Studies on dynamic structures constructed by anisotropic assemblies of tetracyanometallate units

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  • Ohtani Ryo
    Department of Chemistry, Faculty of Science, Kyushu university

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  • テトラシアノ金属錯体を用いた異方的かつ動的な構造体に関する研究

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<p>We have investigated cyanide-based metal complexes, which were synthesized by combining [M(CN)4]2- (M = Pt, Pd, Ni) or [MN(CN)4]2- (M = Mn, Re) with metal complex cations, metal ions, and organic cations, by focusing on their dynamic structures such as thermal expansion (TE) and phase transition. For example, FePd(CN)4 is a three dimensional framework consisting of four-coordinate iron(II) nodes. This metal cyanide demonstrates large anisotropic TE involving negative TE (NTE) and colossal positive TE (PTE) during 100 K-500 K. Other examples are two-dimensional (2D) undulating layer-type coordination polymers of type [M(salen)]2[Ḿ (CN)4] (M = Mn, Fe; Ḿ = MnN, ReN, Pt, Pt(I2)x; x = 0.18, 0.45, 0.85, 1.0). Uniquely, they demonstrate composition-dependent anisotropic TE including 2D-PTE and 2D-NTE with wide range of linear TE coefficient values −45~+63 × 10-6 K-1. Furthermore, the combination of [MN(CN)4]2-(M = Mn, Re) with an ionic liquid cation, 1-ethyl-3-methylimidazolium (EmIm+), provided melting systems of (EmIm)2[MN(CN)4] involving cyanide-bridged architectures. Moreover, we also developing molecular probes incorporating the metal complex moieties, that can work in complex environments such as cell membranes, to investigate and promote membrane functions.</p>

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