Self-assembled Ru(bda) Coordination Oligomers as Efficient Catalysts for Visible Light-Driven Water Oxidation in Pure Water.

Water-soluble multinuclear complexes based on ruthenium 2,2'-bipyridine-6,6'-dicarboxylate (bda) and ditopic bipyridine linker units are investigated in three-component visible light-driven water oxidation catalysis. Systematic studies revealed a strong enhancement of the catalytic efficiency in the absence of organic co-solvents and with increasing oligomer length. In-depth kinetic and morphological investigations suggest that the enhanced performance is induced by the self-assembly of linear Ru(bda) oligomers into aggregated superstructures. The obtained turnover frequencies (up to 14.9 s ) and turnover numbers (more than 1000) per ruthenium center are the highest reported so far for Ru(bda)-based photocatalytic water oxidation systems.