title: Synthesis, structure, magnetic properties and theoretical calculations of methoxy bridged dinuclear iron(III) complex with hydrazone based O,N,N-donor ligand.
abstract: Biomimetic complexes are artificially engineered molecules that aim to reduce the structural complexity of biological systems in order to unveil the key electronic and structural factors relevant to a protein's function. In this work, a novel coordination compound (L2Fe2) which mimics non-heme binuclear proteins was synthesized from the Schiff-base ligand HL = (E)-N′-(phenyl(pyridin-2-yl)methylene)isonicotinohydrazide. The crystal structure of L2Fe2 showed that the intramolecular Fe–Fe distances (3.1–3.2 Å) were analogous to those found in non-heme binuclear ferric proteins. However, in L2Fe2, two methoxide groups act as bridging units for oxidized iron (Fe3+). Such a bridging motif is unprecedented in the biological realm. Magnetic susceptibility measurements demonstrated that L2Fe2 is characterized by a singlet (S = 0) ground state and a very small magnetic coupling constant J (≪ −1 cm(−1)). The J value featured by L2Fe2 differs considerably from the values observed in non-heme binuclear proteins in the oxidized form (−100 cm(−1) < J < −10 cm(−1)), which encompass oxo/hydroxo and carboxylate bridging residues. The singlet ground state of L2Fe2 as well as the weak magnetic interaction between the two ferric cations was successfully predicted by density functional theory (DFT).
authors.affiliation: Department of Chemistry, University of Zanjan 45195-313, Zanjan, IR Iran.
authors.forename: Rahman
authors.initials: R
authors.lastname: Bikas
authors.forename: Hassan
authors.initials: H
authors.lastname: Hosseini-Monfared
authors.forename: Giorgio
authors.initials: G
authors.lastname: Zoppellaro
authors.forename: Radovan
authors.initials: R
authors.lastname: Herchel
authors.forename: Jiri
authors.initials: J
authors.lastname: Tucek
authors.forename: Anita M
authors.initials: AM
authors.lastname: Owczarzak
authors.forename: Maciej
authors.initials: M
authors.lastname: Kubicki
authors.forename: Radek
authors.initials: R
authors.lastname: Zboril
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry; D018360:Crystallography, X-Ray; D005290:Ferric Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D006835:Hydrazones / Q000737:chemistry*; D008024:Ligands; D060526:Magnetic Fields; D008958:Models, Molecular; D015394:Molecular Structure; D011789:Quantum Theory
chemical_list: D056831:Coordination Complexes; D005290:Ferric Compounds; D006835:Hydrazones; D008024:Ligands