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  • Title: A cyanide-bridged FeIII-MnII heterobimetallic one-dimensional coordination polymer: synthesis, crystal structure, experimental and theoretical magnetism investigation.
    Author: Lan W, Zhou Z, Li J, Dou Y, Hao X, Yang L, Liu H, Li D, Liu Q, Zhang D.
    Journal: Acta Crystallogr C Struct Chem; 2019 Nov 01; 75(Pt 11):1475-1481. PubMed ID: 31686657.
    Abstract:
    A new cyanide-bridged FeIII-MnII heterobimetallic coordination polymer (CP), namely catena-poly[[[N,N'-(1,2-phenylene)bis(pyridine-2-carboxamidato)-κ4N,N',N'',N''']iron(III)]-μ-cyanido-κ2C:N-[bis(4,4'-bipyridine-κN)bis(methanol-κO)manganese(II)]-μ-cyanido-κ2N:C], {[FeMn(C18H12N4O2)(CN)2(C10H8N2)2(CH3OH)2]ClO4}n, (1), was prepared by the self-assembly of the trans-dicyanidoiron(III)-containing building block [Fe(bpb)(CN)2]- [bpb2- = N,N'-(1,2-phenylene)bis(pyridine-2-carboxamidate)], [Mn(ClO4)2]·6H2O and 4,4'-bipyridine, and was structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and powder X-ray diffraction (PXRD). Single-crystal X-ray diffraction analysis shows that CP 1 possesses a cationic linear chain structure consisting of alternating cyanide-bridged Fe-Mn units, with free perchlorate as the charge-balancing anion, which can be further extended into a two-dimensional supramolecular sheet structure via inter-chain π-π interactions between the 4,4'-bipyridine ligands. Within the chain, each MnII ion is six-coordinated by an N6 unit and is involved in a slightly distorted octahedral coordination geometry. Investigation of the magnetic properties of 1 reveals an antiferromagnetic coupling between the cyanide-bridged FeIII and MnII ions. A best fit of the magnetic susceptibility based on the one-dimensional alternating chain model leads to the magnetic coupling constants J1 = -1.35 and J2 = -1.05 cm-1, and the antiferromagnetic coupling was further confirmed by spin Hamiltonian-based density functional theoretical (DFT) calculations.
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