Design of molecular materials combining magnetic, electrical and optical properties †

The possibilities offered by hybrid functional materials formed by two molecular networks in the context of crystal engineering are illustrated with two different examples: (i) hybrid magnets constructed from combination of an extended ferromagnetic or ferrimagnetic inorganic network, with a molecular paramagnetic metal complex acting as template. (ii) Hybrid organic–inorganic compounds combining an organic π-electron donor network that furnishes the pathway for electronic conductivity, with inorganic metal complexes that act as structural and/or magnetic components. These examples illustrate how this hybrid approach allows the design of molecular materials combining non-conventional magnet…

Interplay between spin crossover and proton migration along short strong hydrogen bonds

The iron(ii) salt [Fe(bpp)2](isonicNO)2·HisonicNO·5H2O (1) (bpp = 2,6-bis(pyrazol-3-yl)pyridine; isonicNO = isonicotinate N-oxide anion) undergoes a partial spin crossover (SCO) with symmetry breaking at T1 = 167 K to a mixed-spin phase (50% high-spin (HS), 50% low-spin (LS)) that is metastable below T2 = 116 K. Annealing the compound at lower temperatures results in a 100% LS phase that differs from the initial HS phase in the formation of a hydrogen bond (HB) between two water molecules (O4W and O5W) of crystallisation. Neutron crystallography experiments have also evidenced a proton displacement inside a short strong hydrogen bond (SSHB) between two isonicNO anions. Both phenomena can al…

Original packing and unusual molecular conformation of the bis(ethylenedithio)tetrathiafulvalene (ET) donors induced by cation–anion interactions in the radical salt ET5[B10I10]·(CH2Cl2)0.8

The crystal structure of the radical salt ET5[B10I10]·0.8CH2Cl2 has been determined and the packing and molecular conformation of the organic donors are discussed in terms of the C–H⋯I contacts between the ethylene groups of the ET molecules and the iodine atoms of the borane anion [B10I10]2−.

Magnetoresistance studies of the ferromagnetic molecular metal (BEDT-TTF)3[MnCr(C2O4)3] under pressure

(BEDT-TTF)3[MnCr(C2O4)3] is the first ferromagnetic molecular metal, in which organic layers of BEDT-TTF alternate with infinite layers of the bimetallic oxalate complex [MnCr(C2O4)3]-. While the bimetallic layer undergoes a magnetic phase transition into a canted ferromagnetic state at 5.5 K, the metallic character of the conductivity is not affected by the magnetic transition [Nature 408 (2000) 447]. We performed magnetoresistance measurements (B≤17 T) at low temperatures (T≥900 mK) and under hydrostatic pressures of up to 2.0 GPa. Oscillations in the magnetoresistance develop under pressure that can be interpreted as Shubnikov-de Haas oscillations, if an internal magnetic field is taken …

Synthesis and Physical Properties of K4[Fe(C5O5)2(H2O)2](HC5O5)2·4H2O (C5O52– = Croconate): A Rare Example of Ferromagnetic Coupling via H-bonds

The reaction of the croconate dianion (C(5)O(5))(2-) with a Fe(III) salt has led, unexpectedly, to the formation of the first example of a discrete Fe(II)-croconate complex without additional coligands, K(4)[Fe(C(5)O(5))(2)(H(2)O)(2)](HC(5)O(5))(2)·4H(2)O (1). 1 crystallizes in the monoclinic P2(1)/c space group and presents discrete octahedral Fe(II) complexes coordinated by two chelating C(5)O(5)(2-) anions in the equatorial plane and two trans axial water molecules. The structure can be viewed as formed by alternating layers of trans-diaquabis(croconato)ferrate(II) complexes and layers containing the monoprotonated croconate anions, HC(5)O(5)(-), and noncoordinated water molecules. Both …

A decacobalt(ii) cluster with triple-sandwich structure obtained by partial reductive hydrolysis of a pentacobalt(ii/iii) Weakley-type polyoxometalate.

Partial reductive hydrolysis of a penta-CoII/III cluster [CoII4(H2O)2(CoIIIW9O34)(PW9O34)]12− (1) leads to the formation of [Co2{Co3(H2O)(Co(OH)2W7O26)(PW9O34)}2]22− (2). This polyoxometalate is made up of two capping [PW9O34]9− units and two bridging [W7O26]10− units that assemble to encapsulate a novel deca-CoII cluster core comprising octahedral and tetrahedral CoII ions.

Magnetic molecular metals based on the organic donor molecule BET (BET = Bis(ethylenethio)tetrathiafulvalene): The series BET2[MCI4] (M3⊕= Ga, Fe)

Spin crossover complexes as building units of hydrogen-bonded nanoporous structures

The paper reports on the synthesis, crystal structure, differential scanning calorimetry (DSC) and magnetic properties of a spin crossover salt of formula [Fe(bpp)2](cis,cis-1,3,5-Hchtc)·5.5 H2O (1) (bpp = 2,6-bis(pyrazol-3yl)pyridine; cis,cis-1,3,5-Hchtc = monoprotonated cyclohexanetricarboxylate dianion). The salt shows a porous structure with water molecules sitting in the channels. The electronic configuration of the Fe2+ ions is high-spin (HS). Desolvation of 1 yields a material exhibiting an abrupt spin crossover with a thermal hysteresis loop located near room temperature (T1/2↑ = 319 K and T1/2↓ = 309 K). Rehydration of this desolvated salt yields an essentially low-spin (LS) materi…

Polycationic Mn12Single-Molecule Magnets as Electron Reservoirs withS>10 Ground States

Electronic and Magnetic Study of Polycationic Mn-12 Single-Molecule Magnets with a Ground Spin State S=11

International audience; The preparation, magnetic characterization, and X-ray structures of two polycationic Mn-12 single-molecule magnets (Mn12O12(bet)(16)(EtOH)(4)](PF6)(14)center dot 4CH(3)CN center dot H2O (1) and [Mn12O12(bet)(16)(EtOH)(3)(H2O)](PF6)(13)(OH)center dot 6CH(3)CN center dot EtOH center dot H2O (2) (bet = betaine = (CH3)(3)N+-CH2-CO2-) are reported. 1 crystallizes in the centrosymmetric P2/cspace group and presents a (0:2:0:2) arrangement of the EtOH molecules in its structure. 2 crystallizes in the noncentrosymmetric P (4) over bar space group with two distinct Mn-12 polycations, [Mn12O12(bet)(16)(EtOH)(2)(H2O)(2)](14+) (2A) and [Mn12O12(bet)(16)(EtOH)(4)](14+)(2B) per un…

Metal complexes of a picolinate-based nitronyl nitroxide free radical.

A nitronyl nitroxide free radical containing an appended picolinate moiety was synthesized. The resulting tridentate ligand picNN forms neutral mononuclear metal complexes of formula [M(picNN)(2)].3H(2)O (M = Mn, Co, Ni, Zn). These compounds are isostructural and crystallize in the orthorhombic Pnna space group. The metal complexes have a C(2) symmetric structure, with the metal centers lying on the binary axis and surrounded by two equivalent picNN radicals. The magnetic properties of this family of compounds indicate the presence of very strong metal-radical exchange interactions, ranging from J(Ni-rad) = -193 cm(-1) to J(Mn-rad) = -98 cm(-1). Relatively weak (J(rad-rad) = -15 cm(-1)) thr…

Single ion magnets based on lanthanoid polyoxomolybdate complexes

Polyoxometalate (POM) chemistry has recently offered excellent examples of single ion magnets (SIMs) and molecular spin qubits. Compared with conventional coordination compounds, POMs provide rigid and highly symmetric coordination sites. However, all POM-based SIMs reported to date exhibit a very limited range of possibilities for chemical processability. We present herein two new families of POM-based SIMs which are soluble in organic solvents: [Ln(β-Mo8O26)2]5− {LnIII = Tb, Dy, Ho, Er, Tm and Yb} and the functionalised POMs [Ln{Mo5O13(OMe)4NNC6H4-p-NO2}2]3− {LnIII = Tb, Dy, Ho, Er, Yb and Nd}. In addition, these two families represent the first SIMs based on polyoxomolybdates. A magneto-…

A new BEDT-TTF salt and polypyrrole films containing the chiral polyoxometalate [H4Co2Mo10O38]6−

Abstract The chiral polyoxometalate [H4Co2Mo10O38]6− has been used in the preparation of hybrid materials in the form of crystals or polymeric films. A new radical salt of the donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) containing the two enantiomers of this polyoxometalate has been obtained by electrocrystallization. This radical salt shows semiconducting behavior with room temperature conductivity of 9 S.cm−1 and activation energy of 40 meV. Polypyrrole films doped with a racemic mixture of polyoxometalates and also the enantiomerically pure (+)589-[H4Co2Mo10O38]6− have been prepared electrochemically. Circular dichroism experiments suggest that the chiral polyoxometalate…

Nitroxide Radicals as Templating Agents in the Synthesis of Magnets Based on Three-Dimensional Oxalato-Bridged Heterodimetallic Networks

Synthesis, crystal structures and electronic properties of imidazoline nitroxide radicals bearing active groups in electropolymerisation

Thiophene-, phenylthiophene-, and indole-based nitronyl nitroxide (NN) and imino nitroxide (IN) radicals have been synthesised and their electrochemical and magnetic properties have been studied. Cyclic voltammetry measurements show that NN radicals (1–3) exhibit a one-electron quasi-reversible oxidation process that results in the formation of the corresponding nitrosonium cations. This behaviour pushes the oxidation potential of the other redox-active moiety to very high values. The oxidation of the thiophene subunit occurs at 2.35 V, whereas the oxidation of the phenylthiophene and indole moieties takes place at 1.65 and 1.39 V, respectively. Oxidation of IN radicals (4–5) is irreversibl…

Design of chiral magnets: Cyanide-bridged bimetallic assemblies based on cyclohexane-1,2-diamine

Abstract Four magnetic compounds based on chiral ligands trans-(1S,2S)-chxn and trans-(1R,2R)-chxn (chxn: cyclohexane-1,2-diamine), [Ni(trans-(1S,2S)-chxn)2]3[Fe(CN)6]2·2H2O (1), [Ni(trans-(1R,2R)-chxn)2]3[Fe(CN)6]2·2H2O (2), [Cu(trans-(1S,2S)-chxn)2]3[Fe(CN)6]2·4.5H2O (3) and [Cu(trans-(1R,2R)-chxn)2]3[Fe(CN)6]2·4.5H2O (4), are reported. The four compounds are chiral, as confirmed by X-ray analyses and circular dichroism measurements. From the magnetic point of view, 1 and 2 behave as ferromagnets, whereas 3 and 4 show a paramagnetic behavior.

Organic/inorganic molecular conductors based upon perylene and Lindquist-type polyoxometalates

The preparation, structures and physical properties of the organic/inorganic radical salts based upon perylene (per) and Lindquist type polyoxometalates (POMs) are reported. Three new hybrid salts have been prepared: (per)5[Mo6O19] (1), (per)5[W6O19] (2), and (per)5[VW5O19] (3). Only structures 1 (P, Z = 2) and 3 (P, Z = 2) were fully determined as compound 2 was found to have unit cell parameters practically identical to 1 and, therefore, is considered isostructural with the latter. The structures consist of interpenetrated organic and mixed organic/inorganic layers in the ac plane alternating along the a direction. The organic layers present a novel packing mode of the perylene molecules …

Hybrid Materials Based on Polyoxometalates with Solid State Properties

Molecular materials with cooperative physical properties constitute one of the most active focus of interest in contemporary materials science. An attractive chemical feature of these materials derives from the possibility of building them from molecular bricks using the advantages provided by molecular chemistry and the knowledge achieved over the last 20 years in the so-called molecular engineering. From the point of view of the physical properties, it is well known that molecular materials can exhibit the properties typically associated with the inorganic network solids, as for example metallic conductivity and superconductivity [1], ferromagnetism [2] and non-linear optics [3].

Restricting Magnetic Interaction Pathways in Polyoxometalate Salts of Cationic Nitronyl Nitroxide Free Radicals

Abstract : Salts 1 and 2 that combine the [W 6 O 19 ] 2- Lindqvist anion with the cationic nitronyl nitroxide (NN) free radicals p -MepyNN + and n Bu 3 NCH 2 NN + , respectively, have been synthesized and their structural and magnetic properties have been studied. Keywords: Nitroxide radicals, polyoxometalates, magnetism. Introduction Ferromagnetism based on purely organic materials has raised a lot of interest during the last decade [1]. Most of the studies have been performed with nitronyl nitroxide (NN) radicals due to their persistence, stability and ease of functionalization [2]. Bulk ferromagnetism in these compounds arises from ferromagnetic interactions between open-shell molecules …

Hybrid Molecular Materials Based upon Organic π-Electron Donors and Metal Complexes. Radical Salts of Bis(ethylenethia)tetrathiafulvalene (BET-TTF) with the Octahedral Anions Hexacyanoferrate(III) and Nitroprusside. The First Kappa Phase in the BET-TTF Family

The synthesis, structure, and physical characterization of two new radical salts formed with the organic donor bis(ethylenethia)tetrathiafulvalene (BET-TTF) and the octahedral anions hexacyanoferrate(III), [Fe(CN)(6)](3-), and nitroprusside, [Fe(CN)(5)NO](2-), are reported. These salts are (BET-TTF)(4)(NEt(4))(2)[Fe(CN)(6)] (1) (monoclinic space group C2/c with a = 38.867(7) A, b = 8.438(8) A, c = 11.239(6) A, beta = 90.994(9) degrees, V = 3685(4) A(3), Z = 4) and (BET-TTF)(2)[Fe(CN)(5)NO].CH(2)Cl(2) (2) (monoclinic space group C2/c with a = 16.237(6) A, b = 18.097(8) A, c = 12.663(7) A, beta = 106.016(9) degrees, V = 3576(3) A(3), Z = 4). In salt 1 the organic BET-TTF molecules are packed …

Scanning tunnelling spectroscopy study of paramagnetic superconducting β''-ET(4)[(H(3)O)Fe(C(2)O(4))(3)]·C(6)H(5)Br crystals.

Scanning tunnelling spectroscopy (STS) and microscopy (STM) were performed on the paramagnetic molecular superconductor β''-ET(4)[(H(3)O)Fe(C(2)O(4))(3)]·C(6)H(5)Br. Under ambient pressure, this compound is located near the boundary separating superconducting and insulating phases of the phase diagram. In spite of a strongly reduced critical temperature T(c) (T(c) = 4.0 K at the onset, zero resistance at T(c) = 0.5 K), the low temperature STS spectra taken in the superconducting regions show strong similarities with the higher T(c) ET κ-derivatives series. We exploited different models for the density of states (DOS), with conventional and unconventional order parameters to take into accoun…

Bimetallic cyanide-bridged complexes based on the photochromic nitroprusside anion and paramagnetic metal complexes

Abstract Three novel compounds formed by the photochromic nitroprusside anion, [Fe(CN)5NO]2−, and the paramagnetic complexes [Cu(C19H18N6)]2+, [Ni(C6H14N2)2]2+ and [Ni(cyclam)]2+ are reported. The structure of [Cu(C19H18N6)][Fe(CN)5NO] (1) comprises binuclear complexes with a [Fe(CN)5NO]2− anion linked to a [Cu(C19H18N6)]2+ cation. The structure of [Ni(C6H14N2)2][Fe(CN)5NO]·6.5H2O (2) and [Ni(cyclam)][Fe(CN)5NO]·4H2O (3) consists of zigzag chains formed by an alternate array of the paramagnetic cations and [Fe(CN)5NO]2− anions. The three compounds are paramagnets; a fourth compound containing [cis-Ni(en)2]2+ cations and [Fe(CN)5NO]− anions does not show a change in the magnetic properties a…

Coherent manipulation of three-qubit states in a molecular single-ion magnet

We study the quantum spin dynamics of nearly isotropic Gd3+ ions entrapped in polyoxometalate molecules and diluted in crystals of a diamagnetic Y3+ derivative. The full energy-level spectrum and the orientations of the magnetic anisotropy axes have been determined by means of continuous-wave electron paramagnetic resonance experiments, using X-band (9-10 GHz) cavities and on-chip superconducting waveguides and 1.5-GHz resonators. The results show that seven allowed transitions between the 2S+1 spin states can be separately addressed. Spin coherence T2 and spin-lattice relaxation T1 rates have been measured for each of these transitions in properly oriented single crystals. The results sugg…

Synthetic studies on the preparation of oxygenated spongiane diterpenes from carvone

Abstract The paper describes a new diastereoselective approach to oxygenated spongiane diterpenes functionally related to natural dorisenones. The strategy followed for the preparation of the spongiane framework, a B→AB→ABC→ABCD approach, is based on the preparation of epoxydecalone 11 (AB rings) from R-(−)-carvone, followed by an intramolecular Diels–Alder reaction for the construction of the C ring (compound 26 ). Further manipulation of the Diels–Alder adduct functionality allows the completion of the spongiane framework and the elaboration of several oxygenated spongiane-type compounds. The structures of two compounds 27 and 31 , has been established by single-crystal X-ray crystallogra…

Large Magnetic Polyoxometalates Containing the Cobalt Cubane ‘[CoIIICo3II(OH)3(H2O)6–m(PW9O34)]3− (m = 3 or 5) as a Subunit

A synthetic procedure is presented to construct new magnetic polyoxometalates (POMs) containing one or two subunits of ‘[CoIIICo3II(OH)3(H2O)6−m(PW9O34)]3−' (m = 3 or 5). The substitution of the water ligands present in these subunits by oxo or hydroxo ligands belonging to other POM fragments, gives rise to four, larger POM anions: [Co7(OH)6(H2O)6(PW9O34)2]9− (2), [Co7(OH)6(H2O)4(PW9O34)2]n9n- (2′), [Co11(OH)5(H2O)5(W6O24)(PW9O34)3]22− (3) and [{Co4(OH)3(H2O)(PW9O34)}2{K⊂(H2W12O41)2}{Co(H2O)4}2]17− (4). The crystal structures, magnetic characterization and stabilities in aqueous solutions of these POM derivatives are also presented.

ChemInform Abstract: Cobalt Clusters with Cubane-Type Topologies Based on Trivacant Polyoxometalate Ligands.

Four novel cobalt-substituted polyoxometalates having cobalt cores exhibiting cubane or dicubane topologies have been synthesized and characterized by IR, elemental analysis, electrochemistry, UV–vis spectroscopy, X-ray single-crystal analysis, and magnetic studies. The tetracobalt(II)-substituted polyoxometalate [Co4(OH)3(H2O)6(PW9O34)]4– (1) consists of a trilacunary [B-α-PW9O34]9– unit which accommodates a cubane-like {CoII4O4} core. In the heptacobalt(II,III)-containing polyoxometalates [Co7(OH)6(H2O)6(PW9O34)2]9– (2), [Co7(OH)6(H2O)4(PW9O34)2]n9n– (3), and [Co7(OH)6(H2O)6(P2W15O56)2]15– (4), dicubane-like {CoII6CoIIIO8} cores are encapsulated between two heptadentate [B-α-PW9O34]9– (in…

Hybrid molecular materials formed by alternating layers of bimetallic oxalate complexes and tetrathiafulvalene molecules: Synthesis, structure, and magnetic properties of TTF4(Mn(H2O)2)[Cr(ox)3]2)·14 H2O

New conducting radical salts based upon Keggin-type polyoxometalates and perylene

Three new radical salts, Per6[PMo12O40]·CH2Cl2 (1), Per6[PMo12O40]·CH3CN (2), and Per9(NBu4)4[SiW12O40]2 (3) (Per = perylene), have been synthesised and their electrical and magnetic properties characterised. These three salts are diamagnetic and they behave as semiconductors with room temperature conductivities of 69, 3.6 and 0.85 S cm−1. While salt 2 presents hole-type conduction and 3 exhibits electron-dominated electrical transport properties, salt 1 shows at 150 K an abrupt change in the thermal dependence of the electrical conductivity and the Seebeck coefficient suggesting a phase transition.

Molecular conductors based on the mixed-valence polyoxometalates [SMo12O40]n- (n = 3 and 4) and the organic donors bis(ethylenedithio)tetrathiafulvalene and bis(ethylenedithio)tetraselenafulvalene.

The synthesis, crystal structure, and physical characterization of two new radical salts formed by the organic donors bis(ethylenedithio)tetrathiafulvalene (ET) and bis(ethylenediseleno)tetrathiafulvalene (BETS) and the Keggin polyoxometalate (POM) [SMo(12)O(40)](n-) are reported. The salts isolated are ET(8)[SMo(12)O(40)] x 10 H(2)O (1) (crystal data: (1) monoclinic, space group I2/m with a = 13.9300(10) A, b = 43.467(3) A, c = 13.9929(13) A, beta = 107.979(6) degrees, V = 8058.9(11) A(3), Z = 2) and BETS(8)[SMo(12)O(40)] x 10 H(2)O (2) (crystal data: monoclinic, space group I2/m with a = 14.0878(2) A, b = 44.1010(6) A, c = 14.0930(2) A, beta = 106.739(3) degrees, V = 8384.8 A(3), Z = 2). …

Stoichiometric Control of the Magnetic Properties in Copper( II ) Cyano‐Bridged Bimetallic Complexes

Control of the Cu2+ ion coordination environment affords a 1D, magnetically diluted compound, [Cu(cis-chxn)2]3[Fe(CN)6]2·7H2O (1) and the 2D ferromagnetic material [Cu(cis-chxn)]3[Fe(CN)6]2·6H2O (2) with a critical temperature, Tc, of 3.5 K. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

A Novel Chainlike Heteropolyanion Formed by Keggin Units: Synthesis and Structure of(ET)8n[PMnW11O39]n· 2nH2O

A reversible hydrogen‐bond isomerization triggered by an abrupt spin crossover near room temperature.

The spin crossover salt [Fe(bpp) 2 ](isonicNO) 2 ·2.4H 2 O ( 1 ·2.4H 2 O) (bpp = 2,6‐bis(pyrazol‐3‐yl)pyridine; isonicNO = isonicotinate N‐oxide anion) exhibits a very abrupt spin crossover at T 1 /2 = 274.4 K. This triggers a supramolecular linkage (H‐bond) isomerization that responds reversibly towards light irradiation or temperature change. Isotopic effects in the thermomagnetic behaviour reveal the importance of hydrogen bonds in defining the magnetic state. Further, the title compound can be reversibly dehydrated to afford 1 , a material that also exhibits spin crossover coupled to H‐bond isomerization, leading to strong kinetic effects in the thermomagnetic properties.

Hybrid Molecular Materials Based upon Organic π-Electron Donors and Inorganic Metal Complexes. Conducting Salts of Bis(ethylenediseleno)tetrathiafulvalene (BEST) with the Octahedral Anions Hexacyanoferrate(III) and Nitroprusside

Abstract The synthesis, structure and physical characterization of three new radical salts formed by the organic donor bis(ethylenediseleno)tetrathiafulvalene (BEDS-TTF or BEST) and the paramagnetic hexacyanoferrate(III) anion [Fe(CN)6]3− or the photochromic nitroprusside anion [Fe(CN)5NO]2− are reported: (BEST)4[Fe(CN)6] (1), (BEST)3[Fe(CN)6]2·H2O (2) and (BEST)2[Fe(CN)5NO] (3). Salts 1 and 3 show a layered structure with alternating organic (β–type packing) and inorganic slabs. Salt 2 shows an original interpenetrated structure probably due to the unprecedented presence of (BEST)2+ dications. The three salts are semiconductors although salt 1 exhibits a high room temperature conductivity …

The first radical salt of the polyoxometalate cluster [P2W18O62]6⊖with bis(ethylenedithio)tetrathiafulvalene (ET): ET11[P2W18O62] · 3H2O

Hydrogen-bonded networks of [Fe(bpp)2]2+spin crossover complexes and dicarboxylate anions: structural and photomagnetic properties

The paper reports the syntheses, crystal structures, thermal and (photo)magnetic properties of spin crossover salts of formula [Fe(bpp)2](C6H8O4)·4H2O (1·4H2O), [Fe(bpp)2](C8H4O4)·2CH3OH·H2O (2·2MeOH·H2O) and [Fe(bpp)2](C8H4O4)·5H2O (2·5H2O) (bpp = 2,6-bis(pyrazol-3yl)pyridine; C6H8O4 = adipate dianion; C8H4O4 = terephthalate dianion). The salts exhibit an intricate network of hydrogen bonds between low-spin iron(II) complexes and carboxylate dianions, with solvent molecules sitting in the voids. Desolvation is accompanied by a low-spin (LS) to high-spin (HS) transformation in the materials. The dehydrated phase 2 undergoes a two-step transition with a second step showing thermal hysteresis…

Light-induced decarboxylation in a photo-responsive iron-containing complex based on polyoxometalate and oxalato ligands.

A new iron-oxalato polyoxometalate exhibits a remarkable photocoloration effect in the solid state based entirely on an intramolecular process.

Single-molecule magnetic behavior in a neutral terbium(III) complex of a picolinate-based nitronyl nitroxide free radical

The terdentate anionic picolinate-based nitronyl nitroxide (picNN) free radical forms neutral and robust homoleptic complexes with rare earth-metal ions. The nonacoordinated Tb3+ complex Tb(picNN)3• 6H2O is a single-molecule magnet with an activation energy barrier Δ = 22.8 ± 0.5 K and preexponential factor τ0 = (5.5 ± 1.1) × 10-9 s. It shows magnetic hysteresis below 1 K. © 2011 American Chemical Society.

New BEDT-TTF/[Fe(C5O5)3]3- Hybrid System:  Synthesis, Crystal Structure, and Physical Properties of a Chirality-Induced α Phase and a Novel Magnetic Molecular Metal

The paramagnetic and chiral anion [Fe(C5O5)3]3- (C5O52-=croconate) has been combined with the organic donor BEDT-TTF (=ET=bis(ethylenedithio)tetrathiafulvalene) to synthesize a novel paramagnetic semiconductor with the first chirality-induced alpha phase, alpha-(BEDT-TTF)5[Fe(C5O5)3].5H2O (1), and one of the few known paramagnetic molecular metals, beta-(BEDT-TTF)5[Fe(C5O5)3].C6H5CN (2). Both compounds present layers of BEDT-TTF molecules, with the alpha or beta packing modes, alternating with layers containing the high-spin S=5/2 Fe(III) anions and solvent molecules. In the alpha phase, the alternation of the chiral [Fe(C5O5)3]3- anions along the direction perpendicular to the BEDT-TTF cha…

Multifunctionality in hybrid molecular materials: design of ferromagnetic molecular metals and hybrid magnets

We report on the synthesis and physical properties of novel hybrid organic–inorganic molecular materials combining ferromagnetic bimetallic oxalato-based networks and functional organic molecules as the donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) or cationic nitroxide free radicals. # 2002 Elsevier Science B.V. All rights reserved.

Magneto-structural correlations in discrete $Mn^{II}‐W^V$ cyano‐bridged assemblies with polyimine ligands

We present the magneto-structural correlations for two novel discrete cyano-bridged assemblies based on cationic complexes of manganese(II) with diimine ligands and octacyanotungstate(V) ions. The crystal structure of [Mn II (terpy)(dmf)-(H 2 O) 2 ][Mn II (terpy)(H 2 O)(dmf)(μ-NC)W V (CN) 7 ] 2· 6H 2 O (1) (terpy = 2,2';6',2"-terpyridine, dmf = dimethylformamide) contains dinuclear {Mn II W V } - cyano-bridged anions, while the crystal structure of [Mn II (phen) 3 ] 2 [MnII(phen) 2 (μ-NC) 2 -W V (CN) 6 ] 2 (ClO 4 ) 2 ·9H 2 O (2) (phen = 1,10-phenanthroline) is built of tetranuclear {Mn II 2 W V 2} 2- square anions. Intramolecular Mn-W magnetic interactions through the cyano bridges are repr…

A chirality-induced alpha phase and a novel molecular magnetic metal in the BEDT-TTF/tris(croconate)ferrate(iii) hybrid molecular system

The novel paramagnetic and chiral anion [Fe(C5O5)3]32 has been combined with the organic donor BEDT-TTF (= ET = bis(ethylenedithio)tetrathiafulvalene) to yield the first chirality- induced α phase and a paramagnetic metal. Gomez Garcia, Carlos, Carlos.Gomez@uv.es ; Coronado Miralles, Eugenio, Eugenio.Coronado@uv.es ; Gimenez Saiz, Carlos, Carlos.Gimenez@uv.es

Ein aus Keggin-Einheiten aufgebautes, kettenartiges Heteropolyanion: Synthese und Struktur von (ET)8n[PMnW11O39]n · 2nH2O

Hybrid Molecular Materials Based upon Magnetic Polyoxometalates and Organic π-Electron Donors:  Syntheses, Structures, and Properties of Bis(ethylenedithio)tetrathiafulvalene Radical Salts with Monosubstituted Keggin Polyoxoanions

International audience; The syntheses, crystal structures, and physical properties of the series of radical salts made with bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) and monosubstituted α-Keggin polyoxoanions of formula [XZ(H2O)M11O39]5- (XZM11 = Si(IV)Fe(III)Mo11, Si(IV)Cr(III)W11, P(V)Con(II)W11, P(V)Ni(II)W11, P(V)Cu(II)W11 P(V)Zn(II)W11, P(V)Mn(II)W11, and P(V)Mn(II)Mo11) containing a magnetic metal ion Z on a peripheral octahedral site of the Keggin union are reported. They all crystallize in two related series called α2 and α3. The general structure consists of alternating layers of the organic donor and the Keggin polyoxometalates. While the stoichiometry and α-packing a…

Metallic Charge‐Transfer Salts of Bis(ethylenedithio)tetrathiafulvalene with Paramagnetic Tetrachloro(oxalato)rhenate(IV) and Tris(chloranilato)ferrate(III) Anions

The synthesis, crystal structure and physical characterization of three radical salts of the donor bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) and tetrachloro(oxalato)rhenate(IV) {[ReCl4(C2O4)]2–} or tris(chloranilato)ferrate(III) {[Fe(C6O4Cl2)3]3–} anions are reported. The isolated salts with ReIV are (ET)[ReCl4(C2O4)] [1, monoclinic, space group C2/c with a = 18.3409(3) A, b = 10.8414(2) A, c = 11.1285(3) A, β = 99.9714(7)°, V = 2179.38(8) A3, Z = 4] and (ET)4[ReCl4(C2O4)]·C6H5CN [2, monoclinic, space group P21/c with a = 11.8549(2) A, b = 32.9079(5) A, c = 36.4154(5) A, β = 96.742(2)°, V = 14108.1(4) A3, Z = 8]. The salt with FeIII is (ET)6[Fe(C6O4Cl2)3]·(H2O)1.5·(CH2Cl2)0.5 […

Hybrid Magnetic Materials Based on Nitroxide Free Radicals and Extended Oxalato‐Bridged Bimetallic Networks

A series of hybrid organic-inorganic magnets of formula p-rad[MIICr(ox)3] [M = Mn (1), Co (2), Ni (3), Zn (4)] and m-rad[MIICr(ox)3] [M = Mn (5), Co (6)], in which N-methylpyridinium cations bearing a nitronyl nitroxide moiety in positions 3 (m-rad) or 4 (p-rad) of the pyridine ring coexist with the 2D honeycomb-like oxalato-bridged bimetallic lattice, has been prepared and studied by AC and DC magnetic susceptibility measurements and EPR spectroscopy. In general, the physical properties of these magnets are not altered significantly by the insertion of the nitronyl nitroxide radicals although these paramagnetic molecules seem to interact weakly with the inorganic network as demonstrated by…

A Ferroelectric Iron(II) Spin Crossover Material

A dual-function material in which ferroelectricity and spin crossover coexist in the same temperature range has been obtained. Our synthetic strategy allows the construction of acentric crystal structures in a predictable way and is based on the high directionality of hydrogen bonds. The well-known iron(II) spin crossover complex [Fe(bpp)₂]²+ (bpp = 2,6-bis(pyrazol-3-yl)pyridine), a four-fold noncentrosymmetric H-bond donor, was combined with a disymmetric H-bond acceptor such as the isonicotinate (isonic) anion to afford [Fe(bpp)₂](isonic)₂·2H₂O. This low-spin iron(II) compound crystallises in the acentric nonpolar I-4 space group and shows piezoelectricity and SHG properties. Upon dehydra…

Multifunctional molecular materials

Unravelling the spin-state of solvated [Fe(bpp)2]2+ spin-crossover complexes: structure–function relationship

This paper reports firstly the syntheses, crystal structures, and thermal and magnetic properties of spin crossover salts of formulae [Fe(bpp)2]3[Cr(CN)6]2·13H2O (1) and [Fe(bpp)2][N(CN)2]2·H2O (2) (bpp = 2,6-bis(pyrazol-3-yl)pyridine) exhibiting hydrogen-bonded networks of low-spin [Fe(bpp)2]2+ complexes and [Cr(CN)6]3− or [N(CN)2]− anions, with solvent molecules located in the voids. Desolvation of 1 is accompanied by a complete low-spin (LS) to a high-spin (HS) transformation that becomes reversible after rehydration by exposing the sample to the humidity of air. The influence of the lattice water on the magnetic properties of spin-crossover [Fe(bpp)2]X2 complex salts has been documented…

Magnetism in Polyoxometalates: Anisotropic Exchange Interactions in the Co Moiety of [Co3W(D2O)2(ZnW9O34)2]12−—A Magnetic and Inelastic Neutron Scattering Study

The ground-state properties of a Co moiety encapsulated in a polyoxometalate anion were investigated by combining measurements of specific heat, magnetic susceptibility, and low-temperature magnetization with a detailed inelastic neutron scattering (INS) study on a fully deuterated polycrystalline sample of Na12[Co3W(D2O)2(ZnW9O34)2]⋅40 D2O (Co3). The ferromagnetic Co3O14 cluster core consists of three octahedrally oxo-coordinated CoII ions. According to the single-ion anisotropy and spin–orbit coupling of the octahedral CoII ions, the appropriate exchange Hamiltonian to describe the ground-state properties of the Co3 spin cluster is anisotropic and is expressed as ℋ=−2Σ(JŜ1αŜ2α+JŜ2αŜ3α), w…

Temperature dependence of desolvation effects in hydrogen-bonded spin crossover complexes

The synthesis, crystal structure and (photo)magnetic properties of the anhydrous spin crossover salt of formula [Fe(bpp)2](C6H8O4) (1) (bpp = 2,6-bis(pyrazol-3-yl)pyridine; C6H8O4 = adipate dianion), obtained by desolvation at 400 K of the original tetrahydrate in a single-crystal-to-single-crystal (SC–SC) transformation, are reported. This work offers a comparison between this compound and the previously reported hydrated material ([Fe(bpp)2](C6H8O4)·4H2O, 1·4H2O), highlighting the significance of the thermal conditions used in the dehydration-rehydration processes. In both compounds, a hydrogen-bonded network between iron(II) complexes and adipate anions is observed. The original tetrahyd…

Metallic Conductivity Down to 2 K in a Polyoxometalate-Containing Radical Salt of BEDO-TTF

New magnetic conductors and superconductors based on BEDT-TTF and BEDS-TTF

Abstract Here we present our last results in the search for multifunctionality in conducting molecular materials obtained by combining paramagnetic molecular complexes with organic donors to produce paramagnetic molecular metals and superconductors. The structural and physical characterization of two new molecular paramagnetic superconductors ET 4 [H 3 OM(C 2 O 4 ) 3 ].PhBr (M III  = Cr and Fe) are presented (ET = BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene). These salts present a superconductor transition at T c  = 1.5 and 4.0 K, respectively and very anisotropic critical fields H c2a ≈ H c2b ≈0.5 T and H C2C ≈ 8 T for the Fe derivative. We will also present the structural and physica…

Charge Transfer Salts Based on Polyoxometalates and Seleno-Substituted Organic Donors. Synthesis, Structure, and Magnetic Properties of (BEST)3H[PMo12O40]·CH3CN·CH2Cl2 (BEST = Bis(ethylenediseleno)tetrathiafulvalene)

Electrochemical oxidation of the tetrathiafulvalene (TTF) type organic donor bis(ethylenediseleno)tetrathiafulvalene (BEST) in the presence of the Keggin polyoxometalate [PMo12O40]3- affords the radical salt formulated as (BEST)3H[PMo12O40] (crystal data:  triclinic, space group P1 with a = 13.056(1) A, b = 13.957(1) A, c = 22.302(3) A, α = 97.019(9)°, β = 94.17(1)°, γ = 95.847(9)°, and Z = 2). This is the first salt of a selenium-containing donor with a polyoxometalate cluster. The structure of this organic/inorganic hybrid consists of layers of the organic donors that alternate with polyoxometalate layers in the c direction. The organic molecules, which are completely ionized, form two ty…

Layered ferromagnets hosting tetraalkylammonium-substituted nitronyl nitroxide free radicals

This paper describes the structural, magnetic and EPR properties of hybrid organic/inorganic magnets formed by anionic heterometallic oxalato-based layers and cationic nitronyl nitroxide (NN) free radicals of the tetraalkylammonium type. A series of compounds of formula nBu3NCH2NN[MCr(ox)3] (M = Mn (1), Ni (2), Zn (3)) has been prepared and studied by AC and DC magnetic susceptibility measurements and EPR spectroscopy. Magnetic order with critical temperatures ranging from 5 K to 15 K was confirmed. EPR measurements show that the organic spin carriers interact significantly with the inorganic network.

Construction of a General Library for the Rational Design of Nanomagnets and Spin Qubits Based on Mononuclear f-Block Complexes. The Polyoxometalate Case

This paper belongs to a series of contributions aiming at establishing a general library that helps in the description of the crystal field (CF) effect of any ligand on the splitting of the J ground states of mononuclear f-element complexes. Here, the effective parameters associated with the oxo ligands (effective charges and metal-ligand distances) are extracted from the study of the magnetic properties of the first two families of single-ion magnets based on lanthanoid polyoxometalates (POMs), formulated as [Ln(W5O18)2](9-) and [Ln(β2-SiW11O39)2](13-) (Ln = Tb, Dy, Ho, Er, Tm, Yb). This effective CF approach provides a good description of the lowest-lying magnetic levels and the associate…

Three addressable spin qubits in a GdW30 single-ion magnet

Resumen del trabajo presentado a la XXXVI Reunión Bienal de la Real Sociedad Española de Física, celebrada en Santiago de Compostela del 17 al 21 de julio de 2017.

Synthesis, crystal structures and magnetic properties of picolinate-bridged copper(II) chains

The paper reports the synthesis, crystal structures, and magnetic properties of two copper(II) coordination polymers, Cu2(L1)4 (1) and Cu3(L2)6 (2), based on rigid ethynylene-bridged ditopic ligands containing one picolinate subunit (L1 = 5-(pyridin-3-ylethynyl)picolinate anion; L2 = 5-((4-(methoxycarbonyl)phenyl)ethynyl)picolinate anion). Both 1 and 2 have a chain structure. In 1, the repeating unit in the chain is a doubly bridged picolinate dicopper(II) complex, whereas 2 is built upon trimeric units where the Cu2+ ions are also connected by double picolinate bridges. Both compounds exhibit antiferromagnetic interactions in the solid state. The magnetic properties of 1 and 2 were analyze…

A novel paramagnetic molecular superconductor formed by bis(ethylenedithio)tetrathiafulvalene, tris(oxalato)ferrate(iii) anions and bromobenzene as guest molecule: ET4[(H3O)Fe(C2O4)3]·C6H5Br

The new paramagnetic molecular superconductor ET4[(H3O)Fe(C2O4)3]·C6H5Br (1) (Tc = 4.0 K) contains layers of superconducting ET donors alternating with paramagnetic hexagonal layers formed by (H3O)+, [Fe(C2O4)3]3− and guest C6H5Br molecules located in the hexagonal cavities. Conductivity measurements show metallic behavior from room temperature with a minimum in the resistivity at ca. 50 K followed by a smooth increase and a sharp drop in the resistivity with an onset at 4.0 K and a zero resistance at ca. 1.0 K. Magnetoresistance measurements indicate that Hc1 is about 7 mT and that Hc2 is very anisotropic (Hc2⊥ ≥ 5.5 T and Hc2|| ≈ 0.5 T). Magnetic susceptibility measurements show the expec…

Magnetic properties of hybrid molecular materials based on oxalato complexes

Abstract The use of [MIII(ox)3]3− (MIII=Ru, Rh) complexes as building blocks for hybrid molecular materials is highlighted with two different synthetic approaches. The first strategy is the combination of organic donors and [RuIII(ox)3]3− units, resulting in the radical salt of formula TTF3[Ru(ox)3]·0.5EtOH·4H2O (1) which shows coexistence of paramagnetism and semiconducting properties. The second approach is the synthesis of extended 2D bimetallic oxalato-bridged networks of general formula [FeCp2 *][MIIRh(ox)3] in which paramagnetic layers of decamethylferricinium cations are alternated with paramagnetic bimetallic layers.

Recent advances in polyoxometalate-containing molecular conductors

The recent advances in crystalline conducting molecular materials based on polyoxometalates (POMs) and organic donors of the tetrathiafulvalene (TTF) family or perylene are discussed. We emphasise the wide diversity of POM structural types and the variety of packing architectures for the organic molecules that can be induced by these inorganic anions. Besides structural effects, we show that these hybrids can have interesting electric and/or magnetic properties. Thus, in the last years the common belief that this type of radical salts containing such big and highly charged anions could only exhibit poor conducting properties has been refuted by the production of new materials exhibiting hig…

Polyoxometalate salts of cationic nitronyl nitroxide free radicals

The cationic nitronyl nitroxide free radical of the N-methylpyridinium type p-MepyNN + has been combined with [Mo 8 0 26 ] 4- and Keggin [SiW 12 0 40 ] 4- polyanions to afford salts ( p-MepyNN) 4 [Mo 8 0 26 ] DMSO (DMSO = dimethylsulfoxide) (1) and (p-MepyNN)4[SiW 12 0 40 ] 6DMF (DMF = dimethylformamide) (2). Herein, their structural and magnetic properties are described.

The Series of Molecular Conductors and Superconductors ET4[AFe(C2O4)3]·PhX (ET = bis(ethylenedithio)tetrathiafulvalene; (C2O4)2– = oxalate; A+ = H3O+, K+; X = F, Cl, Br, and I): Influence of the Halobenzene Guest Molecules on the Crystal Structure and Superconducting Properties

An extensive series of radical salts formed by the organic donor bis(ethylenedithio)tetrathiafulvalene (ET), the paramagnetic tris(oxalato)ferrate(III) anion [Fe(C(2)O(4))(3)](3-), and halobenzene guest molecules has been synthesized and characterized. The change of the halogen atom in this series has allowed the study of the effect of the size and charge polarization on the crystal structures and physical properties while keeping the geometry of the guest molecule. The general formula of the salts is ET(4)[A(I)Fe(C(2)O(4))(3)]·G with A/G = H(3)O(+)/PhF (1); H(3)O(+)/PhCl (2); H(3)O(+)/PhBr (3), and K(+)/PhI (4), (crystal data at room temperature: (1) monoclinic, space group C2/c with a = 1…

Synthesis, structure and magnetic characterization of [Fe(bpp)2][Cu(pds)2]2·solv (solv=CH3CN and CH3OH)

A novel salt of the Fe(II) cation [Fe(bpp)2]2+ (bpp = 2,6-bis(pyrazol-3-yl)pyridine) with the [CuIII(pds)2]- anion (pds = pirazine-2,3-diselenolate) formulated as [Fe(bpp)2][Cu(pds)2]2·3CH3CN has been prepared and characterized by single crystal X-ray diffraction and magnetic measurements. The salt presents a layered structure where cations and anions alternate along the b direction with many intermolecular short contacts between the cations and anions. The magnetic properties show that the Fe(II) cations [Fe(bpp)2]2+ present a high-spin S = 2 ground spin state with g = 2.073(1) and a zero field splitting (ZFS) of 7.7(1) cm-1 but no the expected spin transition at low temperatures. © 2008 E…

Crystal Engineering of Multifunctional Molecular Materials

In this paper we will focus on the crystal engineering of molecular materials exhibiting magnetic and/or electrical properties. The complexity of these materials needs of a precise design of the molecular building blocks, a control of the intermolecular interactions (hydrogen bonds, host/guest interactions, etc.) and a mastery in crystallization techni- ques in order to design crystal structures exhibiting useful physical proper- ties. We will illustrate this concept through some relevant examples based on two-component hybrid materials.

Cobalt Clusters with Cubane-Type Topologies Based on Trivacant Polyoxometalate Ligands.

Four novel cobalt-substituted polyoxometalates having cobalt cores exhibiting cubane or dicubane topologies have been synthesized and characterized by IR, elemental analysis, electrochemistry, UV-vis spectroscopy, X-ray single-crystal analysis, and magnetic studies. The tetracobalt(II)-substituted polyoxometalate [Co4(OH)3(H2O)6(PW9O34)](4-) (1) consists of a trilacunary [B-α-PW9O34](9-) unit which accommodates a cubane-like {Co(II)4O4} core. In the heptacobalt(II,III)-containing polyoxometalates [Co7(OH)6(H2O)6(PW9O34)2](9-) (2), [Co7(OH)6(H2O)4(PW9O34)2]n(9n-) (3), and [Co7(OH)6(H2O)6(P2W15O56)2](15-) (4), dicubane-like {Co(II)6Co(III)O8} cores are encapsulated between two heptadentate [B…

A new approach for the synthesis of magnetic materials based on nitroxide free radicals and inorganic coordination polymers

The use of nitronyl nitroxide (NN) radicals as spectators inside extended inorganic magnetic lattices is described. Two possibilities are presently being explored, namely, the design of oxalato-bridged bimetallic networks by using cationic NN radicals of the N-alkylpyridinium type as templating agents, and the design of bimetallic lattices based on hexacyanometalates and nickel(II) diaminocomplexes incorporating anionic NN radicals of the carboxyphenyl type.

Comparison among superconducting models for β″-ET4[(H3O)Fe(C2O4)3]·C6H5Br single crystals by scanning tunnelling spectroscopy

Single crystals of the novel superconductor beta ''-(BEDT-TTF)(4)[(H3O)Fe(C2O4)(3)]center dot C6H5Br charge-transfer salt were studied using a scanning tunnelling microscope. The measured samples have an onset critical temperature of about 4.0 K. Features often reported on similar compounds were observed in the tunnelling spectra at 1.4 K. STS spectra are compared with several models for the superconducting density of states. Our analysis evidences inhomogeneous superconductivity and indicates that the presence of a magnetic layer into the sample plays a role in determining the superconducting spectroscopic features. (C) 2008 Elsevier Masson SAS. All rights reserved.

Synthesis, structure and magnetic properties of iron (II), cobalt (II) and nickel (II) complexes of 2,6-bis(pyrazol-3-yl)pyridine and paramagnetic counterions

Abstract Iron (II), cobalt (II) and nickel (II) complexes of 2,6-bis(pyrazol-3-yl)pyridine (bpp) with [Cr(C2O4)3]3− have been prepared. They were characterised by single-crystal X-ray diffraction, magnetic susceptibility measurements and thermal gravimetric analyses. All three compounds are isostructural and they are formed by isolated [MII(bpp)2]2+ and [Cr(C2O4)3]3− complexes and free ClO4 −. As expected, only the salt [Fe(bpp)2]2[Cr(C2O4)3]ClO4·5H2O shows a thermal spin transition with transition temperature (T1/2) around 375 K that is correlated to the loss of water molecules.

A Molecular Metal Ferromagnet from the Organic Donor Bis(ethylenedithio)tetraselenafulvalene and Bimetallic Oxalate Complexes

A new dual-function hybrid molecular material has been obtained from the organic donor bis(ethylenedithio)tetraselenafulvalene and the honeycomb oxalate-based bimetallic network [MnCr(ox)3]-. This multilayer material consists of layers of the inorganic anionic 2D network, responsible for the appearance of ferromagnetic ordering below 5.3 K, alternating with segregated layers of the organic cation radical responsible for the transport properties:  metal-like conductivity is observed from room temperature down to 150 K.

Coexistence of Mobile and Localized Electrons in Bis(ethylene)dithiotetrathiafulvalene(BEDT-TTF) Radical Salts with Paramagnetic Polyoxometalates: Synthesis and Physical Properties of(BEDT-TTF)8[CoW12O40]· 5.5 H2O

Hybrid Organic/Inorganic Molecular Materials Formed by Tetrathiafulvalene Radicals and Magnetic Trimeric Clusters of Dimetallic Oxalate‐Bridged Complexes: The Series (TTF) 4 {M II (H 2 O) 2 [M III (ox) 3 ] 2 }· n H 2 O (M II = Mn, Fe, Co, Ni, Cu and Zn; M III = Cr and Fe; ox = C 2 O 4 2− )

The first examples of trimeric, dimetallic, pure oxalate-bridged complexes [ox = (C2O4)2−] have been synthesized and characterized structurally and magnetically for the two new series of crystalline molecular assemblies formulated as (TTF)4{MII(H2O)2[MIII(ox)3]2}·nH2O [for MIII = Cr; MII = Mn (1), Fe (2), Co (3), Ni (4), Cu (5) and Zn (6); for MIII = Fe; MII = Mn (7), Fe (8), Co (9), Ni (10) and Zn (11)]. Both series (Cr2M and Fe2M) are isostructural. The crystal structure of (TTF)4{Mn(H2O)2[Cr(ox)3]2}⋅14H2O (1) [monoclinic, space group C2/c (no. 15), a = 13.240(5) A, b = 19.450(5) A, c = 27.690(5) A, β = 97.63(5)°, V = 7068(3) A3 and Z = 4] shows alternating layers of the organic radical T…

A New Layered Compound Containing [PMo12O40]3- and Both 5- and 6-Coordinated Homoleptic (1-(2-Chloroethyl)tetrazole)Copper(II) Cations

The synthesis, crystal structure and physical properties of the complex obtained from the reaction between the polyoxometalate anion [PMo12O40]3- copper(II) and the ligand 1-(2-chloroethyl)tetrazole (teec) are described. This compound has been synthesized as a model for designing materials containing both magnetic polyoxometalate anions and iron(II) spin-crossover cations. Keywords. Coordination chemistry; Heterocycles; Polyoxometalates; Structure elucidation; Tetrazole.

( n -Bu 4 N) 2 [Fe(dcbdt) 2 ] 2 . Synthesis, crystal structure and magnetic characterisation

Abstract The ( n -Bu 4 N) 2 [Fe(dcbdt) 2 ] 2 complex, where 4,5-dicyanobenzene-1,2-dithiolate (dcbdt), was prepared and characterised by X-ray diffraction, Mossbauer spectroscopy and magnetisation measurements. The crystal structure as determined by single crystal X-ray diffraction is triclinic, space group P 1 with cell parameters a =9.5660(1) A, b =13.0200(2) A, c =16.0850(2) A, α =67.554°(1), β =86.797°(1), γ =70.523°(1), V =1738.77(4) A 3 and it consists in strongly dimerised [Fe(dcbdt) 2 ] − units, which are stacked side by side as chains along a . The magnetic susceptibility shows that the [Fe(dcbdt) 2 ] − units have a low spin S =1/2 configuration and, besides a strong intradimer ant…

Magnetic polyoxometalates: anisotropic exchange interactions in the moiety of [(NaOH2)Co3(H2O)(P2W15O56)2]17-.

The magnetic exchange interactions in a C0(3)(11) moiety encapsulated in Na(17) [(NaOH(2))Co(3)(H(2)O)(P(2)W(15)O(56))(2)] (NaCo(3)) were studied by a combination of magnetic measurements (magnetic susceptibility and low-temperature magnetization), with a detailed Inelastic Neutron Scattering (INS) investigation. The novel structure of the salt was determined by X-ray crystallography. The ferromagnetic Co(3)O(14) triangular cluster core consists of three octahedrally oxo-coordinated Co(II) ions sharing edges. According to the single-ion anisotropy and spin-orbit coupling usually assumed for octahedral Co(II) ions, the appropiate exchange Hamiltonian to describe the ground-state properties o…

Metallic Conductivity in a Polyoxovanadate Radical Salt of Bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF): Synthesis, Structure, and Physical Characterization ofβ″-(BEDT-TTF)5[H3V10O28]·4H2O

Magnetostructural correlations in CuII−NC−WV linkage: the case of [CuII(diimine)]2+−[WV(CN)8]3− 0D assemblies

International audience; We report on the syntheses, crystal structures, and magnetic properties of two cyano-bridged molecular assemblies: [CuII(phen)3]2{[CuII(phen)2]2[WV(CN)8]2}(ClO4)2·10H2O (phen = 1,10-phenanthroline) (1) and {[CuII(bpy)2]2[WV(CN)8]} {[CuII(bpy)2][WV(CN)8]}·4H2O (bpy = 2,2′-bipyridyl) (2). Compound 1 consists of cyano-bridged [CuII2WV2]2− molecular rectangles and isolated [CuII(phen)3]2+ complexes. The molecular structure of 2 reveals cyano-bridged trinuclear [CuII2WV]+ and dinuclear [CuIIWV]− ions. Magnetic interactions in 1 are interpreted in terms of the model of a tetranuclear moiety consisting of two ferromagnetic CuII−NC−WV units (J1 = +39(4) cm−1) interacting ant…

CCDC 1984964: Experimental Crystal Structure Determination

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CCDC 1577301: Experimental Crystal Structure Determination

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CCDC 1984962: Experimental Crystal Structure Determination

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CCDC 1491308: Experimental Crystal Structure Determination

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CCDC 1973926: Experimental Crystal Structure Determination

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CCDC 1973938: Experimental Crystal Structure Determination

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CCDC 982641: Experimental Crystal Structure Determination

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CCDC 1446096: Experimental Crystal Structure Determination

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CCDC 1491307: Experimental Crystal Structure Determination

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CSD 1790045: Experimental Crystal Structure Determination

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CCDC 1984958: Experimental Crystal Structure Determination

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CCDC 2013419: Experimental Crystal Structure Determination

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CCDC 1538254: Experimental Crystal Structure Determination

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CCDC 1973924: Experimental Crystal Structure Determination

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CCDC 1482838: Experimental Crystal Structure Determination

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CCDC 1446095: Experimental Crystal Structure Determination

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CCDC 1973940: Experimental Crystal Structure Determination

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CCDC 1482841: Experimental Crystal Structure Determination

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CCDC 1435556: Experimental Crystal Structure Determination

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CCDC 1984961: Experimental Crystal Structure Determination

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CCDC 1973936: Experimental Crystal Structure Determination

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CCDC 1482842: Experimental Crystal Structure Determination

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CCDC 1832988: Experimental Crystal Structure Determination

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CCDC 1973941: Experimental Crystal Structure Determination

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CCDC 1984957: Experimental Crystal Structure Determination

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CCDC 1538255: Experimental Crystal Structure Determination

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CCDC 1507864: Experimental Crystal Structure Determination

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CCDC 1974500: Experimental Crystal Structure Determination

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CCDC 1446094: Experimental Crystal Structure Determination

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CCDC 982640: Experimental Crystal Structure Determination

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CCDC 1491309: Experimental Crystal Structure Determination

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CCDC 1832962: Experimental Crystal Structure Determination

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CCDC 1984960: Experimental Crystal Structure Determination

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CCDC 1973928: Experimental Crystal Structure Determination

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CCDC 1446097: Experimental Crystal Structure Determination

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CCDC 1819792: Experimental Crystal Structure Determination

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CCDC 1482839: Experimental Crystal Structure Determination

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CCDC 1577300: Experimental Crystal Structure Determination

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CCDC 1984963: Experimental Crystal Structure Determination

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CCDC 1973929: Experimental Crystal Structure Determination

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CCDC 1482840: Experimental Crystal Structure Determination

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CCDC 984545: Experimental Crystal Structure Determination

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CCDC 1446093: Experimental Crystal Structure Determination

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CCDC 1446092: Experimental Crystal Structure Determination

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CSD 1790044: Experimental Crystal Structure Determination

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CCDC 962306: Experimental Crystal Structure Determination

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CCDC 1538253: Experimental Crystal Structure Determination

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CCDC 1538256: Experimental Crystal Structure Determination

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CCDC 1984959: Experimental Crystal Structure Determination

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CCDC 1873604: Experimental Crystal Structure Determination

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CCDC 1873602: Experimental Crystal Structure Determination

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