The photosensitizing properties of different polymer composites based on triphenylamine, polycarbonate, and chlorotricarbonyl rhenium(I) diimine complexes with various substituents are reported. The quantum efficiency increases with increasing applied electric field, following closely the Onsager theory with a thermalization distance of 1318 A. The primary yield shows a great dependence on the structure of the complexes, with the fluoro-substituted ligand exhibit the highest primary yield of 0.80, which is one order of magnitude higher than those of other complexes. When fabricated into a photovoltaic device, the quantum efficiency and fill factor were measured to be 2% and 0.18, respectively. (C) 2002 Elsevier Science B.V. All rights reserved.