A family of iridium(III) complexes with a general structure, [Ir((CN)-N-boolean AND)(2)((NN)-N-boolean AND)PF6 ((CN)-N-boolean AND is cyclometalating ligand and (NN)-N-boolean AND is bipyridyl ligand), was synthesized and explored as photosensitizers (PSs) for photocatalytic hydrogen generation using a three-component system containing an electron donor, triethylamine (TEA), a colloidal platinum catalyst and water. The introduction of a novel fluorinated (CN)-N-boolean AND ligand, 2-(2,4-difluoropheny1)-4-methylquinoline, leads to much faster electron transfer from TEA to the excited-state Ir-PSs, as confirmed from Stern-Volmer measurements. In combination with the employment of various (NN)-N-boolean AND ligands attached with surface-adsorbing groups including vinyl, formyl, cyano, and pyridyl, the photocatalytic hydrogen-generation duration is significantly extended. This might be related to the fast quenching of the reduced state (Ir-PS-) resulting from the enhanced interaction between the Ir-PSs and the Pt catalyst. In photocatalytic reactions at relatively low Ir-PS concentrations, turnover numbers of over 10,000 for hydrogen generation can be attained using the formyl Ir-PS. (C) 2015 Elsevier Inc. All rights reserved.