Award Accounts
Studies on dynamic structures constructed by anisotropic assemblies of tetracyanometallate units
2023 Volume 81 Pages 50-57
Details
2023 Volume 81 Pages 50-57
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.
