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Single molecule magnets of cobalt and zinc homo- and heterometallic coordination polymers prepared by a one-step synthetic procedure.

ABSTRACT: The synthesis of 1D cobalt and zinc monometallic and heterometallic coordination polymers (CPs) was carried out applying one-pot synthetic methods by using either supercritical carbon dioxide or ethanol as the solvent. A collection of four 1D CPs were thus obtained by the combination of a metal (or a mixture of metals) with the linker 1,4-bis(4-pyridylmethyl)benzene. The used metallic complexes were zinc and cobalt hexafluoroacetylacetonate, which can easily incorporate pyridine ligands in the coordination sphere of the metal centre. Independently of the used solvent, the precipitated phases involving Zn(ii), i.e., homometallic CP of Zn(ii) and bimetallic CP of Zn(ii)/Co(ii), were isostructural. Contrarily, homometallic CPs of Co(ii) were precipitated as an isostructural phase of Zn(ii) or with a different structure, depending on the used solvent. All the structures were resolved by XRD using synchrotron radiation. In addition, the magnetic properties of the new CPs involving Co(ii) were studied. Remarkably, at low temperatures with the application of an external field, they acted as field-induced single molecule magnets.

SUBMITTER: Portoles-Gil N

PROVIDER: S-EPMC9058601 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature

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Single molecule magnets of cobalt and zinc homo- and heterometallic coordination polymers prepared by a one-step synthetic procedure.

Portolés-Gil Núria N Gómez-Coca Silvia S Vallcorba Oriol O Marbán Gregorio G Aliaga-Alcalde Núria N López-Periago Ana A Ayllón José A JA Domingo Concepción C

RSC advances 20201221 73

The synthesis of 1D cobalt and zinc monometallic and heterometallic coordination polymers (CPs) was carried out applying one-pot synthetic methods by using either supercritical carbon dioxide or ethanol as the solvent. A collection of four 1D CPs were thus obtained by the combination of a metal (or a mixture of metals) with the linker 1,4-bis(4-pyridylmethyl)benzene. The used metallic complexes were zinc and cobalt hexafluoroacetylacetonate, which can easily incorporate pyridine ligands in the c ...[more]

PMID: 35516268

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Project description:One-dimensional (1D) oxalate-bridged homometallic {[Mn(bpy)(C2O4)]·1.5H2O}n (1) (bpy = 2,2'-bipyridine) and heterodimetallic {[CrCu3(bpy)3(CH3OH)(H2O)(C2O4)4][Cu(bpy)Cr(C2O4)3]·CH2Cl2·CH3OH·H2O}n (2) coordination polymers, as well as the three-dimensional (3D) heterotrimetallic {[CaCr2Cu2(phen)4(C2O4)6]·4CH3CN·2H2O}n (3) (1,10-phenanthroline) network, have been synthesized by a building block approach using a layering technique, and characterized by single-crystal X-ray diffraction, infrared (IR) and impedance spectroscopies and magnetization measurements. During the crystallization process partial decomposition of the tris(oxalate)chromate(III) happened and 1D polymers 1 and 2 were formed. The antiferromagnetic interactions between the manganese(II) ions was mediated by oxalate ligands in the chain [Mn(bpy)(C2O4)]n of 1, with intra-chain super-exchange interaction ? = (-3.134 ± 0.004) K; magnetic interaction between neighbouring chains is negligible making this system closer than other known Mn-chains to the ideal 1D Heisenberg antiferromagnet. Compound 2 comprises a 1D coordination anion [Cu(bpy)Cr(C2O4)3]nn- (Cr2-Cu4) with alternating [Cr(C2O4)3]3- and [Cu(bpy)]2+ units mutually bridged through the oxalate group. Another chain (Cr1-Cu3) is similar, but involves a homodinuclear unit [Cu(bpy)(H2O)(µ-C2O4)Cu(bpy)(CH3OH)]2+ (Cu1-Cu2) coordinated as a pendant group to a terminal oxalate oxygen. Magnetic measurements showed that the Cu1-Cu2 cationic unit is a strongly coupled antiferromagnetic dimer, independent from the other magnetic ions within ferromagnetic chains Cr1-Cu3 and Cr2-Cu4. A 3D polymer {[CaCr2Cu2(phen)4(C2O4)6]·4CH3CN·2H2O}n (3) comprising three different metal centers (Ca2+, Cr3+ and Cu2+) oxalate-bridged, contains Ca2+ atoms as nodes connected with four Cr3+ atoms through oxalate ligands. The network thus formed can be reduced to an underlying graph of diamondoid (dia) or (66) topology. Magnetization of 3 shows the ferromagnetic oxalate-bridged dimers [CuIICrIII], whose mutual interaction could possibly originate through the spin polarization of Ca2+ orbitals. Compounds 1 and 3 exhibit lower electrical conductivity at room temperature (RT) in comparison to compound 2.

Dataset Information

Single molecule magnets of cobalt and zinc homo- and heterometallic coordination polymers prepared by a one-step synthetic procedure.

Publications

Single molecule magnets of cobalt and zinc homo- and heterometallic coordination polymers prepared by a one-step synthetic procedure.

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