Mixed-metal supramolecular complexes that function as photochemical molecular devices for photoinitiated electron collection serve as photocatalysts for the reduction of water to hydrogen fuel. Component modification of the labile ligands within trimetallic complexes of the design [{(TL)Ru(BL)}2RhX2]5+ (TL = terminal ligand; BL = bridging ligand; X = labile ligand) provides insight into the water reduction processes that occur in a homogeneous molecular system. Upon collection of two reducing equivalents at Rh(III), halide loss is predicted to occur to form the active catalyst, a square planar Rh(I) species. Changes in the observed long-term photocatalytic stability in organic versus aqueous solvent upon variation of the non-chromophoric ligands at Rh(III) will be discussed. Electrochemical and photophysical characterizations for this supramolecular motif will also be examined. Acknowledgement is made to Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Sciences, U.S. Department of Energy DEFG02-05ER15751 for their generous financial contribution.

Mechanistic insight into water reduction provided by labile ligand variation at Rh(III) in Ru(II),Rh(III),Ru(II) supramolecular photocatalysts

249th National Meeting (2015)

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