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…

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…

Novel malonate-containing coordination compounds with ligands having N-And NO-donors: Synthesis, structures, and magnetic properties

In our efforts to tune the structures of mixed-ligands malonate-containing coordination compounds, four copper(II) and two high-spin cobalt(II) complexes of formulas [Cu(mal)(H 2O)(dpo)] n (1), [Cu 2(mal) 2(H 2O) 2(dpp)] n · 7nH 2O (2), [Cu 2(mal) 2(H 2O) 2-(bpe)] n · 2nH 2O (3), {[Cu(mal) 2(H 2O) 2][Cu(dien)]} n · 4nH 2O (4)[Co 2(mal) 2(H 2O) 6(dpo)] ·2H 2O(5) and [Co(mal)(H 2O)(phen)] n · 2nH 2O (6) [H 2mal = malonic acid, dpo =4,4'-bipyridine-N,N'-dioxide, dpp = 2,3-bis(pyridyl)pyrazine, bpe =1,2-bis(4-pyridyl)ethylene, dien = diethylenetriamine and phen = 1,10-phenanthroline] have been synthesized and structurally characterized by X-ray diffraction on single crystals. Complexes 1, 2, 4,…

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 …

{[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- …

ChemInform Abstract: Oxamato-Based Coordination Polymers: Recent Advances in Multifunctional Magnetic Materials

The design and synthesis of novel examples of multifunctional magnetic materials based on the so-called coordination polymers (CPs) have become very attractive for chemists and physicists due to their potential applications in nanoscience and nanotechnology. However, their preparation is still an experimental challenge, which requires a deep knowledge of coordination chemistry and large skills in organic chemistry. The recent advances in this field using a molecular-programmed approach based on rational self-assembly methods which fully exploit the versatility of the coordination chemistry of the barely explored and evergreen family of N-substituted aromatic oligo(oxamato) ligands are prese…

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…

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…

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…

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, …

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)…

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…

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…

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

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…

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…

[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…

Copper(II) complexes with 2,5-bis(2-pyridyl)pyrazine and oxalate and croconate: Synthesis, crystal structure and magnetic properties

Abstract Two new copper(II) complexes of formula [Cu2(2,5-dpp)(C2O4)2(H2O)4] (1) and [Cu2(2,5-dpp)(C5O5)2(H2O)4]·3H2O (2) [2,5-dpp = 2,5-bis(2-pyridyl)pyrazine, C2O42− = oxalate and C5O52− = croconate (dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione)] have been prepared and their structures determined by X-ray crystallographic methods. Compounds 1 and 2 are dinuclear complexes where the 2,5-dpp molecule acts as a bis-bidentate bridge between the two copper(II) ions, the electroneutrality being achieved by the presence of bidentate oxalate (1) and croconate (2) ligands. Each copper(II) ion exhibits an elongated octahedral CuN2O4 environment with two nitrogen atoms from 2,5-dpp and two o…

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 …

[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…

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…

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.…

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

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…

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…

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…

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…

Extending the halogen-bonded supramolecular synthon concept to 1,3,4-oxadiazole derivatives

A series of five crystal structures of 1:1 halogen-bonded complexes were obtained from 4-[5-(4-alkoxyphenyl)-1,3,4-oxadiazole-2-yl]pyridine and 1,3,5-trifluorotriiodobenzene. Electronic structure calculations show that the N(oxadiazole)⋯I interaction in the new synthon is as strong as the classic N(pyridine)⋯I interaction. Oxygen to sulfur atom subsitution on the oxadiazole ring results in a different supramolecular packing where the N(pyridine)⋯I interaction is favored, which could be rationalized by the changes in the molecular electrostatic potential predicted from the theoretical calculations.

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

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 (…

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…

Synthesis, crystal structures and magnetic properties of M(II)Cu(II) chains (M = Mn and Co) with sterically hindered alkyl-substituted phenyloxamate bridging ligands.

A series of neutral oxamato-bridged heterobimetallic chains of general formula [MCu(L(x)2 (S)2] · p S · q H2O [p = 0-1, q = 0-2.5; L1 = N-2,6-dimethylphenyloxamate, S = DMF with M = Mn (1a) and Co (1b); L2 = N-2,6-diethylphenyloxamate, S = DMF with M = Mn (2a) and Co (2b) or S = DMSO with M = Mn (2c) and Co (2 d); L3 = N-2,6-diisopropylphenyloxamate, S = DMF with M = Mn (3a) and Co (3b) or S = DMSO with M = Mn (3c) and Co (3d)] were prepared by treating the corresponding anionic oxamatocopper(II) complexes [Cu(L(x))(2)]2- (x = 1-3) with M(2+) cations (M = Mn and Co) in DMF or DMSO as the solvent. The single-crystal X-ray structures of 2a and 3a reveal the occurrence of well-isolated, zigzag…

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, …

Influence of the presence of divalent first-row transition metal ions on the structure of sodium(i) salts of 1,2,3,4-benzenetetracarboxylic acid (H4bta)

Three different sodium(I)-containing salts of 1,2,4,5-benzenetetracarboxylic (H4bta) of formula [Na4(bta)(H2O)12] (1), [Na2M(H2bta)2(H2O)8]·2H2O] [M = Mn (2) and Ni (3)] were synthesized and their structures were solved by single crystal X-ray diffraction methods. Compound 1 crystallises in orthorhombic system, space group Pc21b with a = 6.9997(4) A, b = 16.4260(9) A, c = 20.3312(18) A, V = 476.30(15) A3 and Z = 4. Compounds 2 and 3 crystallize in the monoclinic system, space group C2/m with a = 7.3778(4) A, b = 20.1493(6) A, c = 10.4963(4) A, β = 103.466(8)°, V = 1517.5(11) A3 and Z = 2 for 1 and a = 7.2862(4) A, b = 20.1165(7) A, c = 10.4032(3) A, β = 103.366(9)°, V = 1483.52(11) A3 and Z…

Synthesis, structural analysis, and magnetic properties of ethylmalonate-manganese(II) complexes

12 páginas, 10 figuras, 6 tablas.-- et al.

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, 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…

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…

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 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 …

Recognition of self-assembled water-nitrate cluster in a Co(III)-2,2′-bipyridine host: Synthesis, X-ray structure, DNA cleavage, molecular docking and anticancer activity

A mononuclear cobalt(III) complex [Co(bpy)2Cl2]NO3⋅2H2O (1) (bpy = 2,2′-bipyridine) has been synthesized and crystallographically characterized. Self-assembly of the lattice water molecules from rectangular tetrameric water cluster interacts with nitrate anion along the c-axis forming a six membered hexagonal water-nitrate cluster. It presents a new mode of association of water molecules with nitrate molecules which is not predicted theoretically or found experimentally. The molecule effectively cleaves bacterial genomic DNA and shows important cytotoxicity against human hepatocarcinoma cell (HepG2).

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.

Postsynthetic Improvement of the Physical Properties in a Metal-Organic Framework through a Single Crystal to Single Crystal Transmetallation

As ingle crystal to single crystal transmetallation process takes place in the three-dimensional (3D) metal- organic framework (MOF) of formula Mg II 2{Mg II 4(Cu II 2- (Me3mpba)2)3}·45 H2 O( 1 ;M e 3mpba 4¢ = N,N'-2,4,6-trimethyl- 1,3-phenylenebis(oxamate)). After complete replacement of the Mg II ions within the coordination network and those hosted in the channels by either Co II or Ni II ions, 1 is transmetallated to yield two novel MOFs of formulae Co2 II {Co II 4(Cu II 2(Me3- mpba)2)3}·56 H2 O( 2 )a nd Ni2 II {Ni II 4(Cu II 2(Me3mpba)2)3}· 54 H2 O( 3). This unique postsynthetic metal substitution affords materials with higher structural stability leading to enhanced gas sorption and m…

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…

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)

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.

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…

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 novel oxalate-based three-dimensional coordination polymer showing magnetic ordering and high proton conductivity

A novel three-dimensional (3D) coordination polymer with the formula (C3N2H5)4[MnCr2(ox)6]·5H2O (2), where ox = oxalate and C3N2H5 = imidazolium cation, is reported. Single crystal X-ray diffraction reveals that this porous coordination polymer adopts a chiral three-dimensional quartz-like architecture, with the guest imidazolium cations and water molecules being hosted in its pores. This novel multifunctional material exhibits both a ferromagnetic ordering at TC = 3.0 K, related to the host MnCr2 network, and high proton conductivity [1.86 × 10−3 S cm−1 at 295 K and 88% relative humidity (RH)] due to the presence of the acidic imidazolium cations and free water molecules. The similarity of…

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)].

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.

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…

Solution and solid state studies with the bis-oxalato building block [Cr(pyim)(C2O4)2]− [pyim = 2-(2′-pyridyl)imidazole]

The preparation, X-ray structure, and variable temperature magnetic study of the new compound {Ba(H2O)3/2[Cr(pyim)(C2O4)2]2}n·9/2nH2O (1) [pyim = 2-(2′-pyridyl)imidazole and C2O42− = dianion of oxalic acid], together with the potentiometric and spectrophotometric studies of the protonation/deprotonation equilibria of the pyim ligand and the ternary complex [Cr(pyim)(C2O4)2]−, are reported herein. The crystal structure of 1 consists of neutral chains, with diamond-shaped units sharing barium(II), with the two other corners occupied by chromium(III). The two metal centers are connected through bis(bidentate) oxalate. Very weak antiferromagnetic interactions between the chromium(III) ions occu…

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…

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…

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.

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…

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.

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…

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

Synthesis, structural analysis, and thermal and spectroscopic studies of methylmalonate-containing zinc(II) complexes

The synthesis, crystal structure, thermal analysis and spectroscopic studies of five zinc(II) complexes of formulae [Zn(Memal)(H2O)]n (1) and [Zn2(L)(Memal)2(H2O)2]n (2-5) [H2Memal = methylmalonic acid, and L = 4,4′-bipyridine (4,4′-bpy) (2), 1,2-bis(4-pyridyl)ethylene (bpe) (3), 1,2-bis(4-pyridyl)ethane (bpa) (4) and 4,4′-azobispyridine (azpy) (5)] are presented here. The crystal structure of 1 is a three-dimensional arrangement of zinc(II) cations interconnected by methylmalonate groups adopting the μ3-κ2O:κO’:κO”:κO”’ coordination mode to afford a rare (10,3)-d utp-network. The structures of the compounds 2-5 are also three-dimensional and they consist of corrugated square layers of meth…

Crystal structure analysis of supramolecular arrangements in bis(1-isoquinolinecarboxamide)alkanes and their Ag(i) complexes

A homologous series of bis(1-isoquinolinecarboxamide)alkane derivatives (3a–f) with two to seven carbon atoms in the alkyl bridge and their Ag(I) complexes (4a–f) have been synthesized. Four ligand and five Ag(I) complex crystal structures were obtained by single crystal X-ray diffraction and analyzed in terms of: a) their structural patterns based on intra- and intermolecular hydrogen bonds which were compared to those of bis(2-quinolinecarboxamide)alkanes (1n) and bis(6-quinolinecarboxamide)alkanes (2n) attending to specific geometrical parameters and b) the Ag(I) coordinate bond effect on these patterns and the amide-to-amide hydrogen bonds. The crystal structures of the ligands 3a, 3c, …

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…

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…

Oxamato-based coordination polymers: recent advances in multifunctional magnetic materials

The design and synthesis of novel examples of multifunctional magnetic materials based on the so-called coordination polymers (CPs) have become very attractive for chemists and physicists due to their potential applications in nanoscience and nanotechnology. However, their preparation is still an experimental challenge, which requires a deep knowledge of coordination chemistry and large skills in organic chemistry. The recent advances in this field using a molecular-programmed approach based on rational self-assembly methods which fully exploit the versatility of the coordination chemistry of the barely explored and evergreen family of N-substituted aromatic oligo(oxamato) ligands are prese…

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…

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…

Cadmium(ii) coordination polymers based on substituted malonic acid: synthesis, characterization and photoluminescence properties

Four novel complexes of cadmium(II) with alkyl/aryl-substituted malonate ligands of formulae {[Cd(Memal)(H2O)]6·0.5H2O}n (1), [Cd(Etmal)(H2O)]n (2), [Cd(Butmal)(H2O)]n (3) and [Cd(Bzmal)(H2O)]n (4), (Memal = methylmalonate, Etmal = ethylmalonate, Butmal = butylmalonate and Bzmal = benzylmalonate) have been prepared and characterized by single crystal X-ray analysis. Their luminescence, UV-Vis absorption properties and thermal behaviour were also investigated. Complex 1 is a three-dimensional compound where each metal centre is connected to four other ones leading to a sodalite network with the point symbol {42·64}. Each cadmium(II) ion in 1 is seven-coordinate with a water molecule and six …

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…

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…

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.

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

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.

CCDC 1867353: Experimental Crystal Structure Determination

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CCDC 294297: 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 941373: Experimental Crystal Structure Determination

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CCDC 1409980: Experimental Crystal Structure Determination

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CCDC 294298: Experimental Crystal Structure Determination

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CCDC 1555659: 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 958833: Experimental Crystal Structure Determination

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CCDC 1409978: Experimental Crystal Structure Determination

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CCDC 984262: Experimental Crystal Structure Determination

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CCDC 1545085: Experimental Crystal Structure Determination

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CCDC 1989325: Experimental Crystal Structure Determination

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CCDC 1030506: Experimental Crystal Structure Determination

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CCDC 958838: Experimental Crystal Structure Determination

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CCDC 1409982: Experimental Crystal Structure Determination

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CCDC 1506154: Experimental Crystal Structure Determination

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CCDC 1524200: Experimental Crystal Structure Determination

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CCDC 1506157: Experimental Crystal Structure Determination

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CCDC 1506155: Experimental Crystal Structure Determination

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CCDC 1901771: Experimental Crystal Structure Determination

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CCDC 996269: Experimental Crystal Structure Determination

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CCDC 996270: Experimental Crystal Structure Determination

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CCDC 996271: Experimental Crystal Structure Determination

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CCDC 1545086: Experimental Crystal Structure Determination

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CCDC 937587: 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 1506156: Experimental Crystal Structure Determination

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CCDC 1510397: Experimental Crystal Structure Determination

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CCDC 937589: Experimental Crystal Structure Determination

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CCDC 946980: Experimental Crystal Structure Determination

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CCDC 984264: 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 937590: Experimental Crystal Structure Determination

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CCDC 958835: Experimental Crystal Structure Determination

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CCDC 1506153: Experimental Crystal Structure Determination

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CCDC 1030504: Experimental Crystal Structure Determination

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CCDC 1857503: Experimental Crystal Structure Determination

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CCDC 1545087: Experimental Crystal Structure Determination

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CCDC 1901770: Experimental Crystal Structure Determination

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CCDC 1545088: Experimental Crystal Structure Determination

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CCDC 1475076: Experimental Crystal Structure Determination

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CCDC 1414395: Experimental Crystal Structure Determination

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CCDC 1506158: Experimental Crystal Structure Determination

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CCDC 937591: Experimental Crystal Structure Determination

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CCDC 958832: Experimental Crystal Structure Determination

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CCDC 1409983: Experimental Crystal Structure Determination

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CCDC 1510399: Experimental Crystal Structure Determination

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CCDC 937588: Experimental Crystal Structure Determination

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CCDC 294299: 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 984260: 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 1857501: Experimental Crystal Structure Determination

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CCDC 1901768: Experimental Crystal Structure Determination

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CCDC 952343: Experimental Crystal Structure Determination

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CCDC 1555658: Experimental Crystal Structure Determination

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CCDC 984265: Experimental Crystal Structure Determination

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CCDC 1409979: Experimental Crystal Structure Determination

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CCDC 1867352: 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 1857500: Experimental Crystal Structure Determination

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CCDC 1506160: Experimental Crystal Structure Determination

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CCDC 1506161: Experimental Crystal Structure Determination

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CCDC 1857502: Experimental Crystal Structure Determination

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CCDC 1524199: Experimental Crystal Structure Determination

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CCDC 958830: Experimental Crystal Structure Determination

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