Photochemical properties of mixed-metal supramolecular complexes


We have prepared a series of mixed-metal trimetallic complexes of the form {[(bpy)2Ru(BL)]2MCl2}n+(bpy 2,2′-bipyridine; BL 2,3-bis(2-pyridyl)pyrazine (dpp), 2,3-bis(2-pyridyl)quinoxaline (dpq) or 2,3-bis(2-pyridyl)-benzoquinozaline (dpb); M Ir(III), Rh(III) or Os(II). This new class of trimetallic complexes can be prepared with a good yield, often as high as 95%, using our building block strategy. The central rhodium and iridium fragments of these trimetallic, namely [M(BL)2Cl2]+, have been shown in our laboratory to be capable of delivering multiple electrons, "stored" on the bridging ligand π* orbitals, to a substrate as they functioned as electrocatalysts for the reduction of carbon dioxide to formate. The two terminal ruthenium metals are good light absorbers designed to give rise to photochemical activity. These bichromophoric systems should be capable of absorbing two photons of light, each giving rise to a desired photochemical reaction, namely excited-state electron transfer. Thus these systems form the basis of a molecular device for photoinitiated electron collection. The properties of these supramolecular complexes have been tuned by variation in the central metal and bridging ligand. Comparison of this array of nine complexes is described herein.

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Journal of Photochemistry and Photobiology, A: Chemistry