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A trinuclear ruthenium complex, 3, was designed and synthesized with the ligand 2,2'-bipyridine-6,6'-dicarboxylic acid (bda) and we found that this complex could function as a highly efficient molecular catalyst for water oxidation in homogeneous systems. This trinuclear molecular water oxidation catalyst, 3, displayed much higher efficiencies in terms of turnover numbers and initial oxygen evolution rate than its counterparts, a binuclear catalyst, 2, and a mononuclear catalyst, 1, in both chemically driven and photochemically driven water oxidation based on either the whole catalytic molecules or just the active Ru centers. The reasons for the superior performance of catalyst 3 were discussed and we believe that multiple Ru centers in a single molecule are indeed beneficial for increasing the probability of the formation of O-O bonds through an intramolecular radical coupling pathway.

SUMMARYEffective capabilities of combined chemo-elasto-plastic and unsaturated soil models to simulate chemohydro-mechanical (CHM) behaviour of clays are examined in numerical simulations through selected boundary value problems. The objective is to investigate the feasibility of approaching such complex material behaviour numerically by combining two existing models. The chemo-mechanical effects are described using the concept of chemical softening consisting of reduction of the pre-consolidation pressure proposed originally by Hueckel (Can. Geotech. J. The equilibrium equations combined with the CHM constitutive relations, and the governing equations for flow of fluids and contaminant transport, are solved numerically using finite element. The emphasis is laid on understanding the role that the individual chemical effects such as chemo-elastic swelling, or chemo-plastic consolidation, or finally, chemical loss of cohesion have in the overall response of the soil mass. The numerical problems analysed concern the chemical effects in response to wetting of a clay specimen with an organic liquid in rigid wall consolidometer, during biaxial loading up to failure, and in response to fresh water influx during tunnel excavation in swelling clay.