A new structural motif for photoinitiated electron collection: Ru,Rh bimetallics providing insight into H-2 production via photocatalysis of water reduction by Ru,Rh,Ru supramolecules

Ru,Rh,Ru complexes are photocatalysts for the reduction of H2O to H-2 via a Rh(I) intermediate. The herein reported Ru, Rh bimetallics undergo PEC but do not catalyze the reduction of H2O, establishing intact supramolecules are photoactive in the Ru, Rh, Ru systems. The Ru, Rh(I) photoproduct dimerizes via Rh-Rh bond formation, deactivating the Rh(I) center sterically prohibited in the Ru,Rh,Ru trimetallic systems.