 1,10-phenanthroline (phen) or 2,2'-bipyridine (bipy), [Cu2(μ-N2,N4-Hdatrz)(phen)2(H2O)(NO3)4] (1) and [Cu2(μ-N1,N2-datrz)2(μ-OH2)(bipy)2](ClO4)2 (2) (Hdatrz = 3,5-diamino-1,2,4-triazole = guanazole), have been prepared and characterized by X-ray diffraction, spectroscopy, and susceptibility measurements. Compounds 1 and 2 differ in the aromatic amine, which acts as a coligand, and in the Cu···Cu'-bridging system. Compound 1, which contains two mono-bridged copper ions, represents the first example of a discrete Cu-(NCN-trz)-Cu' complex. Compound 2, with two triply bridged copper ions, is one of the few compounds featuring a…

Magnetic properties and molecular structures of binuclear (2-pyrazinecarboxylate)-bridged complexes containing Re(iv) and M(ii) (M = Co, Ni)

Three novel Re(iv) compounds, the mononuclear complex Bu(4)N[ReBr(5)(Hpyzc)] (1) and the heterobimetallic complexes [ReBr(5)(mu-pyzc)M(dmphen)(2)].2CH(3)CN [M = Co (2), Ni (3)] (Hpyzc = 2-pyrazinecarboxylic acid, dmphen = 2,9-dimethyl-1,10-phenanthroline), have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. The structure of 1 consists of [ReBr(5)(Hpyzc)](-) complex anions and tetrabutylammonium cations, Bu(4)N(+). The Re(iv) is surrounded by five bromide anions and a N-donor Hpyzc monodentate ligand, in a distorted octahedral environment. The structures of 2 and 3 consist of dinuclear units [ReBr(5)(mu-pyzc)M(dmphen)(2)], with the metal ions li…

Novel Hexanuclear Copper(II) Complex Built from a Simple Tetrachelating Triazole Ligand: Synthesis, Structure, and Magnetism

A new easy symmetric 3,5-disubstituted 1,2,4-triazole ligand (H3diV) by reaction with an excess of copper(II) salt has afforded a novel hexanuclear compound (Cu/HdiV ratio of 6:2) through a bis(trans-cis-cis-trans) binding mode, exhibiting two types of Cu(II) centers and two clearly distinguishable antiferromagnetic J1 (-234 cm(-1)) and J2 (-35 cm(-1)) coupling constants.

The azido ligand: a useful tool in designing chain compounds exhibiting alternating ferro- and antiferro-magnetic interactions

A one-pot reaction of NiII 1, CoII 2, FeII 3 and MnII 4 with 2,2A-bipyridine (bipy) and azide in water leads to [M(bipy)(N3)2]n chains where the metal ion is alternatively bridged by double end-on (EO) and end-to-end (EE) azido bridges; theoretical analysis of the variable-temperature magnetic susceptibility data of 1 and 4 reveals the occurrence of intrachain alternating ferro- (through EO) and antiferro-magnetic (through EE) interactions. Julve Olcina, Miguel, Miguel.Julve@uv.es ; Lloret Pastor, Francisco, Francisco.Lloret@uv.es ; Clemente Juan, Juan Modesto, Juan.M.Clemente@uv.es

Ligand effects on the dimensionality of oxamato-bridged mixed-metal open-framework magnets

Increasing dimensionality [from 2D (1) to 3D (2)] and T(C) [from 10 (1) to 20 K (2)] in two new oxamato-bridged heterobimetallic Mn(II)(2)Cu(II)(3) open-frameworks result from the steric hindrance provided by the different alkyl substituents of the N-phenyloxamate bridging ligands.

Two-Dimensional Coordination Polymers Constructed by [NiIILnIII] Nodes and [WIV(bpy)(CN)6]2– Spacers: A Network of [NiIIDyIII] Single Molecule Magnets

Three isomorphous two-dimensional (2D) coordination polymers of general formula {[Ni(II)(valpn)Ln(III)(NO3)(H2O)(μ-NC)4W(IV)(bipy)(CN)2]·xH2O·yCH3CN}n have been synthesized by reacting Ph4P[W(V)(CN)6(bipy)] with the heterodinuclear [Ni(II)Ln(III)(valpn)(O2NO)3] complexes [H2valpn = 1,3-propanediyl-bis(2-iminomethylene-6-methoxyphenol), bipy = 2,2'-bipyridine, and Ln = Gd (1), Dy (2), and Tb (3) with x = 2 (1), 3.9 (2), and 3.35 (3) and y = 2.50 (1), 2 (2), and 1.8 (3)]. Their crystal structures consist of [Ni(II)Ln(III)] 3d-4f nodes which are connected by [W(IV)(bipy)(CN)6](2-) diamagnetic linkers resulting from the reduction of W(V) to W(IV) during the reaction process. The Ni(II) and Ln(I…

One-dimensional metal-organic framework with unprecedented heptanuclear copper units.

The reaction of copper(II) sulfate, copper(II) chloride, 3,5-diacetylamino-1,2,4-triazole, and 3-acetylamino-5-amino-1,2,4-triazole in water yields green, plate-shaped crystals of [[{Cu3(mu3-OH(1/2))L(H2O)2Cl}2{mu-Cu(H2O)2Cl2}].12H2O]n (1), where L is a new triazole-derived macrocyclic ligand. The structure of 1 consists of heptanuclear (H)OCuII(3)-CuII-CuII(3)O(H) entities linked in pairs through symmetric mu3-O...H...O-mu3 hydrogen bonds to form a double-stranded one-dimensional network. A significant overall antiferromagnetic behavior has been observed for 1.

Ferro- and Antiferromagnetic Interactions in Oxalato-Centered Inverse Hexanuclear and Chain Copper(II) Complexes with Pyrazole Derivatives.

Two novel copper(II) complexes of formulas {[Cu(4-Hmpz)4][Cu(4-Hmpz)2(µ3-ox-κ2O1,O2:κO2′:κO1′)(ClO4)2]}n (1) and {[Cu(3,4,5-Htmpz)4]2[Cu(3,4,5-Htmpz)2(µ3-ox-κ2O1,O2:κO2′:κO1′)(H2O)(ClO4)]2[Cu2(3,4,5-Htmpz)4(µ-ox-κ2O1,O2:κ2O2′,O1′)]}(ClO4)4·6H2O (2) have been obtained by using 4-methyl-1H-pyrazole (4-Hmpz) and 3,4,5-trimethyl-1H-pyrazole (3,4,5-Htmpz) as terminal ligands and oxalate (ox) as the polyatomic inverse coordination center. The crystal structure of 1 consists of perchlorate counteranions and cationic copper(II) chains with alternating bis(pyrazole)(µ3-κ2O1,O2:κO2′:κO1′-oxalato)copper(II) and tetrakis(pyrazole)copper(II) fragments. The crystal structure of 2 is made up of perchlorat…

Preparation, crystal structure and magnetic properties of di-2-pyridylamine (dpa) copper(II) complexes [Cu(dpa)(N3)2]n and [Cu2(dpa)2(NCO)4]

Abstract The preparation, crystal structures and magnetic properties of two copper(II) complexes with di-2-pyridylamine (dpa) as end-cap ligand and azide (1) and cyanate (2) as bridging groups, [Cu(dpa)(N3)2]n (1) and [Cu2(dpa)2(NCO)4] (2), are reported. Compound 1 consists of uniform chains of copper(II) ions bridged by single μ-1,1-azido groups whereas that of compound 2 is made up of centrosymmetric dicopper(II) units with double μ-1,1-N-cyanate bridges, the other two cyanate groups acting as terminal ligands. The copper atoms in 1 and 2 are five-coordinated with two nitrogen atoms of a bidentate dpa ligand (1 and 2), one nitrogen atom from a terminally bound azide (1)/cyanate (2) and tw…

Cyanido-bridged {FeIIILnIII} heterobimetallic chains assembled through the [FeIII{HB(pz)3}(CN)3]−complex as metalloligand: synthesis, crystal structure and magnetic properties

A new series of cyanido-bridged {FeIIILnIII} heterobimetallic chains of general formula {[(NC)FeIII{HB(pz)3}(μ-CN)2LnIII(bpdo)(NO3)2(H2O)]·CH3CN}n [HB(pz)3− = hydrotris(pyrazol-1-yl)borate, bpdo = 2,2′-bipyridine-N,N′-dioxide and Ln = Gd (1), Tb (2), Dy (3) and Ho (4)], were obtained by using the low-spin [Fe{HB(pz)3}(CN)3]− complex as a metalloligand towards the preformed [Ln(bdpo)(NO3)2(H2O)]+ species. Single-crystal X-ray diffraction shows that 1–4 are isostructural compounds that crystallize in the monoclinic P21/c space group. Their crystal structure consists of neutral 1D coordination polymers where the [Fe{HB(pz)3}(CN)3]− fragment adopts a bis-monodentate coordination mode, through t…

Growth of thin films of single-chain magnets on functionalized silicon surfaces

A one-pot strategy for the direct growth of continuous and regular thin films of a neutral oxamato-bridged heterobimetallic chain, synthesized from Co2+ nitrate and the tetramethylammonium salt of the anionic copper(II) complex (Me4N)2[Cu(2,6-Et2pa)2]·6H2O (1) (2,6-Etpa = N-2,6-diethylphenyloxamate) over Si(111) surfaces functionalized with carboxylic acid terminating groups has been developed. Variation of the growth conditions can provide important differences in the morphology of the obtained films when working in H2O at 20 °C. An anisotropic growth of 1-D fibers is observed under stoichiometric conditions (Co2+/1 = 1:1), while an isotropic growth of 3-D particles occurs for an excess of…

Synthesis, structure and magnetic properties of Mn(II) and Cu(II) complexes with the dicyano-acetic acid methyl ester anion

The preparation of the sodium salt of dicyano-acetic acid methyl ester (NaCH 3 OC(O)C(CN) 2 ) (NaL) is reported. The structure of this anion is related to the structure of the dicyanamide, whose chelating capability has been used to develop 2D networks. Two new complexes of formula [M(L) 2 (H 2 O) 2 ] (M=Mn 2+ ( 1 ) and Cu 2+ ( 2 )) have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. The coordination geometry of Mn atom in 1 is approximately octahedral, and the Mn atoms are μ 2 -bridged by two pairs of L − resulting in an infinite one-dimensional chain. Two types of hydrogen bonds link the chains within a 3-dimensional infinite lattice. The coo…

Mono- and Di-chloro-bridged Discrete Dimers and Trimers and Mono-Chloro-Bridged 1D-Coordination Polymer of Copper(II). Magneto-structural Studies

The synthesis, structural characterization, and magnetic properties of three copper(II) complexes, a mono-chloro-bridged [Cu2II(L6)2(μ-Cl)(Cl)(CuIICl4)] (1) and a dichloro-bridged [CuII2(L7)2(μ-Cl)2][ClO4]2 (3) discrete trimers and dimers, and a mono-chloro-bridged 1D-coordination polymer [CuII(L6)(μ-Cl)][ClO4]·CH3CN (2), are reported. Molecular structures were authenticated by X-ray crystallography. Temperature-dependent magnetic measurements carried out on powdered samples of 1–3 indicated a very weak antiferromagnetic exchange-coupling within the {CuII(μ-Cl)CuII(μ-Cl)CuIICl3}+ units in 1 [Curie-Weiss plot: θ = –0.19(1) K and g = 2.07(1)], a ferromagnetic behavior within {CuII(μ-Cl)2CuII}…

Synthesis, crystal structure and magnetic properties of a new [ZnII6DyIII6] dodecanuclear motif

Abstract A new dodecanuclear complex, [{(HL)(L)(dmf)ZnIIDyIII(dmf)(H2O)}6]·3dmf·4.2H2O has been assembled using a supramolecular compartmental ligand (H3L results from the condensation reaction of 3-formylsalicylic acid and hydroxylamine). The six DyIII ions describe an octahedron that is inscribed into the octahedron generated by the zinc(II) ions each DyIII ion from this motif behaving as a single ion magnet.

Spinpolarisierung und Ferromagnetismus in zweidimensionalen CoII-Schichtpolymeren: [Co(L)2(NCS)2] (L = Pyrimidin, Pyrazin)

Wie vorhergesagt antiferro- und ferromagnetisch sind die beiden Schichtpolymere [Co(NCS)2(pyz)2] 1 bzw. [Co(NCS)2(pym)2] 2 (Strukturausschnitt im Bild). Die Verbindungen sowie der einkernige Komplex [Co(NCS)2(pyd)4] 3, der zu Vergleichszwecken synthetisiert wurde, konnten aus Losungen von Co(NCS)2 und Pyrazin (pyz; 1), Pyrimidin (pym; 2) bzw. Pyridazin (pyd; 3) in Methanol erhalten, strukturell charakterisiert und ihre magnetischen Eigenschaften untersucht werden.

A novel supramolecular assembly in an iron(III) compound exhibiting magnetic ordering at 70 K

Ethyl-substituted ammonium cation allows the preparation of an unprecedented oxo- and oxalato-bridged supramolecular three-dimensional network. The compound exhibits magnetic ordering with Tc = 70 K due to a weak spin canting. Julve Olcina, Miguel, Miguel.Julve@uv.es ; Lloret Pastor, Francisco, Francisco.Lloret@uv.es

Aurophilicity as a cofactor in crystal engineering. Dicyanoaurate(I) anion as a building block in a novel Co(II)–Au(I) bimetallic assembly

A 2D grid-shaped cyanide-bridged Co(II)–Au(I) bimetallic coordination polymer, [Co(DMF)2{Au(CN)2}2], has been prepared from the [Au(CN)2]2 building block; sheets associate pair-wise by aurophilic interactions and the compound exhibits zeolite-like properties. Lloret Pastor, Francisco, Francisco.Lloret@uv.es

Field-Induced Slow Magnetic Relaxation in a Mononuclear Manganese(III)-Porphyrin Complex

We report on a novel manganese(III)-porphyrin complex with the formula [Mn(III) (TPP)(3,5-Me2 pyNO)2 ]ClO4 ⋅CH3 CN (2; 3,5-Me2 pyNO=3,5-dimethylpyridine N-oxide, H2 TPP=5,10,15,20-tetraphenylporphyrin), in which the Mn(III) ion is six-coordinate with two monodentate 3,5-Me2 pyNO molecules and a tetradentate TPP ligand to build a tetragonally elongated octahedral geometry. The environment in 2 is responsible for the large and negative axial zero-field splitting (D=-3.8 cm(-1) ), low rhombicity (E/|D|=0.04) of the high-spin Mn(III) ion, and, ultimately, for the observation of slow magnetic-relaxation effects (Ea =15.5 cm(-1) at H=1000 G) in this rare example of a manganese-based single-ion ma…

Solution chemistry of N,N'-ethylenebis(salicylideneimine) and its copper(II), nickel(II) and iron(III) complexes

Abstract Potentiometric determination of protonation-deprotonation equilibria of the N,N'-ethylenebis(salicylideneimine) (H2sal2en), the related N-(2-aminoethyl)salicylideneimine, (Hsalen), and their organic fragments, salicylaldehyde (Hsal) and ethylenediamine (en), has been used to study the equilibria involved in the formation of Schiff bases from Hsal, sal− and en and in their complex formation with copper(II), nickel(II) and iron(III) ions in dimethyl sulfoxide (dmso)-water (80:20 wt./wt.) mixture (25 °C and 0.1 mol dm−3 KClO4 ionic strength): en+Hsal⇔Hsalen; en+2Hsal⇔H2sal2en; en+ sal−⇔salen−; en+2sal−⇔sal2en2−; sal−+en+MN+⇔[M(salen)](n−1)+; 2sal−+en+Mn+⇔ [M(sal2en)](n−2)+. In these t…

Field-induced slow magnetic relaxation in pseudooctahedral cobalt(ii) complexes with positive axial and large rhombic anisotropy

The preparation, X-ray crystal structure, spectroscopic and variable-temperature dc and ac magnetic properties of two six-coordinate cobalt(ii) complexes of formula [Co(bim)4(tcm)2] (1) and [Co(bmim)4(tcm)2] (2) (bim = 1-benzylimidazole, bmim = 1-benzyl-2-methylbenzimidazole and tcm- = tricyanomethanide ion) are reported. 1 and 2 crystallize in the monoclinic P21/n and C2/c space groups with the asymmetric units composed of one tcm- ion and half the [Co(bim)4]2+ and [Co(bmim)4]2+ complex cations, respectively. Their cobalt atoms are in compressed (1)/rhombic (2) CoN6 octahedral environments, the axial positions being occupied by monodentate tricyanomethanide anions. The neutral molecules in…

2D and 3D coordination polymers based on 2,2′-bipyrimidine and cyanide bridging ligands incorporating coordinated and guest ammonia molecules. Synthesis, crystal structures, magnetic properties and thermal analysis of {[Ni(CN)4]2[(Ni(NH3)2)2(bpym)]·2H2O}n and {[Cu2(CN)2(bpym)]·NH3}n

The coordination polymers {[Ni(CN)4]2[(Ni(NH3)2)2(bpym)]·2H2O}n1 and {[Cu2(CN)2(bpym)]·NH3}n2 have been prepared from the reactions of M(NO3)2·nH2O [Cu(II), n = 3 and M = Ni(II), n = 6] with NaCN and bpym (2,2′-bipyrimidine) in concentrated aqueous ammonia, respectively. The structure of 1 is made of bipyrimidine bridged centrosymmetric dinuclear [Ni(NH3)2(μ-bpym)Ni(NH3)2] fragments connected by four [Ni(CN)4]2− anions giving rise to a 2D framework. Layers, which adopt a stair-like conformation, are stacked with an ABAB… repeat pattern. Water molecules are located in the interlayer space and are involved in hydrogen bond interactions with the non-bridging cyanide groups of the [Ni(CN)4]2− a…

Cyanido-Bridged {LnIIIWV} Heterobinuclear Complexes: Synthesis and Magneto-Structural Study

A new series of cyanido-bridged {LnIIIWV} heterobinuclear complexes of formula [LnIII(pyim)2(i-PrOH)(H2O)2(μ-CN)WV(CN)7]·2H2O [Ln = Gd (1), Tb (2), Dy (3), Ho (4), and Er (5); pyim = 2-(1H-imidazol-2-yl)-pyridine) and i-PrOH = isopropyl alcohol] were synthesized by one-pot reaction between (NH3Bu)3[W(CN)8] and [Ln(pyim)2]2+ complexes (generated in situ by mixing the corresponding LnIII ions and the pyim ligand). Compounds 1–5 are isomorphous and crystallize in the monoclinic system P21/n space group. Their crystal structure consists of binuclear units in which the octacyanotungstate(V) anion coordinates to the corresponding LnIII ion through a single cyanide ligand. The tungsten(V) and lant…

One‐Dimensional Coordination Polymers of Mn II , Cu II , and Zn II Supported by Carboxylate‐Appended (2‐Pyridyl)alkylamine Ligands – Structure and Magnetism

Four new complexes [MnII(L1OO)(H2O)][ClO4]·2H2O (1), [ZnII(L1OO)][ClO4]·2H2O (2), [CuII(L3OO)][CF3SO3]·H2O (3), and [ZnII(L3OO)][ClO4] (4) (L1OO– = 3-[(2-(pyridine-2-yl)ethyl){2-(pyridine-2-yl)methyl}amino]propionate; L3OO– = 3-[(2-(pyridine-2-yl)ethyl){(dimethylamino)ethyl}amino]propionate) have been synthesized and characterized by elemental analysis, IR, and UV/Vis spectroscopy. Structural analysis revealed that 1, 3, and 4 are one-dimensional chain-like coordination polymers. In 1 distorted octahedral MnN3O3 and in 3 square-pyramidal CuN3O2 coordination is satisfied by three nitrogen atoms and an appended carboxylate oxygen atom of the ligand, and an oxygen atom belonging to the carboxy…

Theoretical Insights into the Ferromagnetic Coupling in Oxalato-Bridged Chromium(III)-Cobalt(II) and Chromium(III)-Manganese(II) Dinuclear Complexes with Aromatic Diimine Ligands

Two novel heterobimetallic complexes of formula [Cr(bpy)(ox)(2)Co(Me(2)phen)(H(2)O)(2)][Cr(bpy)(ox)(2)]·4H(2)O (1) and [Cr(phen)(ox)(2)Mn(phen)(H(2)O)(2)][Cr(phen)(ox)(2)]·H(2)O (2) (bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, and Me(2)phen = 2,9-dimethyl-1,10-phenanthroline) have been obtained through the "complex-as-ligand/complex-as-metal" strategy by using Ph(4)P[CrL(ox)(2)]·H(2)O (L = bpy and phen) and [ML'(H(2)O)(4)](NO(3))(2) (M = Co and Mn; L' = phen and Me(2)phen) as precursors. The X-ray crystal structures of 1 and 2 consist of bis(oxalato)chromate(III) mononuclear anions, [Cr(III)L(ox)(2)](-), and oxalato-bridged chromium(III)-cobalt(II) and chromium(III)-manganese(II) din…

Synthesis, crystal structure, thermal and magnetic properties of [Mn(H2O)6][Cu(pdta).2H2O (pdta= 1,3-propylenediamine-N,N,N',N'-tetraacetate

[EN] On mixing concentrated aqueous solutions of pdta, Cu(II) and Mn(II) in the ratio 1:1:1 at pH 4.5, single crystals of the complex [Mn(H2O)6][Cu(pdta)]·2H2O (1) (pdta=1,3-propylenediamine-N,N,N'N'-tetraacetate) were obtained. X-ray structural analysis revealed that in the anion [Cu(pdta)]2- the coordination polyhedron around the Cu(II) ion can be described as a tetragonaly distorted CuN2O4 octahedron, whereas the cation [Mn(H2O)6]2+ can be described as a very regular MnO6 octahedron. Thermogravimetric analysis shows that at 110°C compound 1 loses its eight water molecules yielding the anhydrous compound [MnCu(pdta)] (2). Variable-temperature magnetic susceptibility measurements indicate …

Spin Crossover in Double Salts Containing Six- and Four-Coordinate Cobalt(II) Ions

The preparation and spectroscopic and structural characterization of three cobalt(II) complexes of formulas [Co(tppz)2](dca)2 (1), [Co(tppz)2][Co(NCS)4]·MeOH (2), and [Co(tppz)2][Co(NCO)4]·2H2O (3) [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine and dca = dicyanamide] are reported here. Compounds 1–3 have in common the presence of the cationic [Co(tppz)2]2+ entity where each mer-tridentate tppz ligand coordinates to the cobalt(II) ion equatorially through two pyridyl donors and axially via the pyrazine, completing the six-coordination. The electroneutrality is achieved by the organic dca group (1) and the anionic tetrakis(thiocyanato-κN)cobaltate(II) (2) and tetrakis(cyanato-κN)cobaltate(II) (3…

Influence of the pyrazine substituent on the structure and magnetic properties of dicyanamide-bridged cobalt(ii) complexes.

Substituted pyrazines were successfully used to prepare two new coordination polymers of formulas {[Co(dca)2(NH2pyz)2]·H2O}n (1) and [Co3(dca)6(HOpyz)5(H2O)2]n (2) [dca = dicyanamide, NH2pyz = 2-aminopyrazine and HOpyz = 2-hydroxypyrazine] whose structures were determined by single-crystal X-ray crystallography. The structure of 1 consists of a two-dimensional rhombus grid of cobalt(II) ions where the dca ligand adopts the μ1,5 bridging mode with trans-positioned monodentate NH2pyz molecules completing the six-coordination around each metal ion. Compound 2 exhibits a stair-like two-dimensional structure where the intralayer connections are performed by the dca and HOpyz groups exhibiting μ1…

Cyanide-bridged iron(III)-cobalt(II) double zigzag ferromagnetic chains: two new molecular magnetic nanowires.

and opened the perspective of a potential useof 1D magnetic molecular nanowires for information storage.Even though 1D magnetism is a very active area of research,such dynamic behavior was never detected before since it isnot clear how to fulfill experimentally the requirements of aperfect 1D Ising-type chain. This finding prompted us to lookcarefully at 1D systems containing anisotropic elements,suchas cobalt(ii) and low-spin iron(iii) centers that we synthesizedrecently,

Tuning up the Tc in Mn(II)Cu(II) bimetallic planes and design of molecular-based magnets

Abstract A family of related compounds of general formula (PPh4)2Mn2[Cu((L)]3nH2O, where PPh4+ is the tetraphenylphosphonium cation and L stands for ortho-phenylenebis(oxamate) (opba, 1), ortho-phenylene (N′-methyloxamidate) (oxamate) (Meopba, 2) and ortho-phenylenebis (N′-methyloxamidate) (Me2opba, 3), have been synthesized. The X-ray absorption near-edge structure (XANES) and extended X-ray Within absorption fine structure (EXAFS) spectra at both Mn and Cu K-edges for all three compounds, as well as their powder X-ray patterns, are consistent with a layered structure built up of parallel Mn11Cu11 two-dimensional honeycomb networks separated by PPh4+ cations. Within the antonic metallic la…

Chromium(III) complexes with 2-(2′-pyridyl)imidazole: Synthesis, crystal structure and magnetic properties

Abstract The preparation, crystal structure and variable temperature-magnetic investigation of three 2-(2′-pyridyl)imidazole-containing chromium(III) complexes of formula PPh4[Cr(pyim)(C2O4)2]·H2O (1), AsPh4[Cr(pyim)(C2O4)2]·H2O (2) and [Cr2(pyim)2(C2O4)2(OH2)2]·2pyim · 6H2O (3) [pyim = 2-(2′-pyridyl)imidazole, C 2 O 4 2 - = dianion of oxalic acid , PPh 4 + = tetraphenylphosphonium cation and AsPh 4 + = tetraphenylarsonium cation ] are reported herein. The isomorphous compounds are made up of discrete [Cr(pyim)(C2O4)2]− anions, XPh 4 + cations [X = P (1) and As (2)] and uncoordinated water molecules. The chromium environment in 1 and 2 is distorted octahedral with Cr–N and Cr–O bond distanc…

Copper(II) complexes of 1,4,5,8,9,12-hexaazatriphenylene with oxalate, squarate, perchlorate as auxiliary ligands or counter ion

Abstract The crystal structures of [Cu(hat)(H2O)(ox)]·H2O (I), [Cu(hat)(H2O)3(sq)]·3H2O (II) and [Cu(hat)(H2O)2](ClO4)2·4H2O (III) have been determined from X-ray single crystal diffraction data (hat=1,4,5,8,9,12-hexaazatriphenylene, ox=oxalate, sq=squarate=dianion of 3,4-dihydroxy-cyclobut-3-ene-1,2-dione). Compound I crystallises in the triclinic system, space group P 1 with a=6.6626(10), b=9.2001(14), c=12.9954(19) A , α=103.301(15), β=91.414(21), γ=105.523(13)°, Z=2; compound II in the orthorhombic system, space group P212121 with a=6.9274(2), b=8.4327(3), c=34.0577(14) A , Z=4; and compound III in the monoclinic system, space group C2/c with a=22.6652(10), b=9.2220(10), c=16.1400(10) A…

The crystal structure and magnetic properties of 3-pyridinecarboxylate-bridged Re(ii)M(ii) complexes (M = Cu, Ni, Co and Mn)

The novel Re(II) complex NBu4[Re(NO)Br4(Hnic)] (1) and the heterodinuclear compounds [Re(NO)Br4(μ-nic)Ni(dmphen)2]·½CH3CN (2), [Re(NO)Br4(μ-nic)Co(dmphen)2]·½MeOH (3), [Re(NO)Br4(μ-nic)Mn(dmphen)(H2O)2]·dmphen (4), [Re(NO)Br4(μ-nic)Cu(bipy)2] (5) [Re(NO)Br4(μ-nic)Cu(dmphen)2] (5') (NBu4(+) = tetra-n-butylammonium cation, Hnic = 3-pyridinecarboxylic acid, dmphen = 2,9-dimethyl-1,10-phenanthroline, bipy = 2,2'-bipyridine) have been prepared and the structures of 1-5 determined using single crystal X-ray diffraction. The structure of 1 consists of [Re(NO)Br4(Hnic)](-) anions and NBu4(+) cations. Each Re(II) is six-coordinate with four bromide ligands, a linear nitrosyl group and a nitrogen ato…

Chemistry and reactivity of dinuclear manganese oxamate complexes: Aerobic catechol oxidation catalyzed by high-valent bis(oxo)-bridged dimanganese(IV) complexes with a homologous series of binucleating 4,5-disubstituted-o-phennylenedioxamate ligands

[EN] The high-valent bis(oxo)-bridged dimanganese(IV) complexes with the series of binucleating 4.5-X-2-o-phenylenebis(oxamate) ligands (opbaX(2); X = H, Cl, Me) (1a-c) have been synthesized and characterized structurally, spectroscopically and magnetically. Complexes la-c possess unique Mn-2(mu-O)(2) core structures with two o-phenylenediamidate type additional bridges which lead to exceptionally short Mn-Mn distances (2.63-2.65 angstrom) and fairly bent Mn-O-Mn angles (94.1 degrees-94.6 degrees). The cyclovoltammograms of la-c in acetonitrile (25 degrees C, 0.1 M Bu4NPF6) show an irreversible one-electron oxidation peak at moderately high anodic potentials (E-ap = 0.50-0.85 V versus SCE),…

An Azide-Bridged Copper(II) Ferromagnetic Chain Compound Exhibiting Metamagnetic Behavior

The one-dimensional chain complex [Cu(2)(mgr;(2)-1,1-N(3))(2)(mgr;(2)-1,3-NO(3))(2)(mgr;(2)-1,3-Me(3)NCH(2)CO(2))(2)](n)() (1) contains three different bridge groups,mgr;(2)-1,1-azide (end-on),mgr;(2)-nitrate, andmgr;(2)-syn,syn-carboxylate, arranged so that the azide and carboxylate groups bridge equatorially and dictate the intrachain magnetic behavior between the copper magnetic orbitals. Variable-temperature magnetic susceptibility studies at low field, and magnetization studies at variable field, reveal dominant intrachain ferromagnetism (J = 26 cm(-)(1)) but also much weaker interchain ferromagnetism (THETAV; = 2.3 K) and antiferromagnetism (J(eff) = -0.18 cm(-)(1)). The structure has…

Unprecedented coexistence of cyano-bridged Mn4(III)Cr(III) and Mn2(III)Cr(III) heterobimetallic complexes in one single crystal.

The penta-[{MnIII(4-MeO-salen)(H2O)(micro-CN)}4CrIII(CN)2]+ and trinuclear [{MnIII(4-MeO-salen)(H2O)(micro-CN)}2CrIII(CN)4](-) units coexist in 1 with weak antiferromagnetic interactions which are overcome by a dc magnetic field of 2.5 T.

A novel octacyanido dicobalt(iii) building block for the construction of heterometallic compounds

The first bimetallic octacyanido complex of CoIII, (PPh4)2[Co2(μ-2,5-dpp)(CN)8] (1), was synthesized and used as a metalloligand with [Mn(MAC)(H2O)2]Cl2·4H2O to give a new {CoIIIMnII} heterometallic chain of formula [MnII(MAC)(μ-NC)2Co2III(μ-2,5-dpp)(CN)6]n·7nH2O (2) (PPh4+ = tetraphenylphosphonium cation; 2,5-dpp = 2,5-bis(2-pyridyl)pyrazine and MAC = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo-[12.3.1]octadeca-1(18),2,12,14,16-pentaene). Both compounds were characterized by single-crystal X-ray diffraction. Compound 1 contains a diamagnetic 2,5-dpp-bridged dicobalt(III) unit with four peripheral cyanide ligands at each cobalt center achieving a six-coordinate surrounding, the electroneutral…

Synthesis, crystal structure and magnetic properties of the chiral iron(II) chain [Fe(bpym)(NCS)2]n (bpym = 2,2′-bipyrimidine)

Abstract The iron(II) compound of formula [Fe(bpym)(NCS)2]n (bpym = 2,2′-bipyrimidine) has been synthesized and its crystal structure determined by X-ray diffraction methods. It crystallizes in the tetragonal P41 (No. 76) and P43 space groups, a = 8.849(2), c=16.486(3) A , V=1290.9(5) A 3 , Z=4, D c =1.699 g cm −3 , M r =330.2, F(000)=664, λ( Mo K α)=0.71073 A , μ( Mo K α)=14.8 cm −1 and T=295 K. A total of 2449 reflections was collected over the range 3≤2ϑ≤55°; of these, 1657 were unique and 1321 were considered as observed (13σ(I)) and used in the structural analysis. The final R and Rw residuals were 0.027 and 0.026, respectively. The structure is made up of chiral (Δ and Λ enantiomers c…

Building-up host-guest helicate motifs and chains: a magneto-structural study of new field-induced cobalt-based single-ion magnets.

In this work, we present the synthetic pathway, a refined structural description, complete solid-state characterization and the magnetic properties of four new cobalt(II) compounds of formulas [Co(H2O)6][Co2(H2mpba)3]·2H2O·0.5dmso (1), [Co(H2O)6][Co2(H2mpba)3]·3H2O·0.5dpss (2), [Co2(H2mpba)2(H2O)4]n·4nH2O (3), and [Co2(H2mpba)2(CH3OH)2(H2O)2]n·0.5nH2O·2ndpss (4) [dpss = 2,2′-dipyridyldisulfide and H4mpba = 1,3-phenylenebis(oxamic) acid], where 2 and 4 were obtained from [Co(dpss)Cl2] (Pre-I) as the source of cobalt(II). All four compounds are air-stable and were prepared under ambient conditions. 1 and 2 were obtained from a slow diffusion method [cobalt(II) : H2mpba2− molar ratio used 1 : …

Study of the complex formation between the [Cu(bpca)]+ secondary building unit and the aromatic N donors 2,3,5,6-tetra(2-pyridyl)pyrazine (tppz) and 1,3-bis(4-pyridyl)propane (bpp)

Two new complexes of the formula [{Cu(bpca)}2(μ-tppz)](NO3)2·5H2O (1) and [Cu(bpca)(H2O)(ClO4)(μ-bpp)Cu(bpca)(H2O)2]ClO4·H2O (2) [tppz = 2,3,5,6-tetra(2-pyridyl)pyrazine and bpp = 1,3-bis(4-pyridyl)propane] have been prepared by the reaction of the [Cu(bpca)]+ [Hbpca = bis(2-pyridylcarbonyl)imide] building block and the tppz and bpp N donors. An unusual coordination mode of the tppz ligand was observed in 1, which functions as a bis(bidentate) ligand to two copper(II) atoms each coordinated to a nitrogen atom of the pyrazine moiety and a pyridyl nitrogen atom. This compound presents a layered structure of alternating anionic (ca. 1.6 A) and cationic (ca. 10 A) slices, providing the opportun…

Molecular Engineering To Control the Magnetic Interaction between Single-Chain Magnets Assembled in a Two-Dimensional Network

International audience; Two two-dimensional (2D) systems having the formula [{Fe-III(dmbpy)(CN)(4)}(2)(CoL)-L-II](n) [L = pyetNO (1), tvpNO (2)] and consisting of single-chain magnets connected through organic ligands (L) have been prepared, and their magnetic properties have been investigated. The overall magnetic behavior depends on the capacity of the organic pillars to transmit long-range magnetic interactions. 1 is the first example of a 2D compound exhibiting double relaxation of the magnetization, whereas 2 behaves as a metamagnet.

A Chiral, Photoluminescent, and Spin-Canted {Cu(I)Re(IV)2}n Branched Chain.

A new heteroleptic 1D Cu(I)-Re(IV) coordination polymer of the formula {Cu(I)Re(IV)Cl4(μ-Cl)(μ-pyz)[Re(IV)Cl4(μ-bpym)]}n·nMeNO2 (1; pyz = pyrazine, bpym = 2,2'-bipyrimidine) has been prepared through the Cu(I)-mediated self-assembly of two different Re(IV) metalloligands, namely, [ReCl5(pyz)](-) and [ReCl4(bpym)]. 1 consists of chiral branched chains with an overall rack-type architecture displaying photoemission and magnetic ordering. These results constitute a first step toward making new multifunctional magnetic materials based on mixed 3d-5d molecular systems.

A Trinuclear Copper(II) Cryptate and Its μ3-CO3 Cascade Complex: Thermodynamics, Structural and Magnetic Properties

The 2,4,6-triethylbenzene-capped hexaamine macrobicycle with pyridyl spacers (pyr) was able to coordinate three copper(II) ions within its cavity. Potentiometric studies performed at 298.2 K in MeOH/H(2)O (50:50 v/v) and at ionic strength 0.10 mol dm(-3) in KNO(3) revealed that trinuclear species predominate in solution from pH 5.0, the hydroxo complexes being the main species, which start forming at unusual very low pH values. The single-crystal X-ray determination of the trinuclear complex showed that the three copper centres have square-planar geometry, arranged in an almost equilateral triangle, and have carbonate bridging the three metal centres. The presence of carbonate resulted from…

Synthesis, crystal structure and magnetic properties of a new cyanide-bridged iron(III)–nickel(II) ferromagnetic chain

Abstract The reaction of the iron(III) unit fac-[Fe{HB(pz)3}(CN)3]− [ HB ( pz ) 3 - = hydrotris ( 1 - pyrazolyl ) borate ] as the lithium salt (1) with the nickel(II) complex mer-[Ni(dpt)(H2O)3](ClO4)2 [dpt = dipropylenetriamine] in water affords the heterometallic compound of formula {[FeIII{HB(pz)3}(CN)3]2[NiII(dpt)]}n · 3nH2O (2). The structure of 2 has been determined by X-ray diffraction on single crystals and their magnetic properties have been investigated in the temperature range 1.9–300 K. Compound 2 is a zigzag chain compound with regular alternating bis-monodentate [Fe(1){HB(pz)3}(CN)3]− units and [Ni(dpt)]2+ cations, the six coordination around the nickel atom being achieved by …

Oxotris(oxalato)niobate(V) as counterion in cobalt(II) spin-crossover systems

Abstract This work is devoted to the investigation of the thermally induced spin-crossover behavior from a high-spin state (HS, S = 3/2) at higher temperatures to a low-spin phase (LS, S = 1/2) at lower temperatures of the six-coordinate cobalt(II) complex in the compound [Co(terpy)2]3[NbO(C2O4)3]2·3CH​3OH·4H2O (2). The crystal structure of 2 together with that of its counterion as tetraphenylarsonium(V) salt (AsPh4)3[NbO(C2O4)3]·9H2O (1) are also included. The spin-crossover process was followed by the thermal variation of the χMT product between 2.0 and 400 K under the warming mode, with the LS configuration being achieved at T ⩽ 200 K and the LS → HS interconversion being incomplete at 4…

A new manganese(III) oxamato dimer possesing an unprecedented Mn2(μ-O2CR)(μ-OH2⋯O2 CR) core has been synthesised, structurally and magnetically characterised, and used as a catalyst for the oxidation of alkanes to alcohols and ketones by ButO2H and O2 in CH2Cl2 at rt.

Three Co(II) Metal-Organic Frameworks with Diverse Architectures for Selective Gas Sorption and Magnetic Studies.

Three Co(II) metal–organic frameworks, namely, {[Co2(L)2(OBA)2(H2O)4]·xG}n (1), {[Co(L)0.5(OBA)]·xG}n (2), and {[Co2(L)2(OBA)2(H2O)]·DMA·xG}n (3) [where L = 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene, H2OBA = 4,4′-oxybisbenzoic acid, DMF = dimethylformamide, DMA = dimethylacetamide, and G denotes disordered guest molecules], have been synthesized under diverse reaction conditions through self-assembly of a bent dicarboxylate and a linear spacer with a Co(II) ion. While 1 is crystallized at room temperature in DMF to form a 2D layer structure, 2 is formed by the assembly of similar components under solvothermal conditions with a 3D network structure. On the other hand, changing the solvent t…

Selective Gas and Vapor Sorption and Magnetic Sensing by an Isoreticular Mixed-Metal–Organic Framework

A novel isoreticular oxamato-based manganese(II)-copper(II) open metal-organic framework H(2)O@iso1 featuring a pillared square/octagonal layer structure with alternating open and closed octagonal pores has been rationally prepared. The open-framework topology is responsible for a large selectivity in the separation of small gas (CO(2) over CH(4)) and vapor molecules (CH(3)OH over CH(3)CN and CH(3)CH(2)OH). H(2)O@iso1 displays a long-range three-dimensional ferromagnetic ordering with a drastic variation of the critical temperature as a function of the guest molecule [T(C)2.0 K (CO(2)@iso1 and CH(4)@iso1) and T(C) = 6.5 (CH(3)OH@iso1) and 21.0 K (H(2)O@iso1)].

Dinuclear copper(II) complexes as testing ground for molecular magnetism theory

Abstract A leitmotiv in the field of molecular magnetism is the study of the electron exchange (EE) magnetic interactions among distant metal centers through the corresponding bridging ligands in polynuclear coordination compounds. The present review provides a historical perspective on the use of dinuclear copper(II) complexes with either simple inorganic or extended organic bridging ligands as experimental and theoretical models for the fundamental research on the relative importance of the spin delocalization and spin polarization mechanisms of the EE interaction across σ- and π-type orbital pathways. Particular focus is placed on the work by Professor Miguel Julve, outstanding researche…

Redox switching of the antiferromagnetic coupling in permethylated dicopper(ii) paracyclophanes

A unique magnetic electroswitching behavior has been observed in an oxamato-based permethylated dicopper(II) paracyclophane; upon reversible one-electron oxidation of the double tetramethyl-substituted p-phenylenediamidate bridging skeleton, the spin alignment of the two Cu(II) ions (S(Cu) = ½) changes from antiparallel (OFF) to parallel (ON) in the resulting dicopper(II) π-radical cation species.

Manganese(II) complexes with croconate and 2-(2-pyridyl)imidazole ligands: Syntheses, X-ray structures and magnetic properties

Abstract The mixed-ligand complexes of manganese(II) of formula [Mn(pyim)2(C5O5)] (1) and [Mn(pyim)(H2O)(C5O5)]n · 2.5nH2O (2) [pyim = 2-(2-pyridyl)imidazole and C 5 O 5 2 -  = croconate (dianion of 4,5-dihydroxy-4-cyclopentene-1,2,3-trione)] have been prepared and their structures determined by X-ray crystallographic methods. Compound 1 is a tris-chelated mononuclear complex where the manganese atom is six-coordinate: four nitrogen atoms from two pyim molecules and two oxygen atoms from a croconate group build a somewhat distorted octahedral surrounding around the metal atom. The resulting neutral mononuclear units are linked to each other through double bridges which are constituted by th…

Three one-dimensional systems with end-to-end dicyanamide bridges between copper(ii) centres: structural and magnetic properties

The preparation, crystal structures and magnetic properties of three different copper(II) chains of formula [Cu(pyim)(H2O)(dca)]n(NO3)n (1), [Cu(dpa)(dca)2]n (2) and [Cu(bpa)(dca)2]n (3) [pyim = 2-(2-pyridyl)imidazole, dca = dicyanamide anion, dpa = 2,2′-dipyridylamine and bpa = 1,2-bis(4-pyridyl)ethane] are reported. A chain structure with single, symmetrical, end-to-end dca bridges is found in compound 1. This bridging mode, with two short, equatorially coordinated Cu–N bonds has not been previously observed in the [Cu(dca)Xn] (X = coligand) family of compounds. The copper atom in 1 has a distorted square pyramidal geometry with a bidentate pyim ligand and two nitrile nitrogen atoms from …

A Rational Design for Imidazolate-Bridged Linear Trinuclear Compounds from Mononuclear Copper(II) Complexes with 2-[((Imidazol-2-ylmethylidene)amino)ethyl]pyridine (HL):  Syntheses, Structures, and Magnetic Properties of [Cu(L)(hfac)M(hfac)2Cu(hfac)(L)] (M = ZnII, CuII, MnII)

Two mononuclear copper(II) complexes with the unsymmetrical tridentate ligand 2-[((imidazol-2-ylmethylidene)amino)ethyl]pyridine (HL), [Cu(HL)(H2O)](ClO4)2.2H2O (1) and [Cu(HL)Cl2] (2), have been prepared and characterized. The X-ray analysis of 2 revealed that the copper(II) ion assumes a pentacoordinated square pyramidal geometry with an N3Cl2 donor set. When 1 and 2 are treated with an equimolecular amount of potassium hydroxide, the deprotonation of the imidazole moiety promotes a self-assembled process, by coordination of the imidazolate nitrogen atom to a Cu(II) center of an adjacent unit, leading to the polynuclear complexes [[Cu(L)(H2O)](ClO4)]n (3) and [[Cu(L)Cl].2H2O]n (4). Variab…

Synthesis and characterization of binuclear μ-oxalato nickel(II), copper(II) and zinc(II) complexes with 3,3′-diamino-N-methyl-dipropylamine or trans-1,2-diaminocyclohexane

Abstract New binuclear complexes of the type [(Ni(Medpt)NO3)2ox] (1) (Medpt=3,3′-diamino-N-methyl-dipropylamine, H2ox=oxalic acid), [(Ni(dach)2)2ox]NO3·2H2O (2) (dach=trans-1,2-diaminocyclohexane), [(Cu(Medpt))2ox]X2·yH2O (X=NO3, y=2 2/3 (3); X=ClO4, y=0 (4)) and [(Zn(dach)2)2ox](ClO4)2·2H2O (5) have been prepared and characterized by IR and UV–Vis spectroscopies. Spectroscopic data are consistent with oxalate-bridged structures between six-coordinated (N3O3 or N4O2) Ni(II) (compounds 1 or 2), five-coordinated (N3O2) Cu(II) (compounds 3 and 4) or six-coordinated (N4O2) Zn(II) (compound 5). The crystal structure of [(Cu(Medpt))2ox](NO3)2·2 2/3 H2O (3) has been determined by single-crystal X-…

Crystal structure and magnetic properties of the flexible self-assembled two-dimensional square network complex [Cu2(mal)2(H2O)2(4,4′-bpy)] (H2mal=malonic acid and 4,4′-bpy=4,4′-bipyridine)

Abstract The copper(II) complex [Cu 2 (mal) 2 (H 2 O) 2 (4,4′-bpy)] ( 1 ) (H 2 mal=malonic acid and 4,4′-bpy=4,4′-bipyridine) has been prepared and its structure determined by single crystal X-diffraction methods. Compound 1 has a two-dimensional square grid network structure. The square grids are stacked parallel but in a staggered manner on each other along the c -axis, with an interlayer separation of 3.850(1) A. Each layer contains a large cavity of 15.784(1)×15.784(1) A with each edge shared by one malonate group and one 4,4′-bpy ligand and a small planar square of 4.644(1)×4.644(1) A with Cu(II) ions and malonate groups at each corner and side, respectively. Each copper atom is in a d…

Syntheses, crystal structures and magnetic properties of mono- and polynuclear [bis(2-arylcarbonyl)amidate]copper(II) complexes

Abstract Five copper(II) complexes of formulas [Cu(bpcam)(CN)(H2O)] (1), [Cu(bpcam)(N3)(H2O)]2 (2), [Cu(bpcam)(NCS)(H2O)] (3), [Cu(bpcam)(dca)(H2O)]2 (4) and [Cu(bpca)(tcm)]n (5) [bpcam = bis(2-pyrimidylcarbonyl)amidate, bpca = bis(2-pyridylcarbonyl)amidate, dca = dicyanamide and tcm = tricyanomethanide] have been prepared and their structures determined by single crystal X-ray diffraction. Compounds 1 and 3 are mononuclear species where each copper atom is five coordinated with a tridentate bpcam and a terminally bound cyanide (1)/thiocyanate (3) ligands creating a basal plane with a water molecule in the axial position of a distorted square pyramid. Compound 2 is made of neutral di-μ-1,1-…

Isostructural Dinuclear Phenoxo-/Acetato-Bridged Manganese(II), Cobalt(II), and Zinc(II) Complexes with Labile Sites: Kinetics of Transesterification of 2-Hydroxypropyl-p-nitrophenylphosphate

Using the dinucleating phenol-based ligand 2,6-bis[3-(pyridin-2-yl)pyrazol-1-ylmethyl]-4-methylphenol] (HL(2)), in its deprotonated form, the six new dinuclear complexes [M(II)(2)(L(2))(μ-O(2)CMe)(2)(MeCN)(2)][PF(6)] (M = Mn (2a), Co (3a), Zn (4a)) and [M(II)(2)(L(2))(μ-O(2)CMe)(2)(MeCN)(2)][BPh(4)] (M = Mn (2b), Co (3b), Zn (4b)) have been synthesized. Crystallographic analyses on 2b·2MeCN, 3b·2MeCN, and 4b·2MeCN reveal that these complexes have closely similar μ-phenoxo bis(μ-carboxylato) structures. The physicochemical properties (absorption and ESI-MS spectral data, 2a,b, 3a,b, and 4a,b; (1)H NMR, 4a,b) of the cations of 2a-4a are identical with those of 2b-4b. Each metal ion is termina…

Dicopper(II) Metallacyclophanes as Multifunctional Magnetic Devices: A Joint Experimental and Computational Study

Metallosupramolecular complexes constitute an important advance in the emerging fields of molecular spintronics and quantum computation and a useful platform in the development of active components of spintronic circuits and quantum computers for applications in information processing and storage. The external control of chemical reactivity (electro- and photochemical) and physical properties (electronic and magnetic) in metallosupramolecular complexes is a current challenge in supramolecular coordination chemistry, which lies at the interface of several other supramolecular disciplines, including electro-, photo-, and magnetochemistry. The specific control of current flow or spin delocaliz…

Solid-State Molecular Nanomagnet Inclusion into a Magnetic Metal-Organic Framework: Interplay of the Magnetic Properties.

Single-ion magnets (SIMs) are the smallest possible magnetic devices and are a controllable, bottom-up approach to nanoscale magnetism with potential applications in quantum computing and high-density information storage. In this work, we take advantage of the promising, but yet insufficiently explored, solid-state chemistry of metal-organic frameworks (MOFs) to report the single-crystal to single-crystal inclusion of such molecular nanomagnets within the pores of a magnetic MOF. The resulting host-guest supramolecular aggregate is used as a playground in the first in-depth study on the interplay between the internal magnetic field created by the long-range magnetic ordering of the structur…

Magnetism in Heterobimetallic and Heterotrimetallic Chains Based on the Use of [W V (bipy)(CN) 6 ] – as a Metalloligand

Magnetic Properties of a New Hexahalorhenate(IV) Compound and Structural Comparison with Its Hexahaloplatinate(IV) Analog

New alkoxo-bridged mixed-valence cobalt clusters: Synthesis, crystal structures and magnetic properties

Two new Co II /Co III complexes, [{Co II Co III (mea) 3 } 2 (bpe) 3 ](ClO 4 ) 4  · 1.5CH 3 OH · 1.5H 2 O ( 1 ) and [ Co 4 II Co 3 III ( dea ) 6 ( CH 3 COO ) 3 ] ( ClO 4 ) 0.75 ( CH 3 COO ) 1.25 · 0.5 H 2 O ( 2 ) [Hmea = monoethanolamine H 2 dea = diethanolamine and bpe = 1,2-bis(4-pyridyl)ethane], have been obtained by reacting cobalt(II) perchlorate ( 1 and 2 ), Hmea ( 1 )/H 2 dea ( 2 ), bpe ( 1 ) and sodium acetate ( 2 ). The crystal structures of 1 and 2 have been solved by single crystal X-ray diffraction. Crystal 1 contains “Chinese lantern”-like shaped cations, resulting by connecting two {Co II Co III (mea) 3 } moieties with three flexible bpe ligands. The coordination sphere of the …

Topological Versatility of Oxalate-Based Bimetallic One-Dimensional (1D) Compounds Associated with Ammonium Cations

A new family of oxalate-bridged chains of formula (C(1))[Mn(H(2)O)(3)Cr(ox)(3)]·H(2)O (1), (C(2))(4)[Mn(2)(H(2)O)(3)ClCr(2)(ox)(6)]Cl·H(2)O·2C(2)H(6)O (2a), (C(2))(4)[Co(2)(H(2)O)(3)ClCr(2)(ox)(6)]Cl·2H(2)O·2C(2)H(6)O (2b), [Mn(C(3))(H(2)O)(2)Cr(ox)(3)]·H(2)O (3), and (C(4))(4)[Mn(H(2)O){Cr(ox)(3)}(2)]·H(2)O (4) [C(1)(+) = tetramethylammonium, C(2)(+) = 4-N,N-dimethylaminopyridinium, C(3)(+) = 1-hydroxyethyl-4-N,N-dimethylamino-pyridinium, C(4)(+) = 1-hydroxyethyl-4-(4'-dimethylamino-α-styryl)-pyridinium, ox(2-) = oxalate] have been synthesized by self-assembly of the (C(n))(3)[Cr(ox)(3)] (n = 1-4) mononuclear compound and the chloride salts of the corresponding metal(II) ions. The crystal …

High-temperature spin crossover in a mononuclear six-coordinate cobalt(II) complex.

The six-coordinate cobalt(II) complex of formula [Co(tppz)2](tcm)2 exhibits a thermally induced spin-crossover behavior from a high spin (S = 3/2) at higher temperatures to a low spin (S = 1/2) at lower temperatures, with the low-spin phase being achieved at T ≤ 200 K.

Synthesis, crystal structure and magnetic properties of a cyanide-bridged heterometallic {CoIIMnIII} chain

The assembly reaction between the low-spin [CoII(dmphen)(CN)3]- metalloligand and the [MnIII(salen)(H2O)]+ complex cation yielded the one-dimensional compound {[MnIII(salen)(μ-NC)2CoII(dmphen)(CN)]·2H2O}n (1), which behaves as a ferrimagnetic chain, the intrachain magnetic coupling being J = -1.71(1) cm-1.

Dimeric Mn(ii), Co(ii), Ni(ii) and Cu(ii) complexes of a common carboxylate-appended (2-pyridyl)alkylamine ligand: structure, magnetism and DFT study

Four new complexes of composition [MII2(L3)2(CH3OH)2](ClO4)2 (M = Mn, 1; Co, 2; Ni, 3) and [CuII2(L3)2](ClO4)2 (4) (L3(−) = 3-[2-(((6-methyl)pyridin-2-yl)methyl){(dimethylamino)ethyl}-amino]propionate) have been synthesized and characterized. Structural analysis reveals that 1–4 are discrete syn–anti carboxylate-bridged binuclear coordination complexes with a {MII2(–O–C–O–)2}2+ structural motif. In 1–3 distorted octahedral MN3O3 and in 4 distorted square pyramidal CuN3O2 coordination is satisfied at each M(II) center by three N (a pyridyl and two tertiary aliphatic amines) and a carboxylate O of the ligand, and an O of the carboxylate group. In 1–3 the M(II) center is also coordinated by a …

Spin Polarization and Ferromagnetism in Two-Dimensional Sheetlike Cobalt(II) Polymers: [Co(L)2(NCS)2] (L=Pyrimidine or Pyrazine)

Polynuclear copper(II) complexes with μ2-1,1-azide bridges. Structural and magnetic properties

Abstract Two novel, weakly antiferromagnetically coupled, tetranuclear copper(II) complexes [Cu4(PAP)2(μ2-1,1-N3)2(μ2-1,3-N3)2(μ2-CH3OH)2(N3)4 (1) (PAP = 1,4-bis-(2′-pyridylamino)phthalazine) and [Cu4(PAP3Me)2 (μ2-1,1-N3)2(μ2-1,3-N3)2(H2O)2(NO2)2]- (NO3)2 (2) (PAP3Me = 1,4-bis-(3′-methyl-2′-pyridyl)aminophthalazine) contain a unique structural with two μ2-1,1-azide intramolecular bridges, and two μ2-1,3-azide intermolecular bridges linking pairs of copper(II) centers. Four terminal azide groups complete the five-coordinate structures in 1, while two terminal waters and two nitrates complete the coordination spheres in 2. The dinuclear complexes [Cu2(PPD)(μ2-1,1-N3)(N3)2(CF3SO3)]CH3OH) (3) a…

Dicopper(II) metallacyclophanes with photoswitchable oligoacene spacers: a joint experimental and computational study on molecular magnetic photoswitches

Dinuclear copper(II) complexes of the metallacyclophane-type, (nBu4N)4[Cu2(2,6-anba)2] (1) and (nBu4N)4[Cu2(1,5-naba)2]·4H2O (2) with photoactive 2,6-anthracene-(2,6-anba) and 1,5-naphthalenebis(oxamate) (1,5-naba) bridging ligands, are reported. They undergo a thermally reversible, solid-state photomagnetic (ON/OFF) switching between the moderately strong antiferromagnetically coupled dicopper(II) species and the corresponding magnetically uncoupled [4+4] photocycloaddition product. Density functional calculations give further insights on the intramolecular (“pseudo-bimolecular”) photocycloaddition reaction of the two facing 2,6-anthracene or 1,5-naphthalene spacers in this novel family of…

Synthesis, crystal structure and magnetic characterization of a series of CuII-LnIII heterometallic [Ln = La, Ce, Pr, Nd and Sm) metal-organic compounds with an unusual single crystal to single crystal phase transition

The synthesis and structural characterization of five Cu(II)-Ln(III) heteronuclear metal-organic frameworks of formula {[Ln4Cu 4(H2O)26(bta)5]·mH 2O}n and {[Ln4Cu4(H 2O)24(bta)5]·pH2O} n [Ln = LaIII (1A/1B), CeIII (2A/2B), Pr III (3A/3B), NdIII (4A/4B) and SmIII (5A/5B) with m/p = 20 (1A)/16 (1B), 18 (2A)/16 (2B), 14 (3A)/16 (3B), 22 (4A)/16 (4B) and 21 (5A)/14 (5B); H4bta =1,2,4,5-benzenetetracarboxylic acid (1-5)] have been performed. These compounds present a single-crystal to single-crystal phase transition from expanded A phases toward the B shrinking networks, which is triggered only in the presence of a dry environment. This phase transition is accompanied by a compression of the cry…

Binuclear Nickel(II) Complexes Based on Bridging Oxalate and Pseudohalides as Peripheral Ligands: Synthesis, Crystal Structure, DFT Calculations and Magnetic Properties of [{Ni(X)(dien)}2(μ-ox)]·nH2O Complexes (X = N3−, NCS−,n= 0; NCO−,n= 1)

Nickel(II) molecular complexes were obtained by water displacement reactions of [{Ni(dien)(H2O)}2(μ-ox)]Cl2 and the corresponding pseudohalide. The three nickel(II) compounds [{Ni(N3)(dien)}2(μ-ox)] (1), [{Ni(NCO)(dien)}2(μ-ox)] · H2O (2) and [{Ni(NCS)(dien)}2(μ-ox)] (3) are almost isostructural. The structure determinations reveal the presence of a binuclear complex with C2h symmetry, where the oxalate ligand is coordinated in a bis(bidentate) fashion to the twofold related nickel atoms. The distorted octahedral environment of each nickel atom is completed by the three nitrogen atoms of the diethylenetriamine ligand in a fac arrangement and one nitrogen atom from a pseudohalide ligand. Mag…

Synthesis, characterization and crystal structure of 2-dicyanomethylene-1,3-bis(ferrocenylmethyl)-1,3-diazolidine

By reaction of N,N′-ethylenebis(ferrocenylmethylamine)1 with tetracyanoethylene in dichloromethane the yellow compound 2-dicyanomethylene-1,3-bis(ferrocenylmethyl)-1,3-diazolidine 2 can be isolated. The single-crystal structure of 2 has been determined. It crystallizes in the non-centrosymmetric trigonal space group P3221, a= 12.255(2), c= 13.831(7)A, Z= 3. Refinement of the atomic parameters by least-squares techniques gave a final R factor of 0.038 (R′= 0.034) for 1782 observed reflections having I > 2.5δ(I). Anomalous values of the bond distances and the vinyl carbon chemical shift in the 13C NMR spectrum of 2 are explained on the basis of a polarization due to a combination of the elect…

A Unique Discrete Tetranuclear Cu′–Cu(N-N)2Cu–Cu′ Copper(II) Complex, Built from a μ3-1,2,4-Triazolato-μ-carboxylato Ligand, as an Effective DNA Cleavage Agent

The title compound, characterized by means of an X-ray structure analysis, represents an easy example of a noncatena "1 + 2 + 1" tetranuclear copper(II) μ(3)-triazolate compound. [Cu(4)(atc)(2)(dien)(4)(ClO(4))(2)](ClO(4))(2)·2H(2)O (1), where H(2)atc = 5-amino-l,2,4-triazole-3-carboxylic acid and dien = diethylenetriamine = 1,4,7-triazaheptane, contains two copper atoms linked by a double diazinic bridge, each of which is further connected to a third and fourth copper atom (Cu') through the triply bridging triazolato ring and the bidentate carboxylato group of the atc(2-) ligands. The copper-copper distances within the tetranuclear unit are Cu-Cu = 4.059 Å, Cu-Cu' = 5.686 and 6.370 Å, and …

Synthesis, crystal structure and magnetic properties of [Cu(bpym)(mal)(H2O)]·6H2O and [Cu2(bpym)(mal)2(H2O)2]·4H2O (bpym=2,2′-bipyrimidine, H2mal=malonic acid)

Abstract Two new mixed-ligand complexes of formula [Cu(bpym)(mal)(H2O)]·6H2O (1) and [Cu2(bpym)(mal)2(H2O)2]·4H2O (2) (bpym=2,2′-bipyrimidine and H2mal=malonic acid) have been synthesised and characterised by X-ray diffraction methods. The crystal structure of 1 consists of mononuclear [Cu(bpym)(mal)(H2O)] units in which the copper atom shows a slightly distorted square-pyramidal environment with two bpym-nitrogen and two malonate-oxygen atoms forming the equatorial plane and a water molecule in the axial position. The structure of 2 is built by centrosymmetric bpym-bridged dinuclear [Cu2(bpym)(mal)2(H2O)2] units, in which the geometry of each Cu(II) ion is similar to that found in 1. Malon…

Synthesis, crystal structure and magnetic properties of the cyclic tetranuclear compound [Cu4(pz)4(hppa)2(H2O)4] [pz = pyrazolate; hppa = R,S-2-hydroxo-2-phenyl-2-(1-pyrazolyl)acetate]

Abstract The synthesis, X-ray structure and magnetic properties of the neutral tetranuclear copper(II) complex of formula [Cu4(pz)4(hppa)2(H2O)4] (1) [Hpz = pyrazole and hppa = R,S-2-hydroxo-2-phenyl-2-(1-pyrazolyl)acetate] are reported. Remarkably, the structure of 1 reveals the presence of the S- and R-forms of the new hppa ligand which is formed in situ in the complex reaction between copper(II), pyrazole and phenylmalonate in water:methanol solvent mixture under ambient conditions. The two crystallographically independent copper(II) ions [Cu(1)/Cu(2)] are five-coordinate in square pyramidal surroundings. Three nitrogen atoms, from two pz groups and one hppa ligand and one oxygen atom of…

Syntheses, X-ray structures, and physicochemical properties of phenoxo-bridged dinuclear nickel(II) complexes: kinetics of transesterification of 2-hydroxypropyl-p-nitrophenylphosphate.

Four dinuclear nickel(II) complexes [Ni(II)(2)(L(1))(O(2)CMe)(2)(H(2)O)(2)][PF(6)].MeOH.3H(2)O (1), [Ni(II)(2)(L(1))(O(2)CMe)(2)(NCS)] (2), [Ni(II)(2)(L(2))(O(2)CMe)(2)(MeOH)(H(2)O)][ClO(4)] (3), and [Ni(II)(2)(L(2))(O(2)CMe)(2)(MeOH)(H(2)O)][BPh(4)].3MeOH.H(2)O (4) have been synthesized [HL(1): 2,6-bis[N-methyl-N-(2-pyridylethyl)amino]-4-methylphenol; HL(2): 2,6-bis[3-(pyridin-2-yl)pyrazol-1-ylmethyl]-4-methylphenol]. Complexes 1, 3, and 4 are new while complex 2 was reported previously by Fenton and co-workers (the structure of 2 was presented but no physicochemical properties of this complex were reported; in this work such studies have been completed). X-ray crystallographic analyses of…

Oxotris(oxalate)niobate(V): An oxalate delivery agent in the design of building blocks

This work concerns the oxalate delivery process that occurs when using (NH4)3[NbO(C2O4)3]·6H2O as a suitable oxalate source in the synthesis of two compounds, [Cu(dmphen)(C2O4)(H2O)] (1) and [{Cu(dmphen)(CH3OH)}2(μ-C2O4)](ClO4)2 (2) (dmphen = 2,9-dimethyl-1,10-phenanthroline). {[Fe{HB(pz)3}(CN)2(μ-CN)]2[{Cu(dmphen)}2(μ-C2O4)]}∙xCH3OH (3) (2.0 ≤ x ≤ 2.4) was obtained by reacting 2 and PPh4[Fe{HB(pz)3}(CN)3]∙H2O [ = tetraphenylphosphonium and = tris(pyrazolyl)borate]. Crystal structures of 1–3 have been determined by single-crystal X-ray diffraction experiments: 1 is a mononuclear trigonal bipyramidal copper(II) species, 2 is a centrosymmetric oxalato-bridged dicopper(II) complex, and 3 consi…

Solid-state dinuclear-to-trinuclear conversion in an oxalato-bridged chromium(III)-cobalt(II) complex as a new route toward single-molecule magnets.

A novel bis(oxalato)chromium(III) salt of a ferromagnetically coupled, oxalato-bridged dinuclear chromium(III)-cobalt(II) complex of formula [CrL(ox)(2)CoL'(H(2)O)(2)][CrL(ox)(2)]·4H(2)O (1) has been self-assembled in solution using different aromatic α,α'-diimines as blocking ligands, such as 2,2'-bipyridine (L = bpy) and 2,9-dimethyl-1,10-phenanthroline (L' = Me(2)phen). Thermal dehydration of 1 leads to an intriguing solid-state reaction between the S = 3/2 Cr(III) anions and the S = 3 Cr(III)Co(II) cations to give a ferromagnetically coupled, oxalato-bridged trinuclear chromium(III)-cobalt(II) complex of formula {[CrL(ox)(2)](2)CoL'} (2). Complex 2 possesses a moderately anisotropic S =…

In situ generation of Ph3PO in cyanido-bridged heterometallic {FeIIILnIII}2 molecular squares (Ln = Eu, Sm)

Two new examples of cyanido-bridged {FeIIILnIII}2 molecular squares, with pyim and PPh3O as capping ligands at the LnIII sites, exhibit weak antiferromagnetic interactions [Ln = Eu (1), Sm (2), pyim = 2-(1H-imidazol-2-yl)pyridine, PPh3PO = triphenylphosphine oxide].

Synthesis, characterisation, crystal structures, and magnetic properties of one-dimensional oxalato-bridged metal(II) complexes with 3-hydroxypyridine and isoquinoline

One-dimensional oxalato-bridged metal(II) compounds of formula [M(-ox)(L)2]n [L = 3-hydroxypyridine (pyOH) or isoquinoline (isq)] have been synthesised and characterised by FT-IR spectroscopy, TG-DTA techniques, variable-temperature magnetic measurements and X-ray diffraction methods. The complexes [M(-ox)(pyOH)2]n [M= Co (1), Ni (2)] are isomorphous and crystallise in the orthorhombic space group Pnab. The compounds [M(-ox)(isq)2]n [M= Co (3), Ni (4), Cu (5)] are also isomorphous and belong to the monoclinic space group C2/c. Crystal structures consist of zig-zag chains in which cis-[M(L)2] 2 + units are sequentially bridged by bis-bidentate oxalato ligands with intrachain M···M distances …

Electroswitching of the single-molecule magnet behaviour in an octahedral spin crossover cobalt(ii) complex with a redox-active pyridinediimine ligand

Thermal-assisted spin crossover and field-induced slow magnetic relaxation coexist in the solid state for the mononuclear cobalt(II) complex with the non-innocent 2,6-bis(N-4-methoxyphenylformimidoyl)pyridine ligand. One-electron oxidation of the paramagnetic low-spin CoII ion (SCo = 1/2) to the diamagnetic low-spin CoIII ion (SCo = 0) leads to the electroswitching of the slow magnetic relaxation in acetonitrile solution.

Oxamidato complexes. Part 4. Electrochemical study of the copper(III)/copper(II) couple in monomeric N,N?-bis(substituent)oxamidatocopper(II) complexes

The electrochemical behaviour of a series of monomeric N,N′-bis(substituent)oxamidato copper(II) complexes of formula Na2[Cu(3,5,3′,5′-X4obbz)]·4H2O [X = Cl (1), Br (2), I (3) and obbz = oxamidobis(benzoato)], Na2-[Cu(obbz)]·4H2O (4), Na2[Cu(5,5′-Me2obbz)]·4H2O (5), Na2[Cu(4,5,4,5′-(MeO)4obbz)]·4H2O(6),Na2[Cu(obp)]· 3.5H2O (7) (obp = oxamidobis(propionato)) and Na2[Cu(pba)]·6H2O (8), [pba = propylenebis(oxamate)] has been investigated by cyclic voltammetry, rotating disk electrode and coulometry in water and dimethylsulphoxide (dmso) solutions. NaNO3 (0.1 M) and n-Bu4NPF6 (0.1 M) were used as supporting electrolytes in H2O and dmso respectively, all solutions being thermostatted at 25 °C. I…

[MIII(bpym)(CN)4]−: a suitable building block to design ferrimagnetic cyano-bridged heterobimetallic chains (M = Fe, Cr; bpym = 2,2′-bypyrimidine)

Two cyano-bridged M(III)Mn(III) [M = Fe () and Cr ()] ferrimagnetic chains are reported; exhibits metamagnetism with two critical fields of 1250 G and 2.0 T which correspond to the overcoming by the applied dc field of the inter- and intrachain magnetic interactions, respectively.

The Cation as a Tool to Get Spin-Canted Three-Dimensional Iron(III) Networks

Alkyl-substituted ammonium cations (X) allow the preparation of a series of spin-canted oxo- and oxalato-bridged three-dimensional iron(III) networks, exhibiting magnetic ordering at T(c) values ranging from 40 to 56 K. The value of T(c) varies with the cation despite the lack of significant structural modifications.

A new ferromagnetically coupled μ-alkoxo–μ-acetato copper(II) trinuclear complex: [Cu3(H2tea)(Htea)(CH3COO)2](ClO4) (H3tea=triethanolamine)

Abstract A μ-alkoxo–μ-acetato trinuclear copper(II) complex, [Cu3(H2tea)(Htea)(CH3COO)2](ClO4) 1, has been synthesized by reacting copper(II) perchlorate, triethanolamine and sodium acetate. The unit cell contains two centrosymmetric, crystallographically independent trinuclear Cu(II) complexes and two ClO 4 - ions. The crystallographically independent trinuclear Cu(II) complexes differ mainly in some of their geometry parameters. The coordination environment of the central copper atom is square-planar, in one trinuclear entity, and elongated octahedral in the other one (in this last case, the coordination number of the central copper atom increases through the semicoordination of an oxygen…

Unprecedented heptacopper(ii) cluster with body-centred anti-prismatic topology. Structure, magnetism and density functional study

Using a (2-pyridyl)ethylamine-appended carboxylate ligand a new cluster [Cu(II)(7)(L)(4)(μ(3)-OH)(2)(H(2)O)(2)(DMF)(2)][ClO(4)](4)·4H(2)O (1) [L(2-): N-{CH(2)CH(2)(2-pyridyl)}(CH(2)CH(2)CO(2))(2)] is synthesized, as a result of 'coordination-driven self-assembly'. The structure of 1 is unique and consists of a centrosymmetric carboxylato- and hydroxo-bridged heptanuclear copper(II) cation, with body-centred anti-prismatic topology. The four crystallographically independent copper(II) centres differ markedly in their coordination geometry. In addition to establishing cluster authenticity, the structural analysis of 1 discloses two notable features. The existence of {Cu(II)(3)(μ(3)-OH)}(5+) c…

Influence of the coligand in the magnetic properties of a series of copper(ii)–phenylmalonate complexes

This work presents a series of layered systems based on phenylmalonate-containing copper(II) complexes and different coligands. Eight compounds [Cu(L)(Phmal)]n where L = pyrimidine (pym, 1) pyrazine (pyz, 2), 3-cyanopyridine (3-CNpy, 3), 4-cyanopyridine (4-CNpy, 4), 3-fluoropyridine (3-Fpy, 5), 3-chloropyridine (3-Clpy, 6), 3-bromopyridine (3-Brpy, 7) and 3-iodopyridine (3-Ipy, 8), have been synthesized and magneto-structurally characterized. The coligands selected not only modify the coordination environment of the metal ion, blocking or extending the polymerization, but also interact with the phenyl ring of the phenylmalonate ligand and dramatically affect the crystal packing through weak…

Molecular magnetism, quo vadis? A historical perspective from a coordination chemist viewpoint☆

Abstract Molecular magnetism has travelled a long way from the pioneering studies on electron exchange and double exchange or spin crossover and valence tautomerism in small oligonuclear complexes, from mono- to di- and tetranuclear species, to the current investigations about magnetic anisotropy and spin dynamics or quantum coherence of simple mono- or large polynuclear complexes, behaving as switchable bistable molecular nanomagnets for potential applications in information data storage and processing. In this review, we focus on the origin and development of the research in the field of molecular magnetism from a coordination chemistry viewpoint, which dates back to the establishment of …

An original 3D coordination polymer constructed from trinuclear nodes and tetracarboxylato spacers

A novel 3D coordination polymer, ∞3[{Cu3(felden)}4(btec)3]·17H2O, has been assembled using cationic trigonal nodes, [CuII3(felden)]3+, generated by a tricompartmental ligand, H3felden, which results from the Schiff condensation reaction between 2,4,6-triformylphloroglucinol and N,N-dimethylethylenediamine. The tetraanion of the 1,2,4,5-benzenetetracaboxylic acid (H4btec) was employed as a spacer. The structure of 1 shows large icosahedral cavities and channels and the magnetic interaction between the copper(II) ions within the triangles is weak and antiferromagnetic.

Tuning the Spin Ground State in Heterononanuclear Nickel(II)−Copper(II) Cylinders with a Triangular Metallacyclophane Core

3 páginas, 2 figuras, 1 gráfico.-- et al.

Ferromagnetic Coupling Through the End-to-End Thiocyanate Bridge in Cobalt(II) and Nickel(II) Chains

The preparation, spectroscopic characterization, and X-ray crystal structure of two novel one-dimensional compounds of formula [MII(tppz)(NCS)(μ-1,3-NCS)]n [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine and M = Co(1) and Ni (2)] are reported. 1 and 2 are isomorphous compounds, and they crystallize in the P21/n space group. Their structures are made up of zigzag chains of cobalt(II) (1) and nickel(II) ions (2) bridged by single end-to-end thiocyanate groups with a tridentate tppz molecule and a terminally bound thiocyanate-N ligand achieving distorted MN5S octahedral surroundings around each metal center. The main source of the distortion of the ideal octahedron is due to the geometrical constr…

A tribute to Professor Juan Faus Payá

International audience; Pas de résumé

A Novel One-Dimensional Cyano-Bridged Ni3Fe2 Ferromagnet Constructed from Bimetallic Molecular Squares

Reaction of the complex [Ni(rac-CTH)](2+) (rac-CTH = rac-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) with [Fe(CN)(6)](3-) leads to a novel cyano-bridged Ni(3)Fe(2) complex, [[Ni(rac-CTH)](3)[Fe(CN)(6)](2)](4). The structure consists of an alternating arrangement of [Fe(CN)(6)Ni(rac-CTH)](2) squares and trans-planar [Ni(rac-CTH)](2+) units bridged by cyanide groups to give a neutral 1D chain running along the a axis. Magnetic measurements reveal the occurrence of ferromagnetic coupling between Fe(III) and Ni(II) ions and 3D magnetic ordering at 3 K due to interchain interactions. Canting of the moments is inferred from the low value of the magnetization of the saturation bel…

The first metamagnetic one-dimensional molecular material with nickel(ii) and end-to-end azido bridges

A novel single azido bridged one-dimensional Ni(II) chain, which represents the first metamagnetic one-dimensional metal–azido system with only end-to-end azido bridges, has been synthesised and characterised by a low temperature magnetic study. Lloret Pastor, Francisco, Francisco.Lloret@uv.es

Solvent-driven dimensionality control in molecular systems containing CuII, 2,2′-bipyridine and an oxamato-based ligand

A discrete dicopper(II) system, [Cu(bipy)(H2mpba)]2·2H2O (1), and its isomeric chain, [Cu(bipy)(H2mpba)]·dmso (2) [bipy = 2,2′-bipyridine and H4mpba = N,N′-1,3-phenylenebis(oxamic acid)], were obtained by modifying the ratio of the H2O–dmso solvent mixture, and their interconversion was also monitored by changing the solvents during the synthesis. The solvents play an essential role in the formation and crystallization of these complexes, presenting different dimensionalities and connectivities. The double deprotonated H2mpba2− adopts the bidentate/monodentate (1) and bis-bidentate (2) bridging modes toward the (2,2′-bipyridyl)copper(II) units affording a dinuclear compound (1) and a linear…

Cover Picture: Cyanide-Bridged Iron(III)–Cobalt(II) Double Zigzag Ferromagnetic Chains: Two New Molecular Magnetic Nanowires (Angew. Chem. Int. Ed. 13/2003)

Hydrogen-bond tuning of ferromagnetic interactions: synthesis, structure and magnetic properties of polynuclear copper(ii) complexes incorporating p-block oxo-anions

The reaction of copper(II) hydroxide with 2,2'-bipyridine (bipy) (1 : 1) in alkaline aqueous solution (pH 14) at room temperature affords the alternating carbonate/hydroxo-bridged copper(II) polymeric chain compound {[Cu3(bipy)3(mu-OH)2(mu-CO3)2].11H2O}n, 1, as determined by single-crystal X-ray diffraction. The structure of 1 is built up from two similar centro-symmetric dinuclear [(bipy)Cu(mu-OH)]2 cores which link together via bridging carbonate groups to mononuclear [(bipy)Cu] fragments to form the chain. Interdigitation of adjacent chains through pi-pi interactions, which involve each bipy ligand, forms sheets that are separated by the water molecules of crystallisation. Variable-tempe…

Synthesis and characterisation of a novel ferrimagnetic chain based on copper(II) and rhenium(IV)

Abstract A novel one-dimensional copper(II)–rhenium(IV) coordination polymer of formula {[ReIVBr4(μ-ox)CuII(pyim)2]·MeCN}n (1) [ox = oxalate anion, pyim = 2-(2′-pyridyl)imidazole] has been prepared and characterised. Powder X-ray diffraction measurements on a sample of 1 support the purity of the bulk sample, whereas single-crystal X-ray diffraction shows that 1 crystallises in the orthorhombic system with space group Pbca. The crystal structure of 1 is made up of [CuII(pyim)2]2+ cations and [ReBr4(ox)]2− anions linked through bridging bromide and oxalate groups, which generate alternating CuII and ReIV chains. Variable-temperature magnetic susceptibility measurements performed on 1 reveal …

Dicopper(II) Metallacyclophanes with N,N'-2,6-Pyridinebis(oxamate): Solution Study, Synthesis, Crystal Structures, and Magnetic Properties.

The complexing ability of copper(II) in solution by the ligand N,N'-2,6-pyridinebis(oxamic acid) (H4mpyba, H4L) was determined through potentiometric and UV-vis spectroscopy at 25 °C and 0.15 M NaCl. The logarithms of the equilibrium constants for its copper(II) complexes according to the eqs 2H2L + 2Cu ⇆ [Cu2(H2L)2], 2H2L + 2Cu ⇆ [Cu2(H2L) (HL)] + H, 2H2L + 2Cu ⇆ [Cu2(HL)2] + 2H, 2H2L + 2Cu ⇆ [Cu2(HL)(L)] + 3H, and 2H2L + 2Cu ⇆ [Cu2L2] + 4H were 12.02(7), 8.04(5), 1.26(6), -7.51(6), and -16.36(6), respectively. The knowledge of the solution behavior has supported the synthesis of three new compounds bearing the common building block Cu2L2(4-). Their formulas are (Me4N)4[Cu2(mpyba)2(H2O)2]·…

Optical and magnetic properties of ZnCoO thin films synthesized by electrodeposition

Ternary Zn1−xCoxO crystalline films with different compositions were grown by electrodeposition. The Co content in the final compound is linked to the initial Co/Zn ratio in the starting solution. X-ray diffraction reveals a wurtzite structure for the Zn1−xCoxO films. Transmittance spectra show two effects proportional to Co content, a redshift of the absorption edge and three absorption bands, which are both interpreted to be due to the Co incorporated into the ZnO lattice. The amount of deposited charge was used to get a precise control of the film thickness. Magnetic measurements point out that Co(II) ions are isolated from each other, and consequently the films are paramagnetic. Francis…

Double Interpenetration in a Chiral Three-Dimensional Magnet with a (10,3)-a Structure

A unique chiral three-dimensional magnet with an overall racemic double-interpenetrated (10,3)-a structure of the formula [(S)-(1-PhEt)Me3N]4[Mn4Cu6(Et2pma)12](DMSO)3]·3DMSO·5H2O (1; Et2pma = N-2,6-diethylphenyloxamate) has been synthesized by the self-assembly of a mononuclear copper(II) complex acting as a metalloligand toward Mn(II) ions in the presence of a chiral cationic auxiliary, constituting the first oxamato-based chiral coordination polymer exhibiting long-range magnetic ordering.

Metallosupramolecular approach toward multifunctional magnetic devices for molecular spintronics

Abstract The work presented in this review constitutes a successful extension of our group's research on the chemistry and physics of dinuclear copper(II) metallacyclophanes with aromatic polyoxalamide ligands. The design and synthesis of metallacyclic complexes that contain multiple electro- and photoactive (either metal- or ligand-based) spin carriers and the study of their spectroscopic and magnetic properties as well as their redox and photochemical activity are of large interest in the multidisciplinary field of metallosupramolecular chemistry. In doing this, a ligand design approach has been followed which is based on the copper(II)-mediated self-assembly of bis(oxamato) bridging liga…

Single-ion magnet behaviour in mononuclear and two-dimensional dicyanamide-containing cobalt(ii) complexes.

Three cobalt(II) complexes of formulae [Co(dca)2(bim)4] (1), [Co(dca)2(bim)2]n (2) and [Co(dca)2(bmim)2]n (3) [dca = dicyanamide, bim = 1-benzylimidazole and bmim = 1-benzyl-2-methylimidazole] were prepared and structurally analyzed by single-crystal X-ray crystallography. Compound 1 is a mononuclear species where the cobalt(II) ion is six-coordinate with four bim molecules in the equatorial positions [Co–Nbim = 2.1546(15) and 2.1489(15) A] and two trans-positioned dca ligands [Co–Ndca = 2.1575(18) A] in the axial sites of a somewhat distorted octahedral surrounding. The structures of 2 and 3 consist of two-dimensional grids of cobalt(II) ions where each metal atom is linked to the other fo…

Slow relaxation of the magnetization in a {CoIIIMnIII} heterometallic brick-wall network

Abstract The use of the cyanide-bearing dicobalt(III) complex (PPh4)2[Co2III(μ−2,5-dpp)(CN)8] as a metalloligand towards [Mn(salen)(H2O)]ClO4 afforded the heterobimetallic two-dimensional compound of formula [{MnIII(salen)}2{(μ-NC)4Co2III(μ−2,5-dpp)(CN)4}]n (1) [PPh4+ = teraphenylphosphonium cation, 2,5-dpp = 2,5-bis(2-pyridyl)pyrazine and H2salen = N,N’-ethylenebis(salicylideneimine)] whose structure has been determined by single crystal X-ray diffraction. Compound 1 exhibits a neutral brick-wall structure, where each [Co2III(μ−2,5-dpp)(CN)8]2− unit adopts a tetrakis-monodentate bridging mode towards four {MnIII(salen)}+ fragments through four of its eight cyanide ligands. Each cobalt(III)…

Inside Cover: Oligo-m-phenyleneoxalamide Copper(II) Mesocates as Electro-Switchable Ferromagnetic Metal-Organic Wires (Chem. Eur. J. 43/2010)

Phenolate- and acetate (both μ2-1,1 and μ2-1,3 modes)-bridged linear Co(II)3 and Co(II)2Mn(II) trimers: magnetostructural studies.

A full report on the synthesis, crystal structure, spectroscopic characterization, and magnetic properties of two new trinuclear complexes (one homo- and another heterotrinuclear) [(L)2Co(II)3(OAc)4(MeOH)2]·6MeOH (1) and [(L)2Co(II)2Mn(II)(OAc)4(MeOH)2]·6MeOH (2) [HL = N-methyl-N-2-hydroxybenzyl-2-aminoethyl-2-pyridine] is presented. The properties of 1 and 2 are compared to that of three previously communicated complexes [(L)2Ni(II)3(OAc)4(MeOH)2]·6MeOH (3), [(L)2Ni(II)2Mn(II)(OAc)4(H2O)2] (4), and [(L)2Ni(II)2Co(II)(OAc)4(MeOH)2]·6MeOH (5) (Inorg. Chem.2007, 46, 5128-5130). All are centrosymmetric trimers with the central metal ion situated on an inversion center. Adjacent metal ions are …

Crystal structure, magnetic properties and esr studies of (4-apyH)4[CuIIBr4] [CuIBr2]2: a novel Cu(II)⧹Cu(I) system containing bromocuprate(I) chains and isolated tetrabromocuprate(II) anions

Abstract The synthesis, crystal structure, ESR spectra and magnetic properties are reported for the Cu(II)⧹Cu(I) compound (4-apyH)4[Cu3Br8] (4-apyH = C5H7N2 = 4-aminopyridinium). Single-crystals of the compound were grown by slow diffusion of n-hexane on an ethanolic solution of (4-apyH)2[CuBr4] · H2O. The crystal structure is made up of organic cations, isolated [CuIIBr4]2− anions and infinite [CuIBr2]nn− chains composed of edge-sharing CuIBr4 tetrahedra. N–H · · · Br hydrogen bond interactions between organic counter cations and inorganic anionic units are present and contribute to the cohesiveness of the crystal packing. Magnetic susceptibility measurements showed a good isolation of Cu(…

Low-dimensional copper(II) complexes with the trinucleating ligand 2,4,6-tris(di-2-pyridylamine)-1,3,5-triazine: synthesis, crystal structures, and magnetic properties.

The preparation and structural characterization of three new copper(II) complexes of formula [Cu(3)(dipyatriz)(2)(H(2)O)(3)](ClO(4))(6) x 2 H(2)O (1), {[Cu(4)(dipyatriz)(2)(H(2)O)(2)(NO(3))(2)(ox)(2)](NO(3))(2) x 2 H(2)O}(n) (2), and [Cu(6)(dipyatriz)(2)(H(2)O)(9)(NO(3))(3)(ox)(3)](NO(3))(3) x 4 H(2)O (3) [dipyatriz = 2,4,6-tris(di-2-pyridylamine)-1,3,5-triazine and ox = oxalate] are reported. The structure of 1 consists of trinuclear units [Cu(3)(dipyatriz)(2)(H(2)O)(3)](6+) and uncoordinated perchlorate anions. The two dipyatriz molecules in 1 act as tris-bidentate ligands with the triazine cores being in a quasi eclipsed conformation. Each copper atom in 1 exhibits a distorted square pyr…

X-Ray structure of [ReCl4(μ-ox)Cu(pyim)2]: a new heterobimetallic ReIVCuIIferrimagnetic chain

A new heterobimetallic Re(IV)Cu(II) compound has been prepared and its crystal structure determined by single-crystal X-ray diffraction; magnetic susceptibility measurements show that this compound behaves as a ferrimagnetic chain with significant antiferromagnetic interactions between Re(IV) and Cu(II) metal ions.

Field-Induced Slow Magnetic Relaxation in a Six-Coordinate Mononuclear Cobalt(II) Complex with a Positive Anisotropy

International audience; The novel mononuclear Co(II) complex cis-[Co-II(dmphen)(2)(NCS)(2)]center dot 0.25EtOH (1) (dmphen = 2,9-dimethyl-1,10-phenanthroline) features a highly rhombically distorted octahedral environment that is responsible for the strong positive axial and rhombic magnetic anisotropy of the high-spin Co-II ion (D = +98 cm(-1) and E = +8.4 cm(-1)). Slow magnetic relaxation effects were observed for 1 in the presence of a dc magnetic field, constituting the first example of field-induced single-molecule magnet behavior in a mononuclear six-coordinate Co(II) complex with a transverse anisotropy energy barrier.

Synthesis, structural and magnetic characterizations of new complexes of di-2,6-(2-pyridylcarbonyl)pyridine (pyCOpyCOpy) ligand

International audience; Using the di-2,6-(2-pyridylcarbonyl)pyridine ligand (L1) as starting framework, five new mononuclear complexes were obtained: [Cu(L1)(MeCN)(ClO4)2] (1) [Co(L1)(MeCN)(Br)2]*MeCN (2), [Fe(L1)2](BF4)2*MeOH*H2O (3), [Cr(L2a)Cl2]*2MeOH (where HL2a is (6-(hydroxyl(methoxy)(pyridin-2-yl)methyl)pyridin-2-yl)(pyridin-2-yl)methanone) (4) and one trinuclear [NiII3] complex, [Ni3(L2b)2(Bz)2(EtOH)2](ClO4)2*2EtOH (where HL2b is (6-(hydroxyl(ethoxy)(pyridin-2-yl)methyl)pyridin-2-yl)(pyridin-2-yl)methanone; Bz = benzoato) (5). Their structural and magnetic characterizations are herein reported. All the metal ions show octahedral coordination geometry, which is slightly unusual for t…

Novel Bimetallic-Dicyanamide Extended Two- and Three-Dimensional Networks through [Cu(rac-CTH)]2+ Cation Templation

Reaction of [Cu(rac-CTH)]2+ with dicyanamide and Mn2+ or Fe2+ produces three bimetallic extended structures. Complexes 1 and 2, both obtained in the same reaction pot, consist of two different (4,4) two-dimensional (2D) layers, with the [Cu(rac-CTH)(dca)]+ cations noncoordinated and coordinated to the Mn(μ1,5-dca) network for 1 and 2, respectively (rac-CTH = racemic-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). Complex 2 shows an unusual monodentate coordination mode through the central amide nitrogen of the dca ligand which is first reported for a polynuclear complex. The structure of 3 consists of a three-dimensional network which can be described as a stacking of layers m…

Synthesis, Crystal Structures, and Magnetic Properties of Two Novel Cyanido-Bridged Heterotrimetallic {CuIIMnIICrIII} Complexes

The self-assembly process between the heteroleptic [CrIII(phen)(CN)4]− and [CrIII(ampy)(CN)4]− metalloligands and the heterobimetallic {CuII(valpn)MnII}2+ tecton afforded two heterotrimetallic complexes of formula [{CuII(valpn)MnII(μ-NC)2CrIII(phen)(CN)2}2{(μ-NC)CrIII(phen)(CN)3}2]·2CH3CN (1) and {[CuII(valpn)MnII(μ-NC)2CrIII(ampy)(CN)2]2·2CH3CN}n (2) [phen = 1,10-phenanthroline, ampy = 2-aminomethylpyridine, and H2valpn = 1,3-propanedyilbis(2-iminomethylene-6-methoxyphenol)]. The crystal structure of 1 consists of neutral CuII2MnII2CrIII4 octanuclear units, where two [Cr(phen)(CN)4]− anions act as bis-monodentate ligands through cyanide groups toward two manganese(II) ions from two [CuII(v…

Syntheses, crystal structures and magnetic properties of dinuclear copper(II) complexes with pyrazino[2,3-f  ][4,7]phenanthroline (pap) as bridging ligand

Three dinuclear copper(II) complexes with pyrazino[2,3-f][4,7]phenanthroline (pap) as bridging ligand have been prepared; [Cu2(pap)(C2O4)2]·5H2O 1, [Cu2(pap)(H2O)7(SO4)]SO4·3H2O 2 and [Cu2(pap)(H2O)3(NO3)3]NO33. These are the first metal complexes of pap which have been characterized by X-ray crystallography and magnetic susceptibility measurements. In 1 the dinuclear complex is intercepted by a mirror plane; the bridging pap and the terminal oxalate ligands are bidentate in the equatorial plane of copper. In addition copper has weak axial interactions to oxygen atoms of oxalate in two neighbouring molecules. In 2 the two crystallograpically independent copper atoms are both six-co-ordinate…

.Single-Ion Magnetic Behaviour in an Iron(III) Porphyrin Complex: A Dichotomy Between High Spin and 5/2-3/2 Spin Admixture

International audience; A mononuclear iron(III) porphyrin compound exhibiting unexpectedly slow magnetic relaxation, which is a characteristic of single-ion magnet behaviour, is reported. This behaviour originates from the close proximity (approximate to 550 cm(-1)) of the intermediate-spinS=3/2 excited states to the high-spinS=5/2 ground state. More quantitatively, although the ground state is mostlyS=5/2, a spin-admixture model evidences a sizable contribution (approximate to 15 %) ofS=3/2 to the ground state, which as a consequence experiences large and positive axial anisotropy (D=+19.2 cm(-1)). Frequency-domain EPR spectroscopy allowed them(S)= |+/- 1/2⟩->|+/- 3/2&Rig…

Chains and channels in polynuclear copper(II) complexes with 2,3-bis(2-pyridyl)pyrazine (dpp) as bridging ligand; syntheses, crystal structures and magnetic properties

Abstract The preparation and crystal structures for three Cu(II) polynuclear, chain complexes with 2,3-bis(2-pyridyl)pyrazine (dpp) as bridging ligand are reported, [Cu(dpp)(H2O)2]n(NO3)2n·2n/3H2O (1), [Cu(dpp)(H2O)2]n(CF3SO3)2n (2), and [Cu(dpp)(H2O)2]n(BF4)2n·2nH2O (3). For the latter compound the crystal structure at four different temperatures have been studied. Variable-temperature magnetic susceptibility data and ESR measurements of 1–3 and of the related copper(II) chain [Cu(dpp)(H2O)2]n(ClO4)2n·2nH2O (4) (whose structure was previously reported) have been performed. Compounds 1 and 2 crystallize in the same trigonal space group, R 3 c; 3 is orthorhombic, space group Pbca. Complexes …

One-dimensional oxalato-bridged copper(II) complex possessing two structurally different metallic centres

Abstract The crystal structure of the oxalato-bridged copper(II) compound [Cu2(μ-ox)2(ampy)3]n 1 (ox=oxalate dianion, ampy=2-amino-3-methylpyridine) consists of infinite corrugated one-dimensional chains in which two types of copper(II) centres, five- and six-coordinated, are bridged sequentially by asymmetric bis-bidentate oxalato ligands. Magnetic susceptibility measurements show the occurrence of a significant intrachain antiferromagnetic coupling (J=−22.9 cm −1 ) .

Ferromagnetic coupling through spin polarization in the hexanuclear [MnII(3)CuII(3)] complex.

A novel Cu(II)-Mn(II) hexanuclear complex of formula [[MnCuL](3)(tma)](ClO(4))(3).8H(2)O [H(2)L = macrocyclic Robson proligand; H(3)tma = trimesic acid] has been obtained by connecting three heterobinuclear [Cu(II)Mn(II)L](2+) cationic species through the trimesate anion. The complex exhibits a C(3) rotational symmetry, imposed by the geometry of the bridging ligand. The interaction within each Mn(II)-Cu(II) pair is antiferromagnetic (J = -16.7 cm(-1)). A weak ferromagnetic coupling among the three S = 2 resulting spins through the tricarboxylato bridge leads to a S = 6 ground spin state, for which the spin polarization mechanism is responsible.

Molecular squares of Ni(II) and Cu(II): ferromagnetic exchange interaction mediated by syn-anti carboxylate-bridging.

The synthesis of four discrete tetranuclear complexes {[Ni(II)(L(2))][ClO(4)]}(4).MeCN (1), {[Cu(II)(L(1))(O(3)SCF(3))]}(4).H(2)O (), {[Cu(II)(L(3))(OClO(3))]}(4).MeCN () and {[Cu(II)(L(4))][ClO(4)]}(4).3MeCN.4H(2)O (4), supported by a closely similar group of carboxylate-appended (2-pyridyl)alkylamine ligands [L(1)(-): 3-[N-methyl-{2-(pyridin-2-yl)ethyl}amino]propionate; L(2)(-): 3-[(2-(pyridin-2-yl)ethyl){2-(pyridin-2-yl)methyl}amino]propionate; L(3)(-): 3-[N-isopropyl-{2-(pyridin-2-yl)methyl}amino]propionate and L(4)(2-): 3-[N-{2-(pyridin-2-yl)methyl}amino]-bis(propionate)] is described. Structural characterization reveals that each Ni(II) centre in 1 has square-pyramidal Ni(II)N(3)O(2) …

Bis and tris(oxalato)ferrate(iii) complexes as precursors of polynuclear compounds

The preparation and crystal structure of two oxalato-bridged NaI–FeIII compounds, [Na3Fe(ox)3(H2O)4]·H2O (1) and [FeII(phen)3][NaFe(ox)3(H2O)3]·4H2O (5), two mononuclear FeIII complexes AsPh4[Fe(bipy)(ox)2]·H2O (3) and AsPh4[Fe(phen)(ox)2]·H2O (4) and an oxalato-bridged FeIII compound [AsPh4]4[Fe2(ox)5]·5H2O (2) (ox = oxalate dianion, bipy = 2,2′-bipyridine, phen = 1,10-phenantroline and AsPh4+ = tetraphenylarsonium cation) are reported here. The structure of 1 consists of infinite anionic [NaFe(ox)3]2− layers linked trough centrosymmetric [Na4(H2O)8]4+ tetranuclear units yielding a three-dimensional motif. Crystallization water molecules ensure the cohesion of the crystal lattice in 1. The…

Versatile supramolecular self-assembly : Part II. Network formation and magnetic behaviour of copper(ii) malonate anions in ammonium derivatives

Five new metal–organic compounds of formula An[Cu(mal)2(H2O)m] (A being an amine cation and H2mal = malonic acid) have been structurally and magnetically characterized. The crystal structure of these compounds consists of an alternation of malonate-containing copper(II) anionic and amine cationic layers. Depending on the amine cation, the bis(malonate)cuprate(II) units can be connected to other units through carboxylate bridges resulting in anionic networks which exhibit different topologies: monomers (2 and 5), layers (3 and 4) and three-dimensional structures (1). Hydrogen bonding plays an important role in the self-assembling of metal–organic compounds and how the size of the amine catio…

Magnetic order in a CuII–DyIII oxamato-based two-dimensional coordination polymer

Abstract We report the synthesis, crystal structure, and magnetic characterization of a novel two-dimensional copper(II)–dysprosium(III) coordination polymer of formula [LiI(OH2)4]2[DyIIICuII2(Me2pma)4Cl(H2O)] . 4H2O (1) [Me2pma = N-2,6-dimethylphenyloxamate]. Compound 1 was obtained using the mononuclear anionic complex [CuII(Me2pma)2]2–, as a bis(bidentate) metalloligand toward solvated dysprosium(III) cations, and it shows a square [DyIIICuII2] layered structure of (44.62) net topology. Interestingly, the combination of two factors, the well-known efficiency of oxamato ligands to transmit strong magnetic couplings between neighboring atoms and such structural topology, is responsible for…

The flexibility of molecular components as a suitable tool in designing extended magnetic systems

In this work we show how the design of n-dimensional magnetic compounds (nD with n = 1–3) can strongly benefit from the use crystal engineering techniques, which can give rive to structures of different shapes with different properties. We focus on the networks built by assembling the malonato-bridged tetranuclear copper(II) units Cu4(mal)4 (mal2− is the dianion of propanedioic acid, H2mal) through the potentially bridging 2,4′-bipyridine (2,4′-bpy), 4,4′-bipyridine (4,4′-bpy) and pyrazine (pyz). The magneto-structural study of the complexes of formula [Cu4(mal)4(2,4′-bpy)4(H2O)4]·8H2O (1), [Cu4(mal)4(H2O)4(4,4′-bpy)2] (2) (this compound was the subject of a previous report but it is includ…

Versatile supramolecular self-assembly. Part I. Network formation and magnetic behaviour of the alkaline salts of the bis(malonate)cuprate(ii) anion

Five malonate-containing copper(II) compounds of formula {[A(H2O)n]2 [Cu(mal)2(H2O)m]} [A = Li (1), Na (2), K (3), Rb (4) and Cs (5); H2mal = malonic acid] have been synthetized and characterized by X-ray diffraction. The structure of these compounds consists of bis(malonate)cuprate(II) anions and alkaline cations that are held together by means of carboxylate bridges and water molecules leading to 3D networks. A study of the self-assembling of the bis(malonate)cuprate(II) and the alkaline cations is carried out, the size of the alkaline metal ion playing an important role in the control of the resulting malonate-bridged copper(II) structure. A regular alternation of layers of anionic malon…

Ascorbic acid decomposition into oxalate ions: a simple synthetic route towards oxalato-bridged heterometallic 3d-4f clusters.

Two types of oxalato-bridged heterometallic 3d–4f dodeca- and hexanuclear compounds have been obtained by connecting six bi- and, respectively, trinuclear moieties through oxalato bridges arising from the slow decomposition of the L-ascorbic acid.

Crystal Structures and Magnetic Properties of Novel [LnIIICuII4] (Ln = Gd, Dy, Ho) Pentanuclear Complexes. Topology and Ferromagnetic Interaction in the LnIII−CuII Pair

The first pentanuclear complexes of formula {Dy[Cu(apox)](2)[Cu(apox)(H(2)O)](2)}[ClO(4)](3).7H(2)O (1), {Ho[Cu(apox)][Cu(apox)(H(2)O)](3)}[PF(6)](3).4.5H(2)O (2), {Gd[Cu(apox)](2)[Cu(apox)(H(2)O)](2)}[ClO(4)](3).7H(2)O (3) and {Gd[Cu(apox)][Cu(apox) (H(2)O)](3)}[PF(6)](3).4.5H(2)O (4) (H(2)apox = N,N'-bis(3-aminopropyl)oxamide) have been synthesized. The crystal structures of complexes 1 and 2 have been determined by X-ray diffraction methods. Complexes 3 and 4 are isostructural with 1 and 2, respectively. Crystallographic data are as follows: 1 and 3, monoclinic, space group C2/c and Z = 4, with a = 14.646(6) Å, b = 29.496(7) Å, c = 16.002(7) Å, and beta = 111.76(2) degrees for 1 and a = …

C3-symmetric trinuclear copper(ii) species as tectons in crystal engineering

Three new complexes have been obtained using C3-symmetric trinuclear complexes as tectons; [Cu3(felden)(NCS)3(dmf)3] (1), [Cu3(felden)(mand)3]·(C2H5)2O (2), and [Cu3(felden)(dca)3(C2H5OH)]·2H2O (3) (H3felden is the Schiff base resulting from the condensation of 2,4,6-triformylphloroglucinol with N,N-dimethylethylenediamine, mand− is the anion of the R-mandelic acid and dca− is the dicyanamide anion). Compounds 1 and 2 are discrete trinuclear species, while compound 3 is a 2D coordination polymer, constructed from trinuclear nodes and dicyanamido spacers. The variable-temperature magnetic properties of 1–3 have been investigated and they reveal the occurrence of weak antiferromagnetic intera…

Preparation, crystal structures and magnetic properties of three thiocyanato-bridged copper(II) complexes with 2,2′-biimidazole or 2-(2′-pyridyl)imidazole as terminal ligands

The synthesis, crystal structures and variable temperature magnetic investigation of three new thiocyanato-bridged copper(II) complexes with 2,2′-biimidazole (H2bim) or 2-(2′-pyridyl)imidazole) (pyim) as coligands, {[Cu(H2bim)2][Cu(H2bim)(NCS)2(SCN)0.6667(NO3)0.3333]2} · 2H2O (1), [Cu(H2bim)(NCS)2]n (2) and [Cu(pyim)(NCS)2]n (3) are reported. Complex 1 contains centrosymmetric trinuclear species where central [Cu(2)(H2biim)2]2+ cations and peripheral [Cu(1)(H2biim)(NCS)2(SCN)]− anions are linked through single end-to-end thiocyanato bridges. Complexes 2 and 3 are made up of neutral zigzag chains of copper(II) ions linked by single (2) and double (3) end-to-end thiocyanato bridges. A bidenta…

Cover Feature: Design of Magnetic Coordination Polymers Built from Polyoxalamide Ligands: A Thirty Year Story (Eur. J. Inorg. Chem. 3‐4/2018)

Novel cobalt(II) coordination polymers based on 1,2,4,5-benzenetetracarboxylic acid and extended bis-monodentate ligands

Four new high-spin cobalt(II) complexes of formulae [Co2(bta)(4,4′-bpy)2(H2O)2]n (1), {Hbpe[Co(Hbta)(bpe)(H2O)2]}n (2), {[Co(H2bta)(azpy)(H2O)2]·azpy}n (3) and {[Co2(bta)(bpa)2(H2O)4]·8H2O}n (4) with H4bta = 1,2,4,5-benzenetetracarboxylic acid, 4,4′-bpy = 4,4′-bipyridine, bpe = trans-1,2-bis(4-pyridyl)ethene, azpy = 4,4′-azobispyridine and bpa = trans-1,2-bis(4-pyridyl)ethane, have been prepared and characterized by single crystal X-ray diffraction. Compounds 1–4 exhibit two-dimensional networks where the fully (1 and 4) or partially (2 and 3) deprotonated tetracarboxylic ligand connects two (2 and 3) or four (1 and 4) cobalt(II) ions through two trans-carboxylate (1–3) or all the carboxyla…

Syntheses, Characterization, and Magnetic Studies of Copper(II) Complexes with the Ligand N,N,N′,N′-Tetrakis(2-pyridylmethyl)-1,3-benzenediamine (1,3-tpbd) and its Phenol Derivative 2,6-Bis[bis(2-pyridylmethyl)amino]-p-cresol] (2,6-Htpcd)

The copper(II) complexes [Cu4(1,3-tpbd)2(H2O)4(NO3)4]n(NO3)4n·13nH2O (1), [Cu4(1,3-tpbd)2(AsO4)(ClO4)3(H2O)](ClO4)2·2H2O·0.5CH3OH (2), [Cu4(1,3-tpbd)2(PO4)(ClO4)3(H2O)](ClO4)2·2H2O·0.5CH3OH (3), [C...

Metal–Organic Frameworks as Playgrounds for Reticulate Single-Molecule Magnets

Achieving an accurate control on the final structure of Metal-Organic Frameworks (MOFs) is mandatory to obtain target physical properties. Here we describe how the combination of a metalloligand design strategy and a post-synthetic method is a versatile and powerful approach to success on this extremely difficult task. In a first stage, a novel oxamato-based tetranuclear cobalt(III) complex with a tetrahedron-shape geometry is used, for the first time, as metalloligand toward cal-cium(II) cations to lead a diamagnetic Ca(II)-Co(III) three-dimensional (3D) MOF (1). In a second stage, in a single-crystal to single-crystal manner the calcium(II) ions are replaced by terbium (III), dysprosium(I…

A Bioinspired Dinickel(II) Hydrolase: Solvent Vapor-Induced Hydrolysis of Carboxyesters under Ambient Conditions

From the perspective of synthetic metallohydrolases, a phenoxo-bridged dinickel(II) complex [NiII2(L)(H2O)2(CH3OH)][ClO4]·CH3OH (1) (H3L = 2,6-bis[{{(5-bromo-2-hydroxybenzyl)(N′,N″-(dimethylamino)ethyl)}amino}methyl]-4-methylphenol) has been synthesized and structurally characterized. The presence of a vacant coordination site and a weakly bound water molecule provides the scope for substrate binding to act as a metallohydrolase model. Ethyl acetate vapor diffusion at 298 K to a CH3CN/CH3OH solution of 1 results in the formation of a pentanuclear acetato-bridged complex [NiII5(H2L)2(μ3-OH)2(μ-O2CCH3)4][ClO4]2·CH3CO2C2H5 (2), demonstrating for the first time the metal-coordinated water-promo…

Ferrocene containing chelating ligands 3. Synthesis, spectroscopic characterization, electrochemical behaviour and interaction with metal ions of new ligands obtained by condensation of ferrocenecarboxaldehyde with 2-amino-benzoic acid derivatives. Crystal structures of 2-ferrocenylmethylamino-5-methyl-benzoic acid and 2-bis(ferrocenylmethyl)ammonium-5-methyl-benzoic acid perchlorate

Abstract Ferrocenecarboxaldehyde reacts with 2-amino-benzoic acid, 2-amino-5-methyl-benzoic acid or 3-amino-2-naphthoic acid to give the corresponding Schiff-base derivatives 2-ferrocenylmethylidenimino-benzoic acid (1), 2-ferrocenylmethylidenimino-5-methyl-benzoic acid (2) and 3-ferrocenylmethylidenimino-2-naphthoic acid (3). 1, 2 and 3 are stable in the solid state but easily hydrolyze in solution. This hydrolysis has been studied kinetically in a methanol-water medium. In order to increase the stability in solution to use these compounds as ligands, the imino group from 1, 2 and 3 was reduced by NaBH4 to give the amino derivatives 2-ferrocenylmethylamino-benzoic acid (4), 2-ferrocenylmet…

Design of 3d–4f molecular squares through the [Fe{(HB(pz)3)}(CN)3]− metalloligand

A new series of {FeIII2LnIII2} heterobimetallic squares of general formula [FeIII{HB(pz)3}(CN)(μ-CN)2Ln(pyim)x(NO3)2(H2O)y]2·zH2O [Ln = La (1), Gd (2), Tb (3) and Dy (4); {HB(pz)3}− = hydrotris(pyrazolyl)borate and pyim = 2-(1H-imidazol-2-yl)pyridine; x = 2, y = 0 (1), x = y = 1 (2–4) and z = 10 (1), 6 (2), 2.76 (3), 4 (4)] were synthesized by reacting the low-spin [FeIII{HB(pz)3}(CN)3]− complex anion with the preformed [LnIII(pyim)x(NO3)2(H2O)y]+ complex cation [formed in situ by mixing the lanthanide(III) salt and the pyim ligand]. Single-crystal X-ray diffraction shows that 1–4 crystallize in the P triclinic space group, 2–4 being isomorphous. In all cases, the structure comprises neutra…

Bis‐μ‐pyrazolate‐Bridged Dinickel(II) and Dicopper(II) Complexes: An Example of Stereoelectronic Preference of Metal Ions and Stabilization of Mixed‐Valence Ni III Ni II Species

New dimeric nickel(II) and copper(II) complexes [(L)Ni(μ-L′)]2[ClO4]21 and [(L)Cu(μ-L′)]2[ClO4]22, [2-[3-(2′-pyridyl)pyrazol-1-ylmethyl]pyridine (L) and 3-(2-pyridyl)pyrazole (HL′)] have been synthesized, structurally characterized, and their absorption, magnetic, EPR and redox properties investigated. The crystal structure of 1·MeCN reveals a planar {Ni2(μ-L′)2}2+ core [Ni···Ni separation: 4.0765(10) A] in which each distorted octahedral NiII ions is terminally coordinated by a tridentate ligand L and bridged by two HL′ units, in their deprotonated form. The structural analysis of 2·2MeCN reveals two five-coordinate CuII ions, each terminally coordinated by adopting only a bidentate coordi…

Magneto-structural studies on heterobimetallic malonate-bridged M(II)Re(IV) complexes (M = Mn, Co, Ni and Cu).

The mononuclear Re(IV) compound of formula (PPh(4))(2)[ReBr(4)(mal)] (1) was used as a ligand to obtain the heterobimetallic species [ReBr(4)(μ-mal)Co(dmphen)(2)]· MeCN (2), [ReBr(4)(μ-mal)Ni(dmphen)(2)] (3), [ReBr(4)(μ-mal)Mn(dmphen)(2)] (4a), [ReBr(4)(μ-mal)Mn(dmphen)(H(2)O)(2)]·dmphen·MeCN·H(2)O (4b), [ReBr(4)(μ-mal)Cu(phen)(2)]·1/4H(2)O (5) and [ReBr(4)(μ-mal)Cu(bipy)(2)] (6) (mal = malonate dianion, dmphen = 2,9-dimethyl-1,10-phenanthroline, phen = 1,10-phenanthroline and bipy = 2,2'-bipyridine). The structures of 2 and 5 (single-crystal X-ray diffraction) are made up of neutral [ReBr(4)(μ-mal)M(AA)] dinuclear units [AA = dmphen with M = Co (2) and AA = phen with M = Cu (5)] where the …

2,2′-Bipyrimidine- and 2,3-bis(2-pyridyl)pyrazine-containing manganese(II) compounds: Structural and magnetic properties

The preparation, crystal structures and magnetic properties of four different manganese(II) compounds of formula [Mn(bipym)Cl2]n·2nH2O (1), [Mn2(dpp)2(H2O)2Cl4]·2H2O (2), [Mn(dpp)(H2O)2]n(ClO4)2n·1.5nH2O (3) and [Mn(dpp)(dca)2]n (4) [bipym = 2,2′-bipyrimidine, dpp = 2,3-bis(2-pyridyl)pyrazine and dca = dicyanamide anion] are reported. Compounds 1 and 3 are uniform chains of six-coordinated manganese(II) ions bridged by bis(bidentate) bipym (1) and dpp (3) ligands with two chloride groups (1) and two water molecules (3) in cis position. The electroneutrality in 3 is achieved by uncoordinated perchlorate anions. The manganese atom in 1 and 3 exhibits a distorted octahedral environment mainly …

Self-assembly, binding ability and magnetic properties of dicopper(ii) pyrazolenophanes

A novel series of dinuclear copper(II) pyrazolenophanes of the formula [Cu2(μ-4-Mepz)2(μ-ClO4)(ClO4)(bpm)2] (1), [Cu2(μ-pz)2(μ-H2O)(ClO4)(4,7-Me2phen)2]ClO4·H2O·CH3CN (2), [Cu2(μ-pz)2(μ-H2O)(ClO4)3/2(H2O)1/2(phen)2]2[Cu2(μ-pz)2(μ-ClO4)(ClO4)2(phen)2]·8H2O (3), and [Cu2(μ-pz)2(CH3CN)2(3,4,7,8-Me4phen)2](ClO4)2 (4) (Hpz = pyrazole, H-4-Mepz = 4-methylpyrazole, bpm = 2,2'-bipyrimidine, phen = 1,10-phenanthroline, 4,7-Me2phen = 4,7-dimethyl-1,10-phenanthroline, and 3,4,7,8-Me4phen = 3,4,7,8-tetramethyl-1,10-phenanthroline) have been synthesized and magneto-structurally investigated. The crystal structures of 1–4 contain bis(pyrazolate)(perchlorate)- (1 and 3), bis(pyrazolate)(aqua)- (2 and 3), …

Intramolecular versus intermolecular exchange pathways in the binuclear complex [Cu2(H2tea)2(4,4′-bipy)](ClO4)2·3H2O (H3tea=triethanolamine and 4,4′-bipy=4,4′-bipyridine)

Abstract The binuclear copper(II) complex of formula [Cu2(H2tea)2(4,4′-bipy)](ClO4)2·3H2O (1) (H3tea=triethanolamine and 4,4′-bipy=4,4′-bipyridine) has been isolated and characterized by X-ray diffraction. Its structure consists of dinuclear [Cu2(H2tea)2(4,4′-bipy)]2+ cations, uncoordinated perchlorate anions and crystallization water molecules. Each copper atom exhibits a trigonal-bipyramidal environment with the three triethanolamine-oxygen atoms building the equatorial plane, and the triethanolamine-nitrogen and one of the 4,4′-bipy nitrogen atoms defining the three-fold axis. The 4,4′-bipy molecule acts as a bismonodentate bridging ligand, the copper–copper separation across it being 11…

Magnetic coupling in discrete cyano-bridged Mn(III)-Fe(III) motifs: synthesis, crystal structure, magnetic properties and theoretical study.

The preparation, crystal structures and magnetic properties of the heterobimetallic complexes of formula [Mn(III)(n-MeOsalen)(H(2)O)(mu-CN)Fe(III)(bpym)(CN)(3)]·mH(2)O with n = m = 3 (1) and n = 4 and m = 2 (2) [n-MeOsalen(2-) = N,N'-ethylenebis(n-methoxysalicylideneiminate) dianion and bpym = 2,2'-bipyrimidine] are reported. 1 and 2 are dinuclear neutral species where the cyano-bearing low-spin unit [Fe(III)(bpym)(CN)(4)](-) acts as a monodentate ligand towards the [Mn(III)(SB)(solv)(x)](+) entity (SB = tetradentate Schiff-base) through one of its four cyano groups. Adjacent heterobimetallic units are interlinked through hydrogen bonds involving the coordinated water molecule of one dinucl…

Photoluminescent and Slow Magnetic Relaxation Studies on Lanthanide(III)-2,5-pyrazinedicarboxylate Frameworks

In the series described in this work, the hydrothermal synthesis led to oxidation of the 5-methyl-pyrazinecarboxylate anion to the 2,5-pyrazinedicarboxylate dianion (2,5-pzdc) allowing the preparation of three-dimensional (3D) lanthanide(III) organic frameworks of formula {[Ln2(2,5-pzdc)3(H2O)4]·6H2O}n [Ln = Ce (1), Pr (2), Nd (3), and Eu (4)] and {[Er2(2,5-pzdc)3(H2O)4]·5H2O}n (5). Single-crystal X-ray diffraction on 1–5 reveals that they crystallize in the triclinic system, P1 space group with the series 1–4 being isostructural. The crystal structure of the five compounds are 3D with the lanthanide(III) ions linked through 2,5-pzdc2– dianions acting as two- and fourfold connectors, buildi…

Multielectron transfer in a dicopper(II) anthraquinophane.

The new dinuclear copper(II) metallacyclophane with the non-innocent N,N'-1,4-bis(oxamate)-9,10-anthraquinone bridging ligand possesses a dual multielectron redox behavior featuring stepwise one-electron oxidation of the antiferromagnetically coupled Cu(II) ions and two-electron reduction of the anthraquinone spacers in a π-stacked anti conformation.

Crystal structures and magnetic properties of uniform and alternating azido-bridged (2,2′-bipyridyl)copper(II) chains

Abstract Single crystals of four copper(II) complexes of formula [Cu(bipy)(N3)2]n (1,2), [Cu(bipy)2(N3)(ClO4)] (3) and [Cubipy)2(N3)]ClO4 (4) (bipy=2,2′-bipyridine) were obtained from aqueous solutions containing (2,2′-bipyridyl) copper(II) perchlorate and sodium azide, and their crystal structures were determined by X-ray diffraction methods. The structures of compounds 1 and 4 were already known, but the better accuracy of our structural determination of complex 1 led us to reconsider it here. The structures of compounds 1 and 2 are made up of neutral chains of copper(II) ions bridged by two azide groups exhibiting asymmetrical end-on (1) and alternating asymmetrical end-on and end-to-end…

A Ferromagnetic [Cu3(OH)2]4+Cluster Formed inside a Tritopic Nonaazapyridinophane: Crystal Structure and Solution Studies

[Cr(dmbipy)(ox)2]−: a new bis-oxalato building block for metal assembling. Crystal structures and magnetic properties of XPh4[Cr(dmbipy)(ox)2]·5H2O (X = P and As), {Ba(H2O)2[Cr(dmbipy)(ox)2]2}n·17/2nH2O and {Ag(H2O)[Cr(dmbipy)(ox)2]}n·3nH2O

The synthesis, X-ray structure and variable-temperature magnetic study of new compounds of formula PPh4[Cr(dmbipy)(ox)2]·5H2O (1), AsPh4[Cr(dmbipy)(ox)2]·5H2O (2), {Ba(H2O)2[Cr(dmbipy)(ox)2]2}n·17/2nH2O (3) and {Ag(H2O)[Cr(dmbipy)(ox)2]}n·3nH2O (4) (PPh4+ = tetraphenylphosphonium cation; AsPh4+ = tetraphenylarsonium cation; dmbipy = 4,4′-dimethyl-2,2′-bipyridine; ox2− = oxalate dianion) are reported herein. The isomorphous compounds 1 and 2 are made up of discrete [Cr(dmbipy)(ox)2]− anions, XPh4+ cations [X = P (1) and As (2)] and uncoordinated water molecules. The chromium environment in 1 and 2 is distorted octahedral with Cr–O and Cr–N bond distances varying in the ranges 1.950(2)–1.9782…

Design of single cyanide-bridged tetranuclear bimetallic rectangles exhibiting ferromagnetic coupling

Abstract The cyanide-bridged tetranuclear bimetallic rectangles ( XPh 4 ) 4 [ Fe 2 III Cu 2 II ( μ - CN ) 4 ( CN ) 8 ( L ) 2 ] · n H 2 O [X = P (1) and As (2); L = bpcam (1) and bpca (2); n = 4 (1) and 0 (2)] have been prepared and their crystal structures were characterized by single crystal X-ray diffraction; 1 exhibits intramolecular ferromagnetic interactions (J1 = +3.7 cm−1 and J2 = +7.0 cm−1, H = - J 1 [ S Fe ( 1 ) · S Cu ( 1 ) + S Fe ( 1 a ) · S Cu ( 1 a ) ] − J 2 [ S Fe ( 1 ) · S Cu ( 1 a ) + S Fe ( 1 a ) · S Cu ( 1 ) ] + D [ S Fe ( 1 ) z 2 + S Fe ( 1 a ) z 2 ] ) leading to a low-lying S = 2 spin state.

>3 + 1 = 6 + 2> In Cu(ii) coordination chemistry of 1H-pyrazole aza cryptands

A polyazamacrocycle formed from two tris(2-aminoethyl)amine units connected by 1H-pyrazole units shows unique hexanuclear Cu(ii) complexes by combination of two binuclear Cu(ii) cryptand complexes through pyrazolate moieties belonging to both cryptands. The formation of these dimeric entities has been proven both in solution by potentiometric studies and mass spectroscopy and in the solid state by X-ray diffraction of crystals of three different batches of formulae [Cu6(H-3L)2(H2O)2](TsO)6·22H2O (2), [Cu6(H-3L)2(NO3)2](NO3)4·2H2O (3) and [Cu6(H-3L)2Cl2]Cl4·(C4H5N3O2)2·14.35H2O (4). The hexanuclear unit in 2 and 4 can be viewed like three magnetically independent binuclear complexes with J =…

Synthesis, crystal structure and magnetic properties of the first single azido-bridged copper(II) chain [Cu(bpym)(N3)2]n (bpym = 2,2′-bipyrimidine)

Abstract Single crystals of the copper(II) chain of formula [Cu(bpym) (N32]n (bpym = 2,2′-bipyrimidine) were prepared and characterized by X-ray diffraction methods. The structure consists of neutral chains of copper (II) ions bridged by a single azide group exhibiting the asymmetric end-to-end coordination mode. A terminally bound azide ligand and a didentate bpym group complete the square pyramidal geometry of the metal atom. The intrachain copper-copper separation is 5.063(1)A. The magnetic behaviour was investigated in the temperature range 2.0–290 K. The susceptibility curve exhibits a maximum at .9 K showing the occurrence of a weak intrachain antiferromagnetic coupling. Analysis of t…

A new chiral dimanganese(iii) complex: synthesis, crystal structure, spectroscopic, magnetic, and catalytic properties

Two enantiomeric complexes of formula [MnIII2(μ-OCH3)2(R-valBINAM)2]·1.75DMF (1) and [MnIII2(μ-OCH3)2(S-valBINAM)2]·2DMF (2) [valBINAM = 1,1′-binaphthalene-2,2′-bis(3-methoxysalicylideneiminate)] have been synthesized using as a ligand the chiral Schiff bases resulting from the condensation reactions between o-vanillin and the chiral 1,1′-binaphthyl-2,2′-diamine. The structures of 1 and 2 which have been solved by single crystal X-ray diffraction consist of neutral dimers, the manganese(III) ions being bridged by two methoxido anions, arising from the solvent, and by two valBINAM2− ligands. Their circular dichroism spectra at room temperature emphasize the occurrence of the exciton coupling…

Slow relaxation of the magnetization in Oximato-bridged heterobimetallic Copper(II)-Manganese(III) chains

The use of the oximato-containing copper(II) complexes, [Cu(Hdeg)2] (H2deg = diethylglyoxime), [Cu(Hmeg)2] (H2meg = methylethylglyoxime) and [Cu(Hdmg)2] (H2dmg = dimethylglyoxime), as ligands toward manganese(II) acetate in methanol afforded the heterobimetallic compounds of formula [MnCu(deg)2(CH3COO)(H2O)2] (1), [MnCu(meg)2(CH3COO)(H2O)2] (2) and [MnCu(dmg)2(CH3COO)(H2O)2] (3) where the starting manganese(II) ion was oxidized to manganese(III) by air. In the lack of single crystals suitable for X-ray diffraction analysis, X-ray absorption techniques (EXAFS and XANES) at 40 K were used for the structural characterization of 1-3. The analysis of the X-ray absorption data reveals that 1-3 ar…

Influence of Copper(II) and Nickel(II) Ions in the Topology of Systems Based on a Flexible Bis-Oxamate and Bipyridine Building Blocks

Single crystals of the mononuclear bis-oxamate nickel(II) complex [Ni(bipy)(H2edpba)]·dmso (1) are obtained by reacting [Ni(bipy)Cl2]·H2O and the flexible K2(H2edpba) ligand [bipy = 2,2′-bipyridine; H4edpba = N,N′-2,2′-ethylenediphenylenebis(oxamic acid)]. The reaction of 1 with copper(II) ions resulted in two products in which the replacement of the nickel(II) ion by copper(II) took place: the chain compound [Cu(bipy)(H2edpba)]n·3nH2O·ndmso [dmso = dimethyl sulfoxide] (2) and the analogous chain compound without dmso crystallization molecules [Cu(bipy)(H2edpba)]n·1.5nH2O (3a) in its polycrystalline form. The reaction of [Cu(bipy)Cl2] and K2(H2edpba) yielded single crystals of [Cu(bipy)(H2e…

Design of Magnetic Coordination Polymers Built from Polyoxalamide Ligands: A Thirty Year Story

International audience; The aim of this review is to pay tribute to the legacy of O. Kahn. Kahn's credo was to synthesize magnetic compounds with predictable structure and magnetic properties. This is illustrated herein with results obtained by Kahn's group during his Orsay period thirty years ago, but also on the basis of our recent results on the synthesis of coordination polymers with oxamate ligands. The first part of this review is devoted to a short description of the necessary knowledge in physics and theoretical chemistry that Kahn and his group have used to select oxamate ligands, the complex‐as‐ligand strategy and the synthesis of heterobimetallic systems. Then, we describe the st…

Alternating antiferromagnetic and ferromagnetic exchange interactions in the S = 1 Heisenberg chain. Theory and magnetic properties

Abstract We focus on the magnetic properties of the S = 1 Heisenberg chain with alternating antiferromagnetic and ferromagnetic exchange interactions J 1 and J 2 . The magnetic behavior of this system is calculated as a function of the alternation parameter α = J 2 /| J 1 |, from a general numerical procedure based on closed spin chains of increasing length. These theoretical results are fitted to rational unified expressions, which are subsequently used to describe the magnetic behavior of a nickel (II) complex, [Ni(bipy)(N 3 ) 2 ] n , exhibiting an alternating chain structure with a dominant ferromagnetic exchange.

Structural analysis and magnetic properties of the copper(II) dicyanamide complexes [Cu2(dmphen)2(dca)4], [Cu(dmphen)(dca)(NO3)] and [Cu(4,4′-dmbpy)(H2O)(dca)2] (dca=dicyanamide; dmphen=2,9-dimethyl-1,10-phenanthroline; 4,4′-dmbpy=4,4′-dimethyl-2,2′-bipyridine)

Abstract The preparation, crystal structures and magnetic properties of three copper(II) compounds of formulae [Cu2(dmphen)2(dca)4] (1), [Cu(dmphen)(dca)(NO3)]n (2) and [Cu(4,4′-dmbpy)(H2O)(dca)2] (3) (dmphen=2,9-dimethyl-1,10-phenanthroline, dca=dicyanamide and 4,4′-dmbpy=4,4′-dimethyl-2,2′-bipyridine) are reported. The structure of 1 consists of discrete copper(II) dinuclear units with double end-to-end dca bridges whereas that of 2 is made up of neutral uniform copper(II) chains with a single symmetrical end-to-end dca bridge. Each copper atom in 1 and 2 is in a distorted square pyramidal environment: two (1) or one (2) nitrile-nitrogen atoms from bridging dca groups, one of the nitrogen…

2,2'-BIPYRIMIDINEOXALATOCOPPER(II) COMPLEXES - FROM THE MONONUCLEAR COMPLEX TO THE 2D SHEET-LIKE POLYMER

Synthesis, crystal structure and magnetic properties of H2tppz[ReCl6] and [Cu(bpzm)2(μ-Cl)ReCl3(μ-ox)Cu(bpzm)2(μ-ox)ReCl3(μ-Cl)]n.

Two new Re(iv) compounds of formulae H2tppz[ReCl6] (1) and [Cu(bpzm)2(μ-Cl)ReCl3(μ-ox)Cu(bpzm)2(μ-ox)ReCl3(μ-Cl)]n (2) [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine and bpzm = bis(pyrazolyl-1-yl)methane] have been prepared and their crystal structures determined by X-ray diffraction on single crystals. Compound 1 is a mononuclear species whose structure consists of octahedral hexachlororhenate(iv) anions and diprotonated H2tppz(2+) cations which are arranged in the unit cell as alternating anionic and cationic layers, held together by electrostatic forces. The structure of 2 is made up of alternating [Cu(1)(bpzm)2](2+) and [(ox)ReCl3(μ-Cl)Cu(2)(bpzm)2(μ-Cl)ReCl3(ox)](2-) entities interlinked …

Synthesis, Crystal Structures, and Magnetic Properties of a New Family of Heterometallic Cyanide-Bridged FeIII2MII2 (M = Mn, Ni, and Co) Square Complexes

New heterobimetallic tetranuclear complexes of formula [Fe(III){B(pz)(4)}(CN)(2)(μ-CN)Mn(II)(bpy)(2)](2)(ClO(4))(2)·CH(3)CN (1), [Fe(III){HB(pz)(3)}(CN)(2)(μ-CN)Ni(II)(dmphen)(2)](2)(ClO(4))(2)·2CH(3)OH (2a), [Fe(III){B(pz)(4)}(CN)(2)(μ-CN)Ni(II)(dmphen)(2)](2)(ClO(4))(2)·2CH(3)OH (2b), [Fe(III){HB(pz)(3)}(CN)(2)(μ-CN)Co(II)(dmphen)(2)](2)(ClO(4))(2)·2CH(3)OH (3a), and [Fe(III){B(pz)(4)}(CN)(2)(μ-CN)Co(II)(dmphen)(2)](2)(ClO(4))(2)·2CH(3)OH (3b), [HB(pz)(3)(-) = hydrotris(1-pyrazolyl)borate, B(Pz)(4)(-) = tetrakis(1-pyrazolyl)borate, dmphen = 2,9-dimethyl-1,10-phenanthroline, bpy = 2,2'-bipyridine] have been synthesized and structurally and magnetically characterized. Complexes 1-3b have be…

Synthesis, crystal structure and magnetic properties of the malonato-bridged bimetallic chain [Mn(II)Cu(II)(mal)2(H2O)4]·2H2O

Abstract The first malonato-bridged bimetallic chain of formula [MnCu(mal)2(H2O)4]·2H2O (1) (H2mal=malonic acid) was prepared and its structure determined by X-ray diffraction methods. Each copper atom in 1 is in a square planar environment formed by four malonate-oxygens from two malonate ligands. The manganese atom is six-coordinated with four water molecules and two cis-coordinated malonate-oxygens from two malonate groups building a distorted octahedral surrounding. The malonate group acts simultaneously as bidentate and monodentate ligand towards copper and manganese atoms respectively, leading to a bimetallic chain. Two structurally different carboxylato-bridges exhibiting an anti–syn…

Solid‐State Anion–Guest Encapsulation by Metallosupramolecular Capsules Made from Two Tetranuclear Copper(II) Complexes (Eur. J. Inorg. Chem. 29/2007)

The cover picture shows unique examples of homo- and heterochiral, dimeric metal capsules resulting from the self-assembly of two helical, bowl-shaped tetranuclear copper(II) complexes that encapsulate different anions in the solid state, like pearls in an oyster (shown as the background). This kind of self-assembled, coordination-bonded motifs are a major topic in metallosupramolecular chemistry because of their binding capabilities and associated host–guest chemistry. However, their magnetic properties are largely unexplored, and here we provide one of the rare magnetic studies on these host–guest systems. For more details on the combined structural and magnetic investigations of this cla…

A new eight-coordinate complex of manganese(II): synthesis, crystal structure, spectroscopy and magnetic properties of [Mn(Hoxam)2(H2O)4] (H2oxam=oxamic acid)

Abstract The crystal structure of an eight-coordinate manganese(II) compound containing oxamato and water molecules as ligands [Mn(Hoxam)2(H2O)4], were H2oxam=oxamic acid, has been determined by X-ray diffraction on single-crystals. The coordinated oxygen atoms are located at the vertices (corners) of a distorted bicapped trigonal antiprism. Hydrogen bonding is responsible for an extended 3D-network. The magnetic susceptibility data of the compound have been investigated. χMT follows the Curie law, at very low temperatures χMT decreases smoothly due to weak intermolecular interactions and/or due to a small zero field splitting of the sextuplet spin state of the Mn(II).

[Fe(bipy)(CN)4]- as a Versatile Building Block for the Design of Heterometallic Systems:  Synthesis, Crystal Structure, and Magnetic Properties of PPh4[FeIII(bipy)(CN)4]·H2O, [{FeIII(bipy)(CN)4}2MII(H2O)4]·4H2O, and [{FeIII(bipy)(CN)4}2ZnII]·2H2O [bipy = 2,2‘-Bipyridine; M = Mn and Zn]

The new cyano complexes of formulas PPh4[FeIII(bipy)(CN)4]·H2O (1), [{FeIII(bipy)(CN)4}2MII(H2O)4]·4H2O with M = Mn (2) and Zn (3), and [{FeIII(bipy)(CN)4}2ZnII]·2H2O (4) [bipy = 2,2‘-bipyridine and PPh4 = tetraphenylphosphonium cation] have been synthesized and structurally characterized. The structure of complex 1 is made up of mononuclear [Fe(bipy)(CN)4]- anions, tetraphenyphosphonium cations, and water molecules of crystallization. The iron(III) is hexacoordinated with two nitrogen atoms of a chelating bipy and four carbon atoms of four terminal cyanide groups, building a distorted octahedron around the metal atom. The structure of complexes 2 and 3 consists of neutral centrosymmetric […

Homo- and heterometallic complexes constructed from hexafluoroacetylacetonato and Schiff-base complexes as building-blocks

Three new homo- and heterotrimetallic complexes have been synthesized and crystallographically characterized: [Cu2(saldmpn)2(μ-OCH3)2Cu2(hfac)2] (1), [Ni2(valaepy)2(hfac)2] (2), [Cu(saldmpn)Co(hfac)2] (3) [H2saldmpn is the Schiff-base resulting from condensation of salicylaldehyde with 2,2-dimethyl-1,3-diaminopropane and Hvalaepy results from the reaction of o-vanillin with 2-(2-aminoethyl)pyridine)]. The structure of 1 consists of a neutral tetranuclear species that can be viewed as resulting from mutual coordination of one {(hfac)Cu(μ-OCH3)2(Cu(hfac)} and two {Cu(saldmpn)} building blocks. Compound 2 is a binuclear complex that results from two {Ni(hfac)(valaepy} fragments, the nickel(II)…

Structural versatility of the malonate ligand as a tool for crystal engineering in the design of molecular magnets

The synthesis of ferro- and ferri-magnetic systems with a tunable Tc and three-dimensional (3-D) ordering from molecular precursors implying transition metal ions is one of the active branches of molecular inorganic chemistry. The nature of the interactions between the transition metal ions (or transition metal ions and radicals) is not so easy to grasp by synthetic chemists working in this field since it may be either electrostatic (orbital) or magnetic (mainly dipolar). Therefore, the systems fulfilling the necessary requirements to present the expected magnetic properties are not so easy to design on paper and realize in the beaker. In this work we show how the design of one-, two- and t…

Spin Frustration in Triangular Cu 3 II Complexes with 6‐Methyl‐2‐pyridyloxime as Ligand – Synthesis, Structural, and Magnetic Characterization

In the present work, new examples of μ3-OH/oximato Cu3 triangles have been obtained by treatment of different copper salts with 6-methyl-2-pyridylaldoxime [6-MepyC(H)NOH, 6-mepaoH]. Depending on the anion, the compounds [Cu3(OH)(6-mepao)3(O2CPh)2] (1), [Cu6(OH)2(6-mepao)6(NO3)3](NO3)·H2O (2·H2O) and [Cu6(OH)2(6-mepao)6(ClO4)3](ClO4) (3) formed and were characterized. Complex 1 is an isolated triangle, whereas 2 and 3 are hexanuclear compounds with two triangular subunits linked by anionic bridges. Susceptibility measurements show very strong antiferromagnetic interactions and the presence of antisymmetric exchange at low temperature. The magnetic properties of these frustrated triangles hav…

Slow Relaxation of the Magnetization in a {Co <sup>III</sup>Mn <sup>III</sup>} Heterometallic Brick-Wall Network

The use of the cyanide-bearing dicobalt(III) complex (PPh 4 ) 2 [Co 2 III (m-2,5-dpp)(CN) 8 ] as a metalloligand towards [Mn(salen)(H 2 O)]ClO 4 afforded the heterobimetallic two-dimensional compound of formula [{Mn III (salen)} 2 {(m-NC) 4 Co 2 III (m-2,5-dpp)(CN) 4 }] n (1) [PPh 4 + = teraphenylphosphonium cation, 2,5-dpp = 2,5-bis(2-pyridyl)pyrazine and H 2 salen = N,N’ -ethylenebis(salicylideneimine)] whose structure has been determined by single crystal X-ray diffraction. Compound 1 exhibits a neutral brick-wall structure, where each [Co 2 III (m-2,5-dpp)(CN) 8 ] 2- unit adopts a tetrakis-monodentate bridging mode towards four {Mn III (salen)} + fragments through four of its eight cyan…

Syntheses, Crystal Structures, and Magnetic Properties of the Oxalato-Bridged Mixed-Valence Complexes [FeII(bpm)3]2[FeIII2(ox)5]·8H2O and FeII(bpm)3Na(H2O)2Fe(ox)3·4H2O (bpm = 2,2‘-Bipyrimidine)

The preparation and crystal structures of two oxalato-bridged FeII-FeIII mixed-valence compounds, [FeII(bpm)3]2[FeIII2(ox)5].8H2O (1) and FeII(bpm)3Na(H2O)2FeIII(ox)(3).4H2O (2) (bpm = 2,2'-bipyrimidine; ox = oxalate dianion) are reported here. Complex 1 crystallizes in the triclinic system, space group P1, with a = 10.998(2) A, b = 13.073(3) A, c = 13.308(3) A, alpha = 101.95(2) degrees, beta = 109.20(2) degrees, gamma = 99.89(2) degrees, and Z = 1. Complex 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 12.609(2) A, b = 19.670(5) A, c = 15.843(3) A, beta = 99.46(1) degrees, and Z = 4. The structure of complex 1 consists of centrosymmetric oxalato-bridged dinuclear h…

Synthesis, crystal structure and magnetic properties of novel heterobimetallic malonate-bridged MIIReIV complexes (M = Mn, Fe, Co and Ni).

Five novel ReIV-MII bimetallic complexes of formula [ReCl4(mu-mal)M(dmphen)2].MeCN [M = Co (1), Fe (2) and Ni (3)], [ReCl4(mu-mal)Ni(dmphen)(MeCN)2(H2O)].(MeCN)0.5(H2O)0.5 (4), and [ReCl4(mu-mal)Mn(dmphen)(H2O)2].dmphen.MeCN.H2O (5) (mal = malonate dianion, dmphen = 2,9-dimethyl-1,10-phenanthroline) have been synthesized, and the structures of 1, 2, 4, and 5 determined by single-crystal X-ray diffraction. The structures of 1 and 2 consist of neutral [ReCl4(mu-mal)M(dmphen)2] dinuclear units where the metal ions are linked through a malonate ligand which adopts simultaneously the bidentate (at ReIV) and monodentate (at MII) coordination modes. The bridging carboxylate-malonate group in them …

Antisymmetric exchange in triangular tricopper(II) complexes: correlation among structural, magnetic, and electron paramagnetic resonance parameters.

Two new trinuclear copper(II) complexes, [Cu(3)(μ(3)-OH)(daat)(Hdat)(2)(ClO(4))(2)(H(2)O)(3)](ClO(4))(2)·2H(2)O (1) and [Cu(3)(μ(3)-OH)(aaat)(3)(H(2)O)(3)](ClO(4))(2)·3H(2)O (2) (daat = 3,5-diacetylamino-1,2,4-triazolate, Hdat = 3,5-diamino-1,2,4-triazole, and aaat = 3-acetylamino-5-amino-1,2,4-triazolate), have been prepared from 1,2,4-triazole derivatives and structurally characterized by X-ray crystallography. The structures of 1 and 2 consist of cationic trinuclear copper(II) complexes with a Cu(3)OH core held by three N,N-triazole bridges between each pair of copper(II) atoms. The copper atoms are five-coordinate with distorted square-pyramidal geometries. The magnetic properties of 1 …

Rhenium(IV) cyanate complexes: Synthesis, crystal structures and magnetic properties of NBu4[ReBr4(OCN)(DMF)] and (NBu4)2[ReBr(OCN)2(NCO)3]

Abstract Two new rhenium(IV) mononuclear compounds of formula NBu4[ReBr4(OCN)(DMF)] (1) and (NBu4)2[ReBr(OCN)2(NCO)3] (2) (NBu4 = tetrabutylammonium cation, OCN = O-bonded cyanate anion, NCO = N-bonded cyanate anion and DMF = N,N-dimethylformamide) have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. 1 crystallizes in the monoclinic system with the space group P21/n, whereas 2 crystallizes in the triclinic one with P 1 ¯ as space group. In both complexes the rhenium atom is six-coordinated, in 1 by four Br atoms in the equatorial plane, and two trans-oxygen atoms, one of a DMF molecule and another one from a cyanato group, while in 2 by one brom…

Hexahalorhenate(iv) salts of protonated ciprofloxacin: antibiotic-based single-ion magnets

Two novel Re(IV) compounds of formula [H2cip][Hcip][ReCl6]Cl·H2O (1) and [Hcip]2[ReBr6] (2) [(H2cip)2+/(Hcip)+ = ciprofloxacindiium cation / ciprofloxacinium cation] have been synthesized and studied structurally and magnetically. 1 crystallizes in the monoclinic system with space group P21/c, whereas 2 crystallizes in the orthorhombic system with space group Pbca. 1 and 2 are hexahalorhenate(IV) salts obtained with the protonated ciprofloxacin antibiotic. In their crystal lattice, the [ReX6]2− [X = Cl(1) and Br(2)] anions are well separated from each other through the protonated ciprofloxacindiium (1) and ciprofloxacinium (1 and 2) cations, which are arranged without generating intermolecu…

Binuclear Ni(II) complexes based on bridging oxalate and tetracyanometallates.

The trimeric complexes, [{Ni(dien)}2(m-ox){(m-Pd(CN)4)}] (2) and [{Ni(dien)}2(m-ox){(m-Pt(CN)4)}] (3) were synthesised by the reaction of [{Ni(dien)(H2O)}2(m-ox)](PF6)2/2H2O (dien � /dietylenetriamine and ox� /oxalate) with K2Pd(CN)4 and K2Pt(CN)4, respectively. In this reaction, water substitution and molecular reconstruction reactions take place to afford trimer complexes. These compounds are isostructural with the molecular compound [{Ni(dien)}2(m-ox){(m-Ni(CN)4)}] (1). In each complex, the two octahedrally coordinated Ni atoms are oxalate bridged and the sphere of coordination of each Ni is completed by three nitrogen atoms from a diethylenetriamine ligand in fac arrangement and one nit…

Magneto-structural diversity of Co(ii) compounds with 1-benzylimidazole induced by linear pseudohalide coligands

We report the preparation, spectroscopic characterisation, crystal structure determination and cryomagnetic investigation of three cobalt(II) complexes of formula trans-[Co(bim)4(NCS)2] (1), [Co(bim)2(NCO)2] (2) and [Co(bim)2(N3)2]n (3) (bim = 1-benzylimidazole). The structure of 1 is made up of neutral [Co(bim)4(NCS)2] mononuclear units, where the cobalt(II) ion is six-coordinate with four monodentate bim ligands in equatorial positions and two N-thiocyanato groups in the axial sites building a slightly compressed octahedron. In contrast to 1, each cobalt(II) ion in 2 is four-coordinate with two imidazole-nitrogen atoms from two bim molecules and two N-cyanato ligands describing a slightly…

Strukturelle und magnetische Charakterisierung eines neuen, siebenkernigen Hydroxo-verbrückten Kupfer(II)-Clusters mit einem Zentralgerüst aus zwei eckenverknüpften Würfeln

Synthesis, Crystal Structure and Magnetic Properties of Three {Cr III Mn II } Heterodimetallic Complexes Based on Heteroleptic Cyanido‐Bearing Cr III Building Blocks

The use of the heteroleptic [CrIII(AA)(CN)4]- complex as a ligand towards the preformed [MnII(tptz)]2+ and [MnII(pyim)2]2+ species afforded the heterometallic compounds: [MnII(tptz)(H2O)(NO3)(-NC)CrIII(ampy)(CN)3]CH3CN (1), [MnII(tptz)(H2O)(NO3)(-NC)CrIII(phen)(CN)3]H2O (2) and {[MnII(pyim)2][(-NC)Cr(phen)(CN)3]2}3H2O (3) [AA = 2-aminomethylpyridine (ampy) and 1,10-phenanthroline (phen), tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine and pyim = 2-(1H-imidazol-2-yl)pyridine]. 1 and 2 are neutral heterodinuclear complexes where a [CrIII(AA)(CN)4]- building block acts as a monodentate ligand through one cyanide group towards a seven coordinate MnII ion. Compound 3 is a neutral heterotrinuclear co…

[Criii(L)(CN)4]−: a new building block in designing cyanide-bridged 4,2-ribbon-like chains {[Criii(L)(CN)4]2Mn(H2O)2}·nH2O [L = 2-aminomethylpyridine (n = 6) and 1,10-phenanthroline (n = 4)]

The preparation, X-ray crystallography and magnetic study of compounds PPh4[Cr(ampy)(CN)4]·H2O (1), PPh4[Cr(phen)(CN)4]·H2O·CH3OH (2), {[Cr(ampy)(CN)4]2Mn(H2O)2}·6H2O (3) and {[Cr(phen)(CN)4]2Mn(H2O)2}·4H2O (4), with PPh4+ = tetraphenylphosphonium cation, ampy = 2-aminomethylpyridine and phen = 1,10-phenanthroline, are reported here. 1 and 2 are mononuclear complexes whereas 3 and 4 are 4,2-ribbon-like bimetallic chains. The magnetic properties of 1–4 were investigated in the temperature range 1.9–300 K. A quasi Curie law behaviour for a magnetically isolated spin quartet is observed for 1 and 2. Compounds 3 and 4 are ferrimagnetic CrIII2MnII chains, which exhibit a metamagnetic behaviour, …

Two-Dimensional Coordination Polymers Constructed Using, Simultaneously, Linear and Angular Spacers and Cobalt(II) Nodes. New Examples of Networks of Single-Ion Magnets

Two novel bidimensional coordination polymers, [Co(azbbpy)(4,4'-bipy)0.5(DMF)(NCS)2]·MeOH (1) and [Co(azbbpy)(bpe)0.5(DMF)(NCS)2]·0.25H2O (2), resulted from the assembling of cobalt(II) ions by 1,3-bis(4-pyridyl)azulene, using either 4,4'-bipyridyl or 1,2-bis(4-pyridyl)ethylene as neutral spacers. The cobalt(II) nodes in 1 and 2 act as single-ion magnets (SIMs).

Towards multifunctional magnetic systems through molecular-programmed self assembly of Re(IV) metalloligands

Abstract The molecular-programmed approach based on the use as ligands of tailor-made metalloligands containing stable six-coordinate rhenium(IV) as paramagnetic centres is presented in this review article. A relatively large amount of spin density is covalent-delocalized away from the rhenium to the peripheral atoms of the ligands in the case of the Re(IV) metalloligands, as shown by polarized neutron diffraction experiments and density functional theory calculations. This feature accounts for the significant through space-magnetic interactions that occur in most of its mononuclear species and more interestingly it also explains the strengthening of the magnetic interactions in the heterom…

Mononuclear and polynuclear complexes ligated by an iminodiacetic acid derivative: synthesis, structure, solution studies and magnetic properties

Two novel families of coordination polymers, [Ln(bzlida)(Hbzlida)]·H2O (Ln = La, Nd) and [Ln2(bzlida)3]·3H2O (Ln = Nd, Sm, Eu, Gd) were prepared by hydrothermal reaction of Ln2O3 with benzyliminodiacetic acid (H2bzlida). The conditions of synthesis, in particular the pH value, were selected on the basis of previous speciation studies reported in this work. The first type of complex consists of 1D chains built by a fully deprotonated ligand bridging two lanthanide ions and protonated Hbzlida(-) ligands connecting three cations. The second type is formed by [Ln2(bzlida)3] bimetallic units in which the ligand has a tridentate NOO coordination mode. This is expanded to a 2D network through carb…

Ordered mesoporous silicas as host for the incorporation and aggregation of octanuclear nickel(ii) single-molecule magnets: a bottom-up approach to new magnetic nanocomposite materials

Silica-based mesoporous materials have been employed as the support host for a suitably designed small octanuclear nickel(II) guest complex with a moderately anisotropic S = 4 ground spin state (D = −0.23 cm−1), which behaves as a single-molecule magnet at low temperature (TB = 3.0 K). Both unimodal MCM-41 and bimodal UVM-7 porous silica provide appropriate template conditions for the incorporation and aggregation of the Ni8 complex precursor into larger complex aggregates, showing slow relaxation of the magnetization at higher blocking temperatures than the crystalline material. By playing with the initial complex vs. silica concentration, two series of samples with varying complex loading…

Syntheses, crystal structures and magnetic properties of di- and trinuclear croconato-bridged copper(ii) complexes

The new croconato-bridged copper(II) compounds [Cu2(terpy)2(H2O)2(C5O5)](NO3)2·H2O (1) and [Cu3(phen)5(C5O5)2](CF3SO3)2 (2) (C5O52− = croconate, dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione; terpy = 2,2′:6′,2″-terpyridine; phen = 1,10-phenanthroline) have been prepared, and their crystal structures and variable temperature magnetic susceptibilities determined. The structure of complex 1 consists of croconato-bridged dinuclear [Cu2(terpy)2(H2O)2(C5O5)]2+ complex ions, nitrate counter ions and water of hydration. The croconato ligand exhibits an asymmetrical bis-bidentate coordination mode through four of its five oxygen atoms. The two crystallographically independent copper atoms hav…

Structural, photophysical and magnetic properties of transition metal complexes based on the dipicolylamino-chloro-1,2,4,5-tetrazine ligand

International audience; The ligand 3-chloro-6-dipicolylamino-1,2,4,5-tetrazine (Cl-TTZ-dipica) 1, prepared by the direct reaction between 3,6-dichloro-1,2,4,5-tetrazine and di(2-picolyl)-amine, afforded a series of four neutral transition metal complexes formulated as [Cl-TTZ-dipica-MCl2]2, with M = Zn(II), Cd(II), Mn(II) and Co(II), when reacted with the corresponding metal chlorides. The dinuclear structure of the isostructural complexes was disclosed by single crystal X-ray analysis, clearly indicating the formation of [MII–(μ-Cl)2MII] motifs and the involvement of the amino nitrogen atom in semi-coordination with the metal centers, thus leading to distorted octahedral coordination geome…

S-shaped decanuclear heterometallic [Ni8Ln2] complexes [Ln(iii) = Gd, Tb, Dy and Ho]: theoretical modeling of the magnetic properties of the gadolinium analogue

The reaction of 8-quinolinol-2-carboaldoxime (LH2) with Ni(II) and Ln(III) salts afforded the heterometallic decanuclear compounds [Ni8Dy2(μ3-OH)2(L)8(LH)2(H2O)6](ClO4)2·16H2O (1), [Ni8Gd2(μ3-OH)2(L)8(LH)2(H2O)4(MeOH)2](NO3)2·12H2O (2), [Ni8Ho2(μ3-OH)2(L)8(LH)2(H2O)4(MeOH)2](ClO4)2·2MeOH·12H2O (3) and [Ni8Tb2 (μ3-OH)2(L)8(LH)2(MeOH)4(OMe)2]·2CH2Cl2·8H2O (4). While compounds 1-3 are dicationic, compound 4 is neutral. These compounds possess an S-shaped architecture and comprise a long chain of metal ions bound to each other. In all the complexes, the eight Ni(II) and two Ln(III) ions of the multimetallic ensemble are hold together by two μ3-OH, eight dianionic (L(2-)) and two monoanionic oxi…

Stepwise formation of a pentanuclear Ni4Cu heterometallic complex exhibiting a vertex-sharing defective double-cubane core and diphenoxo- and phenoxo/azide bridging groups: a magnetostructural and DFT theoretical study.

Sequential reaction of a N5O3 octadentate tripodal ligand with Ni(2+) and subsequently with Cu(2+) and azide ligand afforded the first example of a heterobridged (phenoxo/μ(1,1)-azido) pentanuclear heterometallic (Ni4Cu) compound, which exhibits a centrosymmetric vertex-sharing defective double-cubane structure. The study of the magnetic properties reveals that the compound shows ferromagnetic interaction interactions, leading to an S = 9/2 spin ground state. Density functional theory calculations on the X-ray structure and model compounds predict ferromagnetic interactions through the magnetic exchange pathways involving each couple of metal ions.

Long-distance magnetic coupling in dinuclear copper(II) complexes with oligo-para-phenylenediamine bridging ligands

Abstract Two novel dinuclear copper(II) complexes of formulae [Cu2(tren)2(bpda)](ClO4)4 (2) and [Cu2(tren)2(tpda)](ClO4)4 (3) containing the tripodal tris(2-aminoethyl)amine (tren) terminal ligand and the 4,4′-biphenylenediamine (bpda) and 4,4″-p-terphenylenediamine (tpda) bridging ligands have been synthesized and structurally, spectroscopically, and magnetically characterized. Their experimentally available electronic spectroscopic and magnetic properties have been reasonably reproduced by DFT and TDDFT calculations. Single crystal X-ray diffraction analysis of 2 shows the presence of dicopper(II) cations where the bpda bridging ligand adopts a bismonodentate coordination mode toward two …

Two-Dimensional 3d–4f Heterometallic Coordination Polymers: Syntheses, Crystal Structures, and Magnetic Properties of Six New Co(II)–Ln(III) Compounds

Six new heterometallic cobalt(II)-lanthanide(III) complexes of formulas [Ln(bta)(H2O)2]2[Co(H2O) 6]·10H2O [Ln = Nd(III) (1) and Eu(III) (2)] and [Ln2Co(bta)2(H2O)8] n·6nH2O [Ln = Eu(III) (3), Sm(III) (4), Gd(III) (5), and Tb(III) (6)] (H4bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized via single-crystal X-ray diffraction. 1 and 2 are isostructural compounds with a structure composed of anionic layers of [Ln(bta)(H2O)2]n n- sandwiching mononuclear [Co(H2O)6]2+ cations plus crystallization water molecules, which are interlinked by electrostatic forces and hydrogen bonds, leading to a supramolecular three-dimensional network. 3-6 are also isostructural compou…

Syntheses, crystal structures and magnetic properties of new oxalato-, croconato- and squarato-containing copper(ii) complexesElectronic supplementary information (ESI) available: Stereoview of the structure of compound 2 (Fig. S1) and X-ray data as described in the text. See http://www.rsc.org/suppdata/nj/b3/b301212n/

The preparation and magnetic investigation of five mononuclear copper(II) complexes of formula [Cu(pyim)(C2O4)(H2O)]·2H2O (1), [Cu(pyim)(C4O4)(H2O)2]·2H2O (2), Cu(pyim)(C5O5)·2.5H2O (3), [Cu(H2bim)(C2O4)(H2O)]·H2O (4) and [Cu(bpz)(C5O5)(H2O)] (5) [pyim=2-(2-pyridyl)imidazole, H2bim=2,2′-biimidazole, bpz=2,2′-bipyrazine, C2O42−=dianion of oxalic acid, C4O42−=dianion of squaric acid and C5O52−=dianion of croconic acid] are reported. The crystal structures of 1, 2, 4 and 5 have been determined. The copper atom has a distorted square pyramidal geometry in this family of complexes: two nitrogen atoms from the bidentate nitrogen donor [pyim (1 and 2), H2bim (4) and bpz (5)] and two oxygen atoms e…

Hexanuclear manganese(III) single-molecule magnets based on oxime and azole-type ligands

Abstract Two novel hexanuclear manganese(III) complexes belonging to the Mn6 family of single-molecule magnets (SMMs), of formulae [Mn6(μ3-O)2(H2N-sao)6(bta)2(EtOH)6]·2EtOH·4H2O (1) and [Mn6(μ3-O)2(H2N-sao)6(pta)2(EtOH)6]·4EtOH (2) [H2N-saoH2 = salicylamidoxime, bta = 1,2,3-benzotriazolate anion, pta = 5-phenyl-tetrazolate anion], have been synthesized and characterized structurally and magnetically. Both compounds crystallize in the triclinic system with space group P 1 ¯ (1 and 2). In their crystal packing, adjacent Mn6 complexes are connected through non-coordinating solvent molecules, which are H-bonded to N atoms of azole rings and –NH2 groups of salicylamidoxime ligand. The study of t…

Crystal structures and magnetic properties of two- and three-dimensional malonato-bridged manganese(ii) complexes

Two new manganese(II) compounds of formula [Mn(mal)(H2O)(2,4′-bpy)]n (1) and [Mn2(mal)2(H2O)2(4,4′-bpy)]n (2) (2,4′-bpy = 2,4′-bipyridine, 4,4′-bpy = 4,4′-bipyridine and H2mal = malonic acid) have been prepared and structurally characterized by X-ray crystallography. Their structures are made up of two- (1) and three-dimensional (2) arrangements of manganese atoms linked by carboxylate-malonate groups in the anti–syn bridging mode (1 and 2) and bis(monodentate) 4,4′-bpy (2). The 2,4′-bpy group in 1 acts as a monodentate ligand. Each manganese atom in 1 and 2 is six-coordinated with four carboxylate-oxygens in the equatorial plane and a nitrogen atom and a water molecule in the axial positio…

Alternating Ferro- and Antiferromagnetic Interactions in a Chainlike CuII Coordination Polymer

Architecture dependence on the steric constrains of the ligand in cyano-bridged copper(I) and copper(II)-copper(I) mixed-valence polymer compounds containing diamines: crystal structures and spectroscopic and magnetic properties.

A family of cyano-bridged copper(II)-copper(I) mixed-valence polymers containing diamine ligands of formula [Cu(pn)(2)][Cu(2)(CN)(4)] (1, pn = 1,2-propanediamine), [Cu(2)(CN)(3)(dmen)] (2, dmen = N,N-dimethylethylenediamine), and [Cu(3)(CN)(4)(tmen)] (3, tmen = N,N,N',N'-tetramethylethylenediamine) have been prepared with the aim of analyzing how their architecture may be affected by steric constraints imposed by the diamine ligands. In the absence of diamine and with use of the voluminous NEt(4)(+) cation, the copper(I) polymer [NEt(4)][Cu(2)(CN)(3)] (4) forms. The structure of 1 consists of a three-dimensional diamond-related anionic framework host, [Cu(2)(CN)(4)](2-), and enclathrated [C…

Heterometallic Pentanuclear [Ni 4 Ln] (Ln III = Gd, Tb, Dy, Ho) Complexes: Accidental Orthogonality Leading to Ferromagnetic Interactions

The reaction of 6-formyl-2-(hydroxymethyl)-4-methylphenol (LH2) with NiII and LnIII salts afforded a series of heterometallic pentanuclear compounds [Ni4Ln(L)4(OAc)2(MeOH)4](NO3)(MeOH) [LnIII = Gd (1), Dy (2), Tb (3), Ho (4)]. Four dianionic L2– ligands and two acetate anions hold together four NiII and one LnIII ion to form a Ni4Ln core possessing a distorted tetrahedral geometry. All the NiII ions are hexacoordinate (6 O) with a distorted octahedral geometry whereas the LnIII ion is octacoordinate (8 O) with a distorted square-antiprism geometry. All the NiII ions are connected to the central LnIII ion through μ2 bridging of one deprotonated phenolic oxygen and two deprotonated alkoxy oxy…

Heterobimetallicd—f Metal Complexes as Potential Single-Source Precursors for MOCVD: Structure and Thermodynamic Study of the Sublimation of [Ni(salen)Ln(hfa)3], Ln = Y, Gd

Heterobimetallic [Ni(salen)Ln(hfa)3] species [H2salen and Hhfa being N,N′-ethylenebis(salicylideneimine) and hexa-fluoroacetylacetone respectively], where Ni(salen) acts as a neutral chelating ligand towards LnIII, form a series of isostructural compounds for Ln = YIII and any lanthanideIII cation from La to Yb. They are also isostructural with some of the [Cu(salen)Ln(hfa)3] compounds. They sublime without decomposition under vacuum which makes them potential single-source precursors in MOCVD. Sublimation, thermal behaviour, pressure and composition of the vapour phase versus temperature have been studied for the yttrium derivative, by means of thermal analyses, and mass spectrometry using…

Dicopper(II) pyrazolenophanes: Ligand effects on their structures and magnetic properties

Abstract The use of simple pyrazolate anions and related polychelating acyclic or macrocyclic pyrazolate derivatives as bridging ligands, and occasionally additional blocking ligands, has led to the stereospecific Cu II -mediated self-assembly of both homo- and heteroleptic di-μ-pyrazolatodicopper(II) complexes of the metallacyclophane type, so-called dicopper(II) pyrazolenophanes. Besides their unique molecular conformation features and binding abilities toward both neutral molecules and charged anionic species, which have illustrated the putative role of weak intramolecular π–π stacking, hydrogen bonding, and coordinative interactions in the self-assembling process, dicopper(II) pyrazolen…

Ligand design for multidimensional magnetic materials: a metallosupramolecular perspective.

The aim and scope of this review is to show the general validity of the ‘complex-as-ligand’ approach for the rational design of metallosupramolecular assemblies of increasing structural and magnetic complexity. This is illustrated herein on the basis of our recent studies on oxamato complexes with transition metal ions looking for the limits of the research avenue opened by Kahn's pioneering research twenty years ago. The use as building blocks of mono-, di- and trinuclear metal complexes with a novel family of aromatic polyoxamato ligands allowed us to move further in the coordination chemistry-based approach to high-nuclearity coordination compounds and high-dimensionality coordination po…

A carboxylate-bridged NiII8 cluster with a distorted cubane topology: structure, magnetism and density functional studies

Using a dicarboxylate ligand appended with (2-pyridyl)ethylamine unit, a new cluster [NiII8(L4)6(DMF)2(CH3OH)2(H2O)6][ClO4]4·2CH3OH·2CH3CO2C2H5 (1) [L4(2−): 3-[N-{2-(pyridin-2-yl)ethyl}amino]-bis(propionate)] has been synthesized, through ‘coordination-driven self-assembly’. The crystal structure of 1 reveals a centrosymmetric octanuclear carboxylate-bridged nickel(II) tetracation, with a distorted cubane topology. The four crystallographically independent nickel(II) centres differ markedly in their coordination environment. Magnetic studies (2–300 K) reveal that in 1 the net magnetic-exchange is antiferromagnetic. Based on geometric parameters associated with two interacting nickel(II) cen…

Copper(II) complexes with 2,5-bis(2-pyridyl)pyrazine and 1,1,3,3-tetracyano-2-ethoxypropenide anion: Syntheses, crystal structures and magnetic properties

International audience; The copper(II) complexes of formula [Cu2(2,5-dpp)(H2O)4(CF3SO3)4] · 2H2O (1) and [Cu2(2,5-dpp)(H2O)2(tcnoet)4]n (2) [2,5-dpp = 2,5-bis(2-pyridyl)pyrazine and tcnoet− = 1,1,3,3-tetracyano-2-ethoxypropenide anion] have been prepared and their structures determined by X-ray crystallographic methods. Compound 1 is a dinuclear complex where the 2,5-dpp molecule acts as a bis-bidentate bridge between the two copper centers, the electroneutrality being achieved by four terminally bound triflate anions. Each copper(II) ion presents an elongated octahedral CuN2O4 environment with two nitrogen atoms from 2,5-dpp and two water molecules in the basal plane and two triflate-oxyge…

Synthesis, crystal structure and magnetic properties of a new cyanide-bridged mixed-valence copper(I)/copper(II) clathrate

A unique cyanide-bridge mixed-valence CuI/CuII clathrate of formula [CuI2(CN)3][{CuII(tren)}2(μ-CN)](CF3SO3)2 [tren = tris(2-aminoethyl)amine] containing cyanide-bridged [{CuII(tren)}2(μ-CN)]3 + binuclear cations stacked between anionic honeycomb layered copper(I) cyanide networks, was synthesized and structurally characterized by single crystal X-ray diffraction. Variable-temperature magnetic susceptibility studies showed that the cyanide bridge mediates a strong antiferromagnetic interaction between the copper(II) centers (J = − 160 cm− 1, the spin Hamiltonian being defined as H = − JSA⋅SB).

Charge transfer salts containing a paramagnetic cyano-complex and iodine substituted organic donor involving –I(donor)···N(anion)-interactions

Abstract The preparation, crystal structures, EHT band calculation and optical properties of two new charge transfer salts, namely (DIET)2[Fe(bpca)(CN)3] (1) and (DIEDO)2[Fe(bpca)(CN)3] (2), where bpca = bis(2-pyridylcarbonyl)amide anion, DIET = diiodoethylenedithotetrathiavalene and DIEDO = diiodoethylenedioxotetrathiavalene are reported. The magnetic properties of 2 and those of the low-spin iron(III) precursor of formula (PPh4)[Fe(bpca)(CN)3]·H2O (3) were also investigated in the temperature range 1.9–205 K. Crystal data; (1): monoclinic P21, a = 8.8238(2)A, b = 13.2891(3) A, c = 18.5042(5) A, β = 91.115(1)°, Z = 2, R = 0.0710 for 7021 independent reflections with I > 2 σ(I) and (2): Mon…

Coordinative Versatility of Guanazole [3,5‐Diamino‐1,2,4‐triazole]: Synthesis, Crystal Structure, EPR, and Magnetic Properties of a Dinuclear and a Linear Trinuclear Copper(II) Complex Containing Small Bridges and Triazole Ligands

New complexes with guanazole (3,5-diamino-1,2,4-triazole = Hdatrz), [Cu 2 (Hdatrz) 2 (μ-OH 2 )(H 2 O) 4 (SO 4 )](SO 4 )·3.5H 2 O (1) and [Cu 3 (Hdatrz) 4 (μ-Cl) 2 (H 2 O) 4 (SO 4 ) 2 ]·11.4H 2 O (2), have been prepared and structurally characterized. Complex 1 is a noncentrosymmetric dinuclear compound in which the cop-per(II) ions are bridged by two triazole ligands and one μ-OH 2 molecule, with a Cu(1)···Cu(2) distance of 3.4945(8) A. The chromophores are Cu(1)N 2 O 2 O' (square pyramidal), and Cu(2)N 2 O 2 O'O" (octahedral). Complex 2 has a linear trinuclear copper(II) structure, with two crystallographically independent copper(II) atoms. Neighboring copper(II) ions are linked by two tri…

Chemical Fixation of Atmospheric CO2 by Copper(II) Complexes of a Tridentate N -donor Ligand

Cd(II) and Cu(II) coordination polymers constructed from the expanded 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene ligand: conventional and ultrasound-assisted synthesis, crystal structure, luminescence and magnetic properties

Shaabani, Behrouz/0000-0001-5576-4604; Kubicki, Maciej/0000-0001-7202-9169; Grzeskiewicz, Anita M./0000-0003-0377-2260 WOS: 000447971700041 A 3D open inorganic/organic framework, {[Cd(mu-L)(mu(3)-SO4)(H2O)]center dot H2O}(n) (1) [L = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene] was synthesized by the reaction of CdSO4 center dot 8H(2)O with L. The treatment of Cu(NO3)(2)center dot 3H(2)O with the same N,N'-donor ligand in two different solvent mixtures, methanol/ dichloromethane (2) and methanol/ chloroform (3), afforded two new ladder-like coordination polymers of formula {[Cu(mu-L)(mu-NO3)(NO3)]center dot solv}(n) [solv = CH2Cl2 (2) and CHCl3 (3)]. The non-interpenetrated ladder motifs 2 a…

Influence of the alkaline earth cations on the topology of MII/CuII mixed-metal-organic frameworks (M = Ca, Sr and Ba)

The use of the mononuclear copper(ii) complex, [Cu II(Me 2pma) 2] 2- (Me 2pma = N-2,6-dimethylphenyloxamate), as a bis(bidentate) metalloligand toward solvated alkaline earth metal cations affords a new series of oxamato-bridged heterobimetallic two-dimensional compounds with mixed square-octagonal [Ca II 2Cu II 3] or square [M II 2Cu II 3] (M = Sr and Ba) layered structures of (4·82) and (44·62) net topologies, respectively. © 2012 The Royal Society of Chemistry.

Syntheses, crystal structures and magnetic properties of copper(ii) dicyanamide complexes; dinuclear, chain and ladder compounds

The preparation, crystal structures and magnetic properties of three heteroleptic copper(II) complexes with dicyanamide (dca) bridges, [Cu(bpca)(H2O)(dca)]2 (1) (bpca = bis(2-pyridylcarbonyl)amidate), [Cu(bpy)(dca)2]n (2) (bpy = 2,2′-bipyridine), [Cu2(bpm)(dca)4]n (3) (bpm = 2,2′-bipyrimidine) are reported. In addition, magnetic susceptibility measurements of the sheetlike polymer [Cu(phen)(dca)2] (4) (phen = 1,10-phenanthroline), structurally characterized previously, have been performed. In complex 1 pairs of mononuclear structural building blocks, [Cu(bpca)(dca)(H2O)], are loosely connected through a 1,3-dca bridge in which nitrile is equatorially bound and the amide is semi-coordinated …

[W(bipy)(CN)6]−: A Suitable Metalloligand in the Design of Heterotrimetallic Complexes. The First CuIILnIIIWV Trinuclear Complexes

The first 3d-4f-5d heterotrimetallic complexes using [W(V)(bipy)(CN)(6)](-) as a metalloligand were synthesized (bipy = 2,2'-bipyridine). The structural and magnetic properties of three [Cu(II)Ln(III)W(V)] complexes (Ln = Gd, Ho, Tb) are discussed.

Ferromagnetic dinuclear mixed-valence Mn(II)/Mn(III) complexes: building blocks for the higher nuclearity complexes. structure, magnetic properties, and density functional theory calculations.

A series of six mixed-valence Mn(II)/Mn(III) dinuclear complexes were synthesized and characterized by X-ray diffraction. The reactivity of the complexes was surveyed, and structures of three additional trinuclear mixed-valence Mn(III)/Mn(II)/Mn(III) species were resolved. The magnetic properties of the complexes were studied in detail both experimentally and theoretically. All dinuclear complexes show ferromagnetic intramolecular interactions, which were justified on the basis of the electronic structures of the Mn(II) and Mn(III) ions. The large Mn(II)-O-Mn(III) bond angle and small distortion of the Mn(II) cation from the ideal square pyramidal geometry were shown to enhance the ferromag…

Self-assembly and magnetic properties of a double-propeller octanuclear copper(II) complex with a meso-helicate-type metallacryptand core.

An octanuclear copper(II) complex possessing a dimer-of-tetramers structure self-assembles from a binuclear oxamatocopper(II) metallacryptand of the meso-helicate type; its magnetic behaviour is consistent with its unique double-propeller molecular topology. Pardo Marín, Emilio José, Emilio.Pardo@uv.es ; Julve Olcina, Miguel, Miguel.Julve@uv.es ; Lloret Pastor, Francisco, Francisco.Lloret@uv.es ; Ruiz Garcia, Rafael, Rafael.Ruiz@uv.es

[Cr(AA)(C2O4)2]− and [Cu(bpca)]+ as building blocks in designing new oxalato-bridged CrIIICuII compounds [AA=2,2′-bipyridine and 1,10-phenanthroline; bpca=bis(2-pyridylcarbonyl)amide anion]

Abstract The monouclear complex PPh4[Cr(bipy)(ox)2]·H2O (1) and the heterodinuclear compounds [Cu(bpca)(H2O)Cr(bipy)(ox)2]·2.5H2O (2) and [Cu(bpca)(H2O)Cr(phen)(ox)2]·2H2O (3) [PPh4+=tetraphenylphosphonium cation, bpca=bis(2-pyridylcarbonyl)amide anion, ox=oxalate dianion, bipy=2,2′-bipyridine and phen=1,10-phenanthroline] have been synthesized and characterized by single-crystal X-ray diffraction. Discrete [Cr(bipy)(ox)2]− mononuclear anions and tetraphenylphosphonium cations are present in 1 whereas the structures of 2 and 3 are made up neutral oxalato-bridged bimetallic CrIIICuII units. The chromium environment is distorted octahedral in the three complexes: two nitrogen atoms from a bi…

One-dimensional coordination polymers constructed from di- and trinuclear {3d–4f} tectons. A new useful spacer in crystal engineering: 1,3-bis(4-pyridyl)azulene

Four new heterometallic 3d–4f complexes have been obtained using bi- and trinuclear building blocks: 1∞[Ni(L1)Gd(NO3)3(azbbpy)]·CH3CN (1), [Zn(L1)Eu(NO3)3(azbbpy)]·H2O (2), 1∞[(CuL2)2Gd(NO3)2(dca)] 3 and 1∞[(NiL2)2Dy(H2O)4(oxy-bbz)]NO3·3H2O (4), [H2L1 = 1,3-propanediyl-bis(2-iminomethylene-6-methoxyphenol), H2L2 = 2,6-di(acetoacetyl)pyridine, azbbpy = 1,3-bis(4-pyridyl)azulene, dca− = dicyanamide anion, and oxy-bbz = the dianion of the 4,4′-oxy-bis(benzoic) acid]. 1 and 2 represent the first complexes containing 1,3-bis(4-pyridyl)azulene as a ligand. 1, 3, and 4 are one-dimensional coordination polymers constructed from heterometallic nodes connected by the exo-dentate ligands. Helical chai…

Syntheses, crystal structures and magnetic properties of chromato-, sulfato-, and oxalato-bridged dinuclear copper(II) complexes

Abstract Four dinuclear copper(II) complexes of formula [Cu2(bpca)2(H2O)3(CrO4)]·H2O (1), [Cu2(bpca)2(H2O)3(SO4)]·H2O (2), [Cu2(bpca)2(H2O)2(C2O4)]·2H2O (3), and [Cu2(bpca)2(C2O4)] (4) [bpca=bis(2-pyridylcarbonyl)amide anion] have been synthesized and their magnetic behavior has been investigated as a function of temperature. The structures of 1–3 have been determined by single-crystal X-ray diffraction, whereas the structure of 4 was already known. The structures of this family of complexes are made up of neutral chromateO1,O1′ (1), sulfateO1,O1′ (2) and oxalateO1,O2:O1′,O2′-bridged (3 and 4) dinuclear copper(II) units. The two copper atoms within the dinuclear unit of the isomorphous c…

Synthesis, crystal structure and magnetic properties of two-dimensional malonato-bridged cobalt(ii) and nickel(ii) compounds

Two isostructural malonato-bridged complexes of formula {[M(H2O)2][M(mal)2(H2O)2]}n [M = Co(II) (1), Ni(II) (2); H2mal = malonic acid] have been synthesised and characterized by X-ray diffraction. Their structure consists of corrugated layers of trans-diaquabismalonatemetalate(II) and trans-diaquametal(II) units bridged by carboxylate–malonate groups in the anti–syn conformation. Two crystallographycally independent metal atoms occur in 1 and 2. The malonate anion acts simultaneously as a bidentate and bis-monodentate ligand. Variable-temperature (1.9–295 K) magnetic susceptibility measurements indicate the occurrence of weak antiferro- (1) and ferromagnetic (2) interactions between the cob…

Trinuclear Nickel(II) and Cobalt(II) Complexes Constructed from Mannich–Schiff‐Base Ligands: Synthesis, Crystal Structures, and Magnetic Properties

Anion-Directed Self-Assembly of Unusual Discrete and One-Dimensional Copper(II) Complexes of 3,6-Bis(2′-pyridyl)pyridazine

The preparation and crystal structures of six new copper(II) compounds of formula [Cu(dppn)2(ClO4)]ClO4 (1), [Cu2(dppn)(OH)(ClO4)3(H2O)3]·H2O (2), [Cu2(dppn)2(H2O)2](ClO4)4 (3), [Cu2(dppn)2(ClO4)4] (4), {[Cu2(dppn)(N3)4]·H2O/[Cu2(dppn)(N3)4(H2O)]}n (5) and {[Cu2(dppn)(OH)(dca)3]·H2O}n (6) [dppn = 3,6-bis(2′-pyridyl)pyridazine and dca = dicyanamide] are reported. 1 is a mononuclear complex where two bidentate dppn molecules and a monodentate perchlorate build an intermediate square pyramidal/trigonal bipyramidal (sp/tbp) five-coordinate environment around the copper(II) ion, the overall positive charge being balanced by a free perchlorate anion. 2–4 are dinuclear complexes with either one (2…

A rare isostructural series of 3d–4f cyanido-bridged heterometallic squares obtained by assembling [FeIII{HB(pz)3}(CN)3]− and LnIII ions: synthesis, X-ray structure and cryomagnetic study

A new series of cyanido-bridged {FeIIILnIII}2 neutral molecular squares of general formula [Fe{HB(pz)3}(CN)(μ-CN)2Ln(NO3)2(pyim)(Ph3PO)]2·2CH3CN [Ln = Ce (1), Pr (2), Nd (3), Gd (4), Tb (5), Dy (6) and Er (7); {HB(pz)3}− = hydrotris(pyrazolyl)borate, pyim = 2-(1H-imidazol-2-yl)pyridine and Ph3PO = triphenylphosphine oxide] were obtained by reacting the low-spin [Fe{HB(pz)3}(CN)3]− species with the preformed [LnIII(pyim)(NO3)2(pyim)(Ph3PO)]+ complex anions (generated in situ by mixing the nitrate salt of each Ln(III) ion with pyim and Ph3PO molecules). Single-crystal X-ray diffraction studies show that 1–7 are isostructural compounds that crystallize in the triclinic P space group. Their cry…

Holmium(III) Single-Ion Magnet for Cryomagnetic Refrigeration Based on an MRI Contrast Agent Derivative

The coexistence of field-induced blockage of the magnetization and significant magnetocaloric effects in the low-temperature region occurs in a mononuclear holmium(III) diethylenetriamine-N,N,N′,N″,N″-pentaacetate complex, whose gadolinium(III) analogue is a commercial MRI contrast agent. Both properties make it a suitable candidate for cryogenic magnetic refrigeration, thus enlarging the variety of applications of this simple class of multifunctional molecular nanomagnets.

A Metallacryptand-Based Manganese(II)–Cobalt(II) Ferrimagnet with a Three-Dimensional Honeycomb Open-Framework Architecture

Copper(II)-assisted hydrolysis of 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (tpymt): syntheses, crystal structures and magnetic properties of [Cu(bpcam)(H2O)2]ClO4·3H2O, [Cu(bpcam)(H2O)2][Cu(bpcam)(H2O)(SO4)]·2H2O and [Cu2(bpcam)2(H2O)2(SO4)]·H2O [bpcam=bis(2-pyrimidylcarbonyl)amidate]

Abstract The reaction of the 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (tpymt) ligand with copper(II) perchlorate or sulfate in aqueous solution affords complexes [Cu(bpcam)(H2O)2]ClO4 · 3H2O (1), [Cu(bpcam)(H2O)2][Cu(bpcam)(H2O)(SO4)] · 2H2O (2) and [Cu2(bpcam)2(H2O)2(SO4)] · H2O (3) [bpcam = bis(2-pyrimidylcarbonyl)amidate], whose structures have been determined by single-crystal X-ray diffraction studies. Copper(II) promotes the hydrolysis of tpymt in mild conditions yielding the bpcam group which is present in the structures of 1–3 as a tridentate ligand. The structure of 1 consists of mononuclear [Cu(bpcam)(H2O)2]+ cations, uncoordinated perchlorate anions and water of crystallization. Th…

Hexanuclear Manganese(III) Single-Molecule Magnets

Magneto-structural versatility of copper(II)-3-phenylpropionate coordination polymers with N-donor coligands.

A novel series of copper(II) coordination polymers [Cu2(O2CC8H9)4(pyz)]n (1), [Cu2(O2CC8H9)4(dps)]n (2), {[Cu(O2CC8H9)2(dps)(H2O)]·H2O}n (3), {[NaCu(O2CC8H9)2(bpm)(NO3)]·H2O}n (4), and [Cu4(O2CC8H9)6(OH)2(bpp)2]n (5) [O2CC8H9− = 3-phenylpropionate anion, pyz = pyrazine, dps = di(4-pyridyl)sulfide, bpm = 2,2′-bipyrimidine, and bpp = 1,3-bis(4-pyridyl)propane] have been synthesized and magneto-structurally investigated. Compounds 1 and 2 belong to a large group of copper(II) carboxylates where bis-monodentate pyz (1) and dps (2) ligands connect the paddle-wheel [CuII2(μ-O2CC8H9)4] units leading to alternating copper(II) chains. The structure of 3 consists of uniform chains of trans-[CuII(O2CC…

Hexachlororhenate(IV) salts of organic radical cations

Abstract The ionic salts ( p -rad) 2 [ReCl 6 ] ( 1 ) and ( m -rad) 2 [ReCl 6 ] ( 2 ) ( p / m -rad = 2-(4/3- N -methylpyridinium)-4,4,5,5-tetramethyl-4,5-dihydro-1 H -imidazol-1-oxyl-3- N -oxide) have been prepared and their crystal structures determined by single-crystal X-ray diffraction. The nitronyl nitroxide cations in compound 1 show a layered disposition, whereas the [ReCl 6 ] 2− units are placed between these layers. The nitronyl nitroxide cations in compound 2 adopt an hexagonal array but they do not result in layers. Bulk magnetic properties of 1 and 2 have been investigated in the temperature range 2–300 K. Both compounds show weak but significant intermolecular antiferromagnetic …

A Study of the Lack of Slow Magnetic Relaxation in Mononuclear Trigonal Bipyramidal Cobalt(II) Complexes

Solvothermal synthesis, crystal structure and magnetic properties of homometallic Co(II) and Cu(II) chains with double di(4-pyridyl)sulfide as bridges

Abstract Two new coordination polymers {[Co(μ-4,4′-dps)2(H2O)2](NO3)2·2(4,4′-dps)·4H2O}n (1) and {[Cu(μ-4,4′-dps)2(H2O)2](NO3)2·2H2O}n (2) [4,4′-dps = di(4-pyridyl)sulfide] have been synthesized by solvothermal reactions between the nitrate salts of cobalt(II) (1) and copper(II) (2) and the 4,4′-dps molecule. Compounds 1 and 2 have been characterized by elemental analysis, thermal analysis (TG/DTA), vibrational spectroscopy, single crystal X-ray diffraction analysis and variable-temperature magnetic measurements. Compounds 1 and 2 are cationic chain compounds of formula {[M(μ-4,4′-dps)2(H2O)2]n2n+ [M = Co(II) (1) and Cu(II) (2)] with double 4,4′-dps bridges, uncoordinated nitrate anions, an…

Cyanide-bridged Fe(III)–Co(II) bis double zigzag chains with a slow relaxation of the magnetisation

Reaction of [FeIII(bipy)(CN)4]¯ with fully solvated MII cations [M = Co (1) and Mn (2)] produces the isostructural bis double zigzag chains [[FeIII(bipy)(CN)4]2MII(H2O)]·MeCN·1/2H2O; 1 exhibits intrachain ferromagnetic and interchain antiferromagnetic couplings, slow magnetic relaxation and hysteresis effects. Luminita Marilena, Toma, Luminita.Toma@uv.es ; Lescouezec, Alain Francois Rodri, Alain.Lescouezec@uv.es ; Lloret Pastor, Francisco, Francisco.Lloret@uv.es ; Julve Olcina, Miguel, Miguel.Julve@uv.es

Inter-string arrays of bimetallic assemblies with alternative Cu2+-Cl-Cu2+ and Cu-NC-M (M = Co3+, Fe+3, Cr+3) bridges: syntheses, crystal structure, and magnetic properties.

Three bimetallic assemblies with alternate homometallic bridges through chloride ligands and heterometallic bridges through cyanide ligands of formula [(323)(2)Cu(2)(Cl)M(CN)(6)](n).2n(H(2)O), where 323 = N,N'-bis(3-aminopropyl)ethylenediamine and M = Co(3+) for 1, Fe(3+) for 2, and Cr(3+) for 3, were synthesized. They have been characterized structurally, analytically, spectroscopically, and magnetically. All three assemblies crystallize in the monoclinic system in the same space group P2(1)/n, with a = 11.642(2) A, b = 10.285(3) A, c = 13.622(2) A, beta = 95.69(3) degrees, V = 1623.1(6) A(3), and Z = 4 for 1; a = 11.681(4) A, b = 10.315(3) A, c = 13.567(5) A, beta = 95.62(3) degrees, V = …

The construction of open GdIII metal–organic frameworks based on methanetriacetic acid: New objects with an old ligand

11 páginas, 11 figuras, 2 esquemas.-- et al.

Theoretical design of magnetic wires from acene and nanocorone derivatives

Theoretical calculations on a series of molecular models based on amino derivatives of linear and cycled acenes acting as organic linkers between two copper(ii) ions have shown a wire-like magnetic behaviour, so that the intermetallic magnetic communication does not vanish when the linker becomes larger due to its polyradical nature. Hence, these models can be considered as molecular magnetic wires, which can be used as active components for molecular spintronics, where the information transport is based on spin carriers instead of the more conventional charge transport. The nature of the spin ground state along these two series of models is governed by the topology of the organic linker, i…

CCDC 995944: Experimental Crystal Structure Determination

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CCDC 995946: Experimental Crystal Structure Determination

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CCDC 1496680: Experimental Crystal Structure Determination

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CCDC 2070862: Experimental Crystal Structure Determination

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CCDC 1582396: Experimental Crystal Structure Determination

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CCDC 1580448: Experimental Crystal Structure Determination

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CCDC 1867353: Experimental Crystal Structure Determination

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CCDC 1016163: Experimental Crystal Structure Determination

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CCDC 1469224: Experimental Crystal Structure Determination

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CCDC 1818142: Experimental Crystal Structure Determination

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CCDC 983736: Experimental Crystal Structure Determination

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CCDC 1520091: Experimental Crystal Structure Determination

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CCDC 1938637: Experimental Crystal Structure Determination

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CCDC 1938635: Experimental Crystal Structure Determination

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CCDC 995943: Experimental Crystal Structure Determination

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CCDC 1972102: Experimental Crystal Structure Determination

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CCDC 928583: Experimental Crystal Structure Determination

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CCDC 294297: Experimental Crystal Structure Determination

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CCDC 1969476: Experimental Crystal Structure Determination

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CCDC 1424158: Experimental Crystal Structure Determination

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CCDC 1416018: Experimental Crystal Structure Determination

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CCDC 983489: Experimental Crystal Structure Determination

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CCDC 1482464: Experimental Crystal Structure Determination

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CCDC 1520092: Experimental Crystal Structure Determination

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CCDC 941373: Experimental Crystal Structure Determination

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CCDC 878930: Experimental Crystal Structure Determination

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CCDC 2089144: Experimental Crystal Structure Determination

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CCDC 920638: Experimental Crystal Structure Determination

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CCDC 1471985: Experimental Crystal Structure Determination

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CCDC 1992815: Experimental Crystal Structure Determination

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CCDC 1049500: Experimental Crystal Structure Determination

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CCDC 1025298: Experimental Crystal Structure Determination

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CCDC 1055519: Experimental Crystal Structure Determination

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CCDC 1418715: Experimental Crystal Structure Determination

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CCDC 1567091: Experimental Crystal Structure Determination

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CCDC 294298: Experimental Crystal Structure Determination

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CCDC 1486650: Experimental Crystal Structure Determination

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CCDC 1898457: Experimental Crystal Structure Determination

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CCDC 1580449: Experimental Crystal Structure Determination

Related Article: Oleh Stetsiuk, Abdelkrim El-Ghayoury, Francesc Lloret, Miguel Julve, Narcis Avarvari|2018|Eur.J.Inorg.Chem.||449|doi:10.1002/ejic.201701224

CCDC 1866837: Experimental Crystal Structure Determination

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CCDC 1867830: Experimental Crystal Structure Determination

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CCDC 909392: Experimental Crystal Structure Determination

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CCDC 1469225: Experimental Crystal Structure Determination

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CCDC 1049932: Experimental Crystal Structure Determination

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CCDC 1424159: Experimental Crystal Structure Determination

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CCDC 1938638: Experimental Crystal Structure Determination

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CCDC 919615: Experimental Crystal Structure Determination

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CCDC 1898455: Experimental Crystal Structure Determination

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CCDC 958829: Experimental Crystal Structure Determination

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CCDC 1510396: Experimental Crystal Structure Determination

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CCDC 987581: Experimental Crystal Structure Determination

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CCDC 1047962: Experimental Crystal Structure Determination

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CCDC 958833: Experimental Crystal Structure Determination

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CCDC 995947: Experimental Crystal Structure Determination

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CCDC 984262: Experimental Crystal Structure Determination

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CCDC 1400954: Experimental Crystal Structure Determination

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CCDC 927026: Experimental Crystal Structure Determination

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CCDC 1484384: Experimental Crystal Structure Determination

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CCDC 1957553: Experimental Crystal Structure Determination

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CCDC 1867829: Experimental Crystal Structure Determination

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CCDC 909388: Experimental Crystal Structure Determination

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CCDC 1992813: Experimental Crystal Structure Determination

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CCDC 2044634: Experimental Crystal Structure Determination

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CCDC 1045096: Experimental Crystal Structure Determination

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CCDC 1550041: Experimental Crystal Structure Determination

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CCDC 1989325: Experimental Crystal Structure Determination

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CCDC 1424160: Experimental Crystal Structure Determination

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CCDC 1495414: Experimental Crystal Structure Determination

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CCDC 1049499: Experimental Crystal Structure Determination

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CCDC 1957556: Experimental Crystal Structure Determination

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CCDC 1471984: Experimental Crystal Structure Determination

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CCDC 1969477: Experimental Crystal Structure Determination

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CCDC 958838: Experimental Crystal Structure Determination

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CCDC 919043: Experimental Crystal Structure Determination

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CCDC 1055523: Experimental Crystal Structure Determination

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CCDC 1055520: Experimental Crystal Structure Determination

Related Article: Mario Pacheco, Alicia Cuevas, Javier González-Platas, Francesc Lloret, Miguel Julve, Carlos Kremer|2015|Dalton Trans.|44|11636|doi:10.1039/C5DT01321F

CCDC 2073773: Experimental Crystal Structure Determination

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CCDC 1049501: Experimental Crystal Structure Determination

Related Article: Alina S. Dinca, Sergiu Shova, Adrian E. Ion, Catalin Maxim, Francesc Lloret, Miguel Julve, Marius Andruh|2015|Dalton Trans.|44|7148|doi:10.1039/C5DT00778J

CCDC 1874222: Experimental Crystal Structure Determination

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CCDC 879928: Experimental Crystal Structure Determination

Related Article: Albert Escuer, Gina Vlahopoulou, Francesc Lloret, Franz A. Mautner|2014|Eur.J.Inorg.Chem.||83|doi:10.1002/ejic.201300910

CCDC 1580450: Experimental Crystal Structure Determination

Related Article: Oleh Stetsiuk, Abdelkrim El-Ghayoury, Francesc Lloret, Miguel Julve, Narcis Avarvari|2018|Eur.J.Inorg.Chem.||449|doi:10.1002/ejic.201701224

CCDC 1965761: Experimental Crystal Structure Determination

Related Article: Munirathnam Manda, Himanshu Arora, Arunava Sengupta, Shashi Kant, Francesc Lloret, Rabindranath Mukherjee|2021|New J.Chem.|45|16019|doi:10.1039/D1NJ01150B

CCDC 1036871: Experimental Crystal Structure Determination

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CCDC 1972100: Experimental Crystal Structure Determination

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CCDC 1529277: Experimental Crystal Structure Determination

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CCDC 1991872: Experimental Crystal Structure Determination

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CCDC 1486651: Experimental Crystal Structure Determination

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CCDC 995948: Experimental Crystal Structure Determination

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CCDC 1866835: Experimental Crystal Structure Determination

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CCDC 1901540: Experimental Crystal Structure Determination

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CCDC 1471982: Experimental Crystal Structure Determination

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CCDC 1449346: Experimental Crystal Structure Determination

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CCDC 1896306: Experimental Crystal Structure Determination

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CCDC 987580: Experimental Crystal Structure Determination

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CCDC 1883575: Experimental Crystal Structure Determination

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CCDC 1025299: Experimental Crystal Structure Determination

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CCDC 923163: Experimental Crystal Structure Determination

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CCDC 1524200: Experimental Crystal Structure Determination

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CCDC 1907945: Experimental Crystal Structure Determination

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CCDC 1816300: Experimental Crystal Structure Determination

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CCDC 989258: Experimental Crystal Structure Determination

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CCDC 1969470: Experimental Crystal Structure Determination

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CCDC 987982: Experimental Crystal Structure Determination

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CCDC 1046978: Experimental Crystal Structure Determination

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CCDC 1049546: Experimental Crystal Structure Determination

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CCDC 1901771: Experimental Crystal Structure Determination

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CCDC 940301: Experimental Crystal Structure Determination

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CCDC 1582395: Experimental Crystal Structure Determination

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CCDC 996269: Experimental Crystal Structure Determination

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CCDC 2073771: Experimental Crystal Structure Determination

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CCDC 2070865: Experimental Crystal Structure Determination

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CCDC 996270: Experimental Crystal Structure Determination

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CCDC 986609: Experimental Crystal Structure Determination

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CCDC 1965763: Experimental Crystal Structure Determination

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CCDC 989260: Experimental Crystal Structure Determination

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CCDC 1892383: Experimental Crystal Structure Determination

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CCDC 996271: Experimental Crystal Structure Determination

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CCDC 927025: Experimental Crystal Structure Determination

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CCDC 1567349: Experimental Crystal Structure Determination

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CCDC 1529275: Experimental Crystal Structure Determination

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CCDC 1969471: Experimental Crystal Structure Determination

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CCDC 864757: Experimental Crystal Structure Determination

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CCDC 1045094: Experimental Crystal Structure Determination

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CCDC 1432272: Experimental Crystal Structure Determination

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CCDC 937587: Experimental Crystal Structure Determination

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CCDC 1039720: Experimental Crystal Structure Determination

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CCDC 984263: Experimental Crystal Structure Determination

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CCDC 996274: Experimental Crystal Structure Determination

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CCDC 995949: Experimental Crystal Structure Determination

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CCDC 1945945: Experimental Crystal Structure Determination

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CCDC 1449347: Experimental Crystal Structure Determination

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CCDC 1510397: Experimental Crystal Structure Determination

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CCDC 928580: Experimental Crystal Structure Determination

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CCDC 1045095: Experimental Crystal Structure Determination

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CCDC 1811037: Experimental Crystal Structure Determination

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CCDC 1896307: Experimental Crystal Structure Determination

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CCDC 1039718: Experimental Crystal Structure Determination

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CCDC 1524159: Experimental Crystal Structure Determination

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CCDC 2073772: Experimental Crystal Structure Determination

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CCDC 1047964: Experimental Crystal Structure Determination

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CCDC 2011616: Experimental Crystal Structure Determination

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CCDC 1031230: Experimental Crystal Structure Determination

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CCDC 1400958: Experimental Crystal Structure Determination

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CCDC 953096: Experimental Crystal Structure Determination

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CCDC 1574907: Experimental Crystal Structure Determination

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CCDC 919613: Experimental Crystal Structure Determination

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CCDC 2073774: Experimental Crystal Structure Determination

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CCDC 949950: Experimental Crystal Structure Determination

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CCDC 1538260: Experimental Crystal Structure Determination

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CCDC 945084: Experimental Crystal Structure Determination

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CCDC 1983533: Experimental Crystal Structure Determination

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CCDC 1402554: Experimental Crystal Structure Determination

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CCDC 1039719: Experimental Crystal Structure Determination

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CCDC 1400956: Experimental Crystal Structure Determination

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CCDC 937589: Experimental Crystal Structure Determination

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CCDC 1868872: Experimental Crystal Structure Determination

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CCDC 1530054: Experimental Crystal Structure Determination

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CCDC 1909209: Experimental Crystal Structure Determination

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CCDC 1559171: Experimental Crystal Structure Determination

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CCDC 942308: Experimental Crystal Structure Determination

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CCDC 1486649: Experimental Crystal Structure Determination

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CCDC 1402553: Experimental Crystal Structure Determination

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CCDC 907781: Experimental Crystal Structure Determination

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CCDC 1482465: Experimental Crystal Structure Determination

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CCDC 1901541: Experimental Crystal Structure Determination

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CCDC 1885666: Experimental Crystal Structure Determination

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CCDC 986612: Experimental Crystal Structure Determination

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CCDC 968170: Experimental Crystal Structure Determination

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CCDC 1964202: Experimental Crystal Structure Determination

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CCDC 2011615: Experimental Crystal Structure Determination

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CCDC 984264: Experimental Crystal Structure Determination

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CCDC 1883574: Experimental Crystal Structure Determination

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CCDC 1063253: Experimental Crystal Structure Determination

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CCDC 1582397: Experimental Crystal Structure Determination

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CCDC 928579: Experimental Crystal Structure Determination

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CCDC 1047963: Experimental Crystal Structure Determination

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CCDC 989261: Experimental Crystal Structure Determination

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CCDC 987985: Experimental Crystal Structure Determination

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CCDC 958834: Experimental Crystal Structure Determination

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CCDC 949613: Experimental Crystal Structure Determination

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CCDC 983272: Experimental Crystal Structure Determination

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CCDC 1055521: Experimental Crystal Structure Determination

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CCDC 983271: Experimental Crystal Structure Determination

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CCDC 1872265: Experimental Crystal Structure Determination

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CCDC 937590: Experimental Crystal Structure Determination

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CCDC 1045093: Experimental Crystal Structure Determination

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CCDC 958835: Experimental Crystal Structure Determination

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CCDC 1431249: Experimental Crystal Structure Determination

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CCDC 1898602: Experimental Crystal Structure Determination

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CCDC 1868871: Experimental Crystal Structure Determination

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CCDC 1857503: Experimental Crystal Structure Determination

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CCDC 1957555: Experimental Crystal Structure Determination

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CCDC 1469223: Experimental Crystal Structure Determination

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CCDC 953476: Experimental Crystal Structure Determination

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CCDC 983274: Experimental Crystal Structure Determination

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CCDC 1454962: Experimental Crystal Structure Determination

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CCDC 953097: Experimental Crystal Structure Determination

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CCDC 1046977: Experimental Crystal Structure Determination

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CCDC 949949: Experimental Crystal Structure Determination

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CCDC 1819913: Experimental Crystal Structure Determination

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CCDC 1883576: Experimental Crystal Structure Determination

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CCDC 1898601: Experimental Crystal Structure Determination

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CCDC 968171: Experimental Crystal Structure Determination

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CCDC 1469222: Experimental Crystal Structure Determination

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CCDC 1053439: Experimental Crystal Structure Determination

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CCDC 1965760: Experimental Crystal Structure Determination

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CCDC 1029369: Experimental Crystal Structure Determination

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CCDC 1965762: Experimental Crystal Structure Determination

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CCDC 2089145: Experimental Crystal Structure Determination

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CCDC 1866836: Experimental Crystal Structure Determination

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CCDC 1036537: Experimental Crystal Structure Determination

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CCDC 904908: Experimental Crystal Structure Determination

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CCDC 987579: Experimental Crystal Structure Determination

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CCDC 949948: Experimental Crystal Structure Determination

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CCDC 1818144: Experimental Crystal Structure Determination

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CCDC 1496651: Experimental Crystal Structure Determination

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CCDC 919614: Experimental Crystal Structure Determination

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CCDC 925074: Experimental Crystal Structure Determination

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CCDC 1901770: Experimental Crystal Structure Determination

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CCDC 1910060: Experimental Crystal Structure Determination

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CCDC 1484386: Experimental Crystal Structure Determination

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CCDC 1475076: Experimental Crystal Structure Determination

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CCDC 1867783: Experimental Crystal Structure Determination

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CCDC 1049497: Experimental Crystal Structure Determination

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CCDC 1414395: Experimental Crystal Structure Determination

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CCDC 1818143: Experimental Crystal Structure Determination

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CCDC 1898454: Experimental Crystal Structure Determination

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CCDC 1029370: Experimental Crystal Structure Determination

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CCDC 937591: Experimental Crystal Structure Determination

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CCDC 1495415: Experimental Crystal Structure Determination

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CCDC 1018429: Experimental Crystal Structure Determination

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CCDC 1530055: Experimental Crystal Structure Determination

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CCDC 1567346: Experimental Crystal Structure Determination

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CCDC 1400955: Experimental Crystal Structure Determination

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CCDC 958832: Experimental Crystal Structure Determination

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CCDC 987983: Experimental Crystal Structure Determination

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CCDC 1409933: Experimental Crystal Structure Determination

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CCDC 1550042: Experimental Crystal Structure Determination

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CCDC 999841: Experimental Crystal Structure Determination

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CCDC 1957554: Experimental Crystal Structure Determination

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CCDC 1964204: Experimental Crystal Structure Determination

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CCDC 945083: Experimental Crystal Structure Determination

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CCDC 1481782: Experimental Crystal Structure Determination

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CCDC 1849001: Experimental Crystal Structure Determination

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CCDC 986611: Experimental Crystal Structure Determination

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CCDC 1582340: Experimental Crystal Structure Determination

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CCDC 1993352: Experimental Crystal Structure Determination

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CCDC 1909208: Experimental Crystal Structure Determination

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CCDC 1510399: Experimental Crystal Structure Determination

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CCDC 864758: Experimental Crystal Structure Determination

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CCDC 2070864: Experimental Crystal Structure Determination

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CCDC 1909207: Experimental Crystal Structure Determination

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CCDC 1496758: Experimental Crystal Structure Determination

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CCDC 937588: Experimental Crystal Structure Determination

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CCDC 1529486: Experimental Crystal Structure Determination

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CCDC 1409935: Experimental Crystal Structure Determination

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CCDC 2076621: Experimental Crystal Structure Determination

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CCDC 1992814: Experimental Crystal Structure Determination

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CCDC 1432273: Experimental Crystal Structure Determination

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CCDC 907780: Experimental Crystal Structure Determination

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CCDC 1585318: Experimental Crystal Structure Determination

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CCDC 294299: Experimental Crystal Structure Determination

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CCDC 942307: Experimental Crystal Structure Determination

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CCDC 1579781: Experimental Crystal Structure Determination

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CCDC 1053438: Experimental Crystal Structure Determination

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CCDC 1047965: Experimental Crystal Structure Determination

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CCDC 983273: Experimental Crystal Structure Determination

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CCDC 958831: Experimental Crystal Structure Determination

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CCDC 1901769: Experimental Crystal Structure Determination

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CCDC 1891550: Experimental Crystal Structure Determination

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CCDC 984260: Experimental Crystal Structure Determination

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CCDC 1811038: Experimental Crystal Structure Determination

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CCDC 903521: Experimental Crystal Structure Determination

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CCDC 909389: Experimental Crystal Structure Determination

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CCDC 928582: Experimental Crystal Structure Determination

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CCDC 958836: Experimental Crystal Structure Determination

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CCDC 996272: Experimental Crystal Structure Determination

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CCDC 903522: Experimental Crystal Structure Determination

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CCDC 1964203: Experimental Crystal Structure Determination

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CCDC 1857501: Experimental Crystal Structure Determination

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CCDC 1496674: Experimental Crystal Structure Determination

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CCDC 948414: Experimental Crystal Structure Determination

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CCDC 1049498: Experimental Crystal Structure Determination

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CCDC 987984: Experimental Crystal Structure Determination

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CCDC 1471986: Experimental Crystal Structure Determination

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CCDC 1567347: Experimental Crystal Structure Determination

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CCDC 931371: Experimental Crystal Structure Determination

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CCDC 1991873: Experimental Crystal Structure Determination

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CCDC 989259: Experimental Crystal Structure Determination

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CCDC 1053437: Experimental Crystal Structure Determination

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CCDC 1530056: Experimental Crystal Structure Determination

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CCDC 1567348: Experimental Crystal Structure Determination

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CCDC 1469226: Experimental Crystal Structure Determination

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CCDC 1901768: Experimental Crystal Structure Determination

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CCDC 1983534: Experimental Crystal Structure Determination

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CCDC 1046979: Experimental Crystal Structure Determination

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CCDC 1036873: Experimental Crystal Structure Determination

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CCDC 927027: Experimental Crystal Structure Determination

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CCDC 1579780: Experimental Crystal Structure Determination

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CCDC 1969473: Experimental Crystal Structure Determination

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CCDC 1527528: Experimental Crystal Structure Determination

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CCDC 952343: Experimental Crystal Structure Determination

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CCDC 903520: Experimental Crystal Structure Determination

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CCDC 909390: Experimental Crystal Structure Determination

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CCDC 2069070: Experimental Crystal Structure Determination

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CCDC 1409934: Experimental Crystal Structure Determination

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CCDC 1892384: Experimental Crystal Structure Determination

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CCDC 978949: Experimental Crystal Structure Determination

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CCDC 1816301: Experimental Crystal Structure Determination

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CCDC 983737: Experimental Crystal Structure Determination

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CCDC 2112864: Experimental Crystal Structure Determination

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CCDC 1403663: Experimental Crystal Structure Determination

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CCDC 1896308: Experimental Crystal Structure Determination

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CCDC 984265: Experimental Crystal Structure Determination

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CCDC 1559172: Experimental Crystal Structure Determination

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CCDC 1553972: Experimental Crystal Structure Determination

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CCDC 1867352: Experimental Crystal Structure Determination

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CCDC 903519: Experimental Crystal Structure Determination

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CCDC 1409932: Experimental Crystal Structure Determination

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CCDC 1400953: Experimental Crystal Structure Determination

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CCDC 1400957: Experimental Crystal Structure Determination

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CCDC 1484383: Experimental Crystal Structure Determination

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CCDC 1868873: Experimental Crystal Structure Determination

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CCDC 1495416: Experimental Crystal Structure Determination

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CCDC 1969472: Experimental Crystal Structure Determination

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CCDC 953098: Experimental Crystal Structure Determination

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CCDC 2054785: Experimental Crystal Structure Determination

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CCDC 925073: Experimental Crystal Structure Determination

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CCDC 978951: Experimental Crystal Structure Determination

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CCDC 1558468: Experimental Crystal Structure Determination

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CCDC 1036872: Experimental Crystal Structure Determination

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CCDC 1945944: Experimental Crystal Structure Determination

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CCDC 1898456: Experimental Crystal Structure Determination

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CCDC 909391: Experimental Crystal Structure Determination

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CCDC 1553973: Experimental Crystal Structure Determination

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CCDC 1496742: Experimental Crystal Structure Determination

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CCDC 1574908: Experimental Crystal Structure Determination

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CCDC 928584: Experimental Crystal Structure Determination

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CCDC 978950: Experimental Crystal Structure Determination

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CCDC 1911272: Experimental Crystal Structure Determination

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CCDC 958837: Experimental Crystal Structure Determination

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CCDC 2070863: Experimental Crystal Structure Determination

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CCDC 949947: Experimental Crystal Structure Determination

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CCDC 1443218: Experimental Crystal Structure Determination

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CCDC 1857500: Experimental Crystal Structure Determination

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CCDC 995945: Experimental Crystal Structure Determination

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CCDC 986610: Experimental Crystal Structure Determination

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CCDC 945082: Experimental Crystal Structure Determination

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CCDC 1055522: Experimental Crystal Structure Determination

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CCDC 1524158: Experimental Crystal Structure Determination

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CCDC 1524157: Experimental Crystal Structure Determination

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CCDC 1867351: Experimental Crystal Structure Determination

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CCDC 1400952: Experimental Crystal Structure Determination

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CCDC 2073463: Experimental Crystal Structure Determination

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CCDC 1510395: Experimental Crystal Structure Determination

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CCDC 904907: Experimental Crystal Structure Determination

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CCDC 1907944: Experimental Crystal Structure Determination

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CCDC 1510398: Experimental Crystal Structure Determination

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CCDC 996273: Experimental Crystal Structure Determination

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CCDC 1403662: Experimental Crystal Structure Determination

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CCDC 1045097: Experimental Crystal Structure Determination

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CCDC 1036536: Experimental Crystal Structure Determination

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CCDC 2047766: Experimental Crystal Structure Determination

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CCDC 931372: Experimental Crystal Structure Determination

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CCDC 1567090: Experimental Crystal Structure Determination

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CCDC 1577623: Experimental Crystal Structure Determination

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CCDC 1960115: Experimental Crystal Structure Determination

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CCDC 1892797: Experimental Crystal Structure Determination

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CCDC 911161: Experimental Crystal Structure Determination

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CCDC 984261: Experimental Crystal Structure Determination

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CCDC 1495417: Experimental Crystal Structure Determination

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CCDC 1567092: Experimental Crystal Structure Determination

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CCDC 921556: Experimental Crystal Structure Determination

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CCDC 1883577: Experimental Crystal Structure Determination

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CCDC 1957552: Experimental Crystal Structure Determination

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CCDC 2011617: Experimental Crystal Structure Determination

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CCDC 1529276: Experimental Crystal Structure Determination

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CCDC 1972101: Experimental Crystal Structure Determination

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CCDC 1849015: Experimental Crystal Structure Determination

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CCDC 1964201: Experimental Crystal Structure Determination

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CCDC 2112865: Experimental Crystal Structure Determination

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CCDC 1480787: Experimental Crystal Structure Determination

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CCDC 1910059: Experimental Crystal Structure Determination

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CCDC 904906: Experimental Crystal Structure Determination

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CCDC 1868874: Experimental Crystal Structure Determination

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CCDC 1857502: Experimental Crystal Structure Determination

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CCDC 854108: Experimental Crystal Structure Determination

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CCDC 1818145: Experimental Crystal Structure Determination

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CCDC 925071: Experimental Crystal Structure Determination

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CCDC 1510890: Experimental Crystal Structure Determination

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CCDC 1432274: Experimental Crystal Structure Determination

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CCDC 1524199: Experimental Crystal Structure Determination

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CCDC 1484385: Experimental Crystal Structure Determination

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CCDC 1898600: Experimental Crystal Structure Determination

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CCDC 1969475: Experimental Crystal Structure Determination

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CCDC 958830: Experimental Crystal Structure Determination

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CCDC 919612: Experimental Crystal Structure Determination

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CCDC 1867784: Experimental Crystal Structure Determination

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CCDC 928581: Experimental Crystal Structure Determination

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CCDC 1471983: Experimental Crystal Structure Determination

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CCDC 1016161: Experimental Crystal Structure Determination

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CCDC 1553971: Experimental Crystal Structure Determination

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CCDC 1016162: Experimental Crystal Structure Determination

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CCDC 927028: Experimental Crystal Structure Determination

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CCDC 993408: Experimental Crystal Structure Determination

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CCDC 925072: Experimental Crystal Structure Determination

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CCDC 1471279: Experimental Crystal Structure Determination

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CCDC 2076622: Experimental Crystal Structure Determination

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CCDC 1938636: Experimental Crystal Structure Determination

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CCDC 1409936: Experimental Crystal Structure Determination

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CCDC 1989324: Experimental Crystal Structure Determination

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CCDC 879927: Experimental Crystal Structure Determination

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