Advanced Functions of Multinuclear Metal Complexes Modified with Cyclic Tetrapyrroles

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In this project, we have developed synthetic methods for discrete cyclic assemblies where redox-active transition-metal components are linked together with a series of bidentate spacers in a well-defined number and geometry. These high-nuclearity clusters are formed from a soluble triruthenium cluster^1 and organic linkers, such as pyrazine. The pyrazine-bridged systems show multiple-step redox processes arising from strong electronic communications between the redox components, where the extent of the communication is varied, depending on the geometry and nuclearity of the resulting structures, π-level of the organic spacers, and the nature of electrolyte media. The synthesis of wire-shaped and box-shaped clusters has been also achieved. Synthesis and molecular structures of a series of six-coordinate Ru(II) complexes of porphycene have been investigated. Kinetic studies on the axial pyridine exchange reactions of these compounds have been achieved.