金属- 金属結合の一次元伸張化: Frontier Orbital Engineering

抄録

Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University Kazuhiro Uemura Although many one-dimensional chain complexes bridged by halide ions or organic molecules have been reported, relatively few are extended by direct metal–metal bonds, and the metals involved are limited to Rh, Pd, Ir, and Pt. In this paper, several one-dimensional complexes in which two or three metals are regularly aligned with metal–metal bonds will be shown, utilizing the HOMO–LUMO interaction at the σ* orbitals between two types of complexes. The obtained single crystals of the heterometallic one-dimensional complexes exhibit an attractive color with a metallic luster. In addition, while one-dimensional complexes consisting of a single species have a partially oxidized σ-type orbital as the HOMO, heterometallic one-dimensional complexes can exhibit an unusual electronic structure in which another metal orbital is inserted between the σ-type valence and conduction bands as the HOMO, enabling paramagnetism and band gap modulation. Our research group has also found that these complexes exhibit strong magnetic interactions via metal–metal bonds.