title: Pentacoordinate and Hexacoordinate Mn(III) Complexes of Tetradentate Schiff-Base Ligands Containing Tetracyanidoplatinate(II) Bridges and Revealing Uniaxial Magnetic Anisotropy.
abstract: Crystal structures and magnetic properties of polymeric and trinuclear heterobimetallic MnIII···PtII···MnIIIcoordination compounds, prepared from the Ba[Pt(CN)₄] and [Mn(L4A/B)(Cl)] (1a/b) precursor complexes, are reported. The polymeric complex [{Mn(L4A)}₂{μ⁴-Pt(CN)₄}]n(2a), where H₂L4A =N,N'-ethylene-bis(salicylideneiminate), comprises the {Mn(L4A)} moieties covalently connected through the [Pt(CN)₄]2-bridges, thus forming a square-grid polymeric structure with the hexacoordinate MnIIIatoms. The trinuclear complex [{Mn(L4B)}₂{μ-Pt(CN)₄}] (2b), where H₂L4B =N,N'-benzene-bis(4-aminodiethylene-salicylideneiminate), consists of two [{Mn(L4B)} moieties, involving pentacoordinate MnIIIatoms, bridged through the tetracyanidoplatinate (II) bridges to which they are coordinated in atransfashion. Both complexes possess uniaxial type of magnetic anisotropy, withD(the axial parameter of zero-field splitting) = -3.7(1) in2aand -2.2(1) cm-1in2b. Furthermore, the parameters of magnetic anisotropy2aand2bwere also thoroughly studied by theoretical complete active space self-consistent field (CASSCF) methods, which revealed that the former is much more sensitive to the ligand field strength of the axial ligands.
authors.affiliation: Department of Inorganic Chemistry, Faculty of Science, Palacký University, 17. listopadu 12, CZ-771 46 Olomouc, Czech Republic. ivan.nemec@upol.cz.
authors.forename: Ivan
authors.initials: I
authors.lastname: Nemec
authors.affiliation: Department of Inorganic Chemistry, Faculty of Science, Palacký University, 17. listopadu 12, CZ-771 46 Olomouc, Czech Republic. radovan.herchel@upol.cz.
authors.forename: Radovan
authors.initials: R
authors.lastname: Herchel
authors.affiliation: Department of Inorganic Chemistry, Faculty of Science, Palacký University, 17. listopadu 12, CZ-771 46 Olomouc, Czech Republic. zdenek.travnicek@upol.cz.
authors.forename: Zdeněk
authors.initials: Z
authors.lastname: Trávníček
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D008280:Magnetics; D008345:Manganese / Q000737:chemistry*; D015394:Molecular Structure; D017671:Platinum Compounds / Q000737:chemistry*; D012545:Schiff Bases / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D008024:Ligands; D017671:Platinum Compounds; D012545:Schiff Bases; D008345:Manganese
keywords: crystal structures; magnetic anisotropy; manganese(III); platinum(II); zero-field splitting