Preparation and properties of conducting complexes based on 3-D conjugation system by δ-π interaction

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This project explored novel transition metal cluster complexes with moderate to high electrical conductivities based on δ-π interaction in paddlewheel-type dinuclear complexes. (1)We prepared dirhodium complexes with tetrathiafulalenyldiphenylphosphine as axial ligands and also those with tetrathiafulvalenylcarboxylate bridging ligands. In their crystals, intermolecular π-stack of TTF moieties has been observed. Their electrochemical behaviors showed that intermolecular TTF-TTF electronic interaction is not very strong. (2)Crystal structures of diruthenium complexes with 2-aminothiazolate bridging ligand showed that the RuRu δ^* orbital is located above the RuRu πorbital in energy due to δ-π interaction and the stronp donating nature of the bridging ligand. (3) A mixed oxidation-state complex having a diamondoid extended structure has been prepared from dirhodium tetraacetamidate, its cation radical and ssodium iodide. It is a semiconductor and its electrical conductivity oscillates over a order of 10^5 upon dehydration-rehydration cycles of its hydration water molecules. (4) The crystal of the cationic radical salt of a dirhodium complex with 4-phenanthridinolate bridging ligand has been shown to, a semiconductor. (5) A series of Co-Rh mixed mixed-element trinuclear complexes has been studied. The metal-metal interaction in this series of complexes has been shown to have a trend that heavier metal has stronger M-M interaction.