Re(bpy)(CO)3 Cl Immobilized on Bipyridine-Periodic Mesoporous Organosilica for Photocatalytic CO2 Reduction.

This paper describes the physicochemical properties of a rhenium (Re) complex [Re(bpy)(CO)3 Cl] immobilized on a bipyridine-periodic mesoporous organosilica (BPy-PMO) acting as a solid support. The immobilized Re complex generated a metal-to-ligand charge transfer absorption band at 400 nm. This wavelength is longer than that exhibited by Re(bpy)(CO)3 Cl in the polar solvent acetonitrile (371 nm) and is almost equal to that in nonpolar toluene (403 nm). The photocatalytic activity of this heterogeneous Re complex was lower than that of a homogeneous Re complex due to the reduced phosphorescence lifetime resulting from immobilization. However, the catalytic activity was enhanced by the co-immobilization of the ruthenium (Ru) photosensitizer [Ru(bpy)3 ]2+ on the PMO pore surfaces. Quantum chemical calculations suggest that electron transfer between the Ru and Re complexes occurs through interactions between the molecular orbitals in the pore walls. These results should have applications to the design of efficient heterogeneous CO2 reduction photocatalysis systems.