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

本项目基于桨轮型双核配合物中的δ-π相互作用，探索具有中到高电导率的新型过渡金属簇合物。(1)We制备了以四硫富瓦烯基二苯基膦为轴向配体的二铑配合物以及以四硫富瓦烯基羧酸酯为桥连配体的二铑配合物。在它们的晶体中，观察到TTF部分的分子间π堆叠。其电化学行为表明TTF分子间电子相互作用不是很强。（2）2-氨基噻唑桥联配体双钌配合物的晶体结构表明，由于δ-π相互作用和桥联配体的强施主性质，RuRu δ^* 轨道的能量位于RuRu π轨道之上。(3)本文报道了由四乙酰氨基二铑及其阳离子自由基和碘化钠合成的具有类金刚烷伸展结构的混合氧化态配合物。它是一种半导体，其电导率在其水合水分子的脱水-再水化循环中振荡超过10^5的数量级。(4)具有4-菲啶根桥联配体的二铑配合物的阳离子自由基盐的晶体已被证明是半导体。(5)本文研究了一系列钴铑混合元素三核配合物。这一系列配合物中金属间的相互作用表现出重金属具有较强的M-M相互作用的趋势。

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.