多座ホスフィンにより支持された分子性金属鎖の開発

概要

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This account reports recent development of linearly ordered multinuclear transition-metal complexes, or molecular metal atom chains, supported by multidentate phosphines, which could be important motifs for nano-structured molecular devices. In particular, it focuses on our recent results of platinum-based homo- and hetreromultimetallic complexes supported by a triphosphine ligand, bis(diphenylphosphinomethyl)phenylphosphine (dpmp), in which strategic synthetic methods of cluster core expansion have been established from Pt2 complexes to Pt-Pt-M (M = Pt, Pd, Ir, Rh, Au, Ag, Cu) and Pt-M-Pt (M = Pt, Pd), and to the linear Pt2M2Pt2 molecular chains (M = Pt, Pd) as well as one-dimensional assemblage of the linear Pt3 units connected by bisisocyanide linkers. A linear tetraphosphine, meso-bis{(diphenylphosphinomethyl)phenylphosphino}methane (dpmppm), was synthesized to support linearly ordered tetranuclear metal chains, leading to successful isolation of the linear Pd8 complexes, [Pd8(μ-dpmppm)4]4+ and [Pd8(μ-dpmppm)4(XylNC)2]4+ (Xyl = 2,6-xylyl) which showed a Pd-Pd bonded linear structure and an interesting thermochromic behavior. The dpmppm ligand also supported flexibly bending Au4 complexes with a photochemical switch upon recognizing counter anions, and Au4M2Cu2 heterometallic rings, [{Au2MCuCl2(μ-dpmppm)2}2]4+ (M = Au, Ag, Cu), exhibiting strong inclusion behavior for a BF4- anion into pore of the Au4Ag2Cu2 ring.