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Pentacoordinate and Hexacoordinate Mn(III) Complexes of Tetradentate Schiff-Base Ligands Containing Tetracyanidoplatinate(II) Bridges and Revealing Uniaxial Magnetic Anisotropy

Department of Inorganic Chemistry, Faculty of Science, Palacký University, 17. listopadu 12, CZ-771 46 Olomouc, Czech Republic
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Academic Editor: Derek J. McPhee
Molecules 2016, 21(12), 1681; https://doi.org/10.3390/molecules21121681
Received: 25 October 2016 / Revised: 30 November 2016 / Accepted: 2 December 2016 / Published: 8 December 2016
(This article belongs to the Section Organometallic Chemistry)
Crystal structures and magnetic properties of polymeric and trinuclear heterobimetallic MnIII···PtII···MnIII coordination compounds, prepared from the Ba[Pt(CN)4] and [Mn(L4A/B)(Cl)] (1a/b) precursor complexes, are reported. The polymeric complex [{Mn(L4A)}24-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 MnIII atoms. 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 MnIII atoms, bridged through the tetracyanidoplatinate (II) bridges to which they are coordinated in a trans fashion. Both complexes possess uniaxial type of magnetic anisotropy, with D (the axial parameter of zero-field splitting) = −3.7(1) in 2a and −2.2(1) cm−1 in 2b. Furthermore, the parameters of magnetic anisotropy 2a and 2b were 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. View Full-Text
Keywords: manganese(III); platinum(II); zero-field splitting; magnetic anisotropy; crystal structures manganese(III); platinum(II); zero-field splitting; magnetic anisotropy; crystal structures
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Nemec, I.; Herchel, R.; Trávníček, Z. Pentacoordinate and Hexacoordinate Mn(III) Complexes of Tetradentate Schiff-Base Ligands Containing Tetracyanidoplatinate(II) Bridges and Revealing Uniaxial Magnetic Anisotropy. Molecules 2016, 21, 1681.

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