Structure-Activity Relationship for Di- up to Tetranuclear Macrocyclic Ruthenium Catalysts in Homogeneous Water Oxidation.

Two di- and tetranuclear Ru(bda) (bda: 2,2'-bipyridine-6,6'-dicarboxylate) macrocyclic complexes were synthesized and their catalytic activities in chemical and photochemical water oxidation investigated in a comparative manner to our previously reported trinuclear congener. Our studies have shown that the catalytic activities of this homologous series of multinuclear Ru(bda) macrocycles in homogeneous water oxidation are dependent on their size, exhibiting highest efficiencies for the largest tetranuclear catalyst. The turnover frequencies (TOFs) have increased from di- to tetranuclear macrocycles not only per catalyst molecule but more importantly also per Ru unit with TOF of 6 s to 8.7 s and 10.5 s in chemical and 0.6 s to 3.3 s and 5.8 s in photochemical water oxidation per Ru unit, respectively. Thus, for the first time, a clear structure-activity relationship could be established for this novel class of macrocyclic water oxidation catalysts.