ABSTRACT
Three different iridium(III) complexes, labelled as Ir1-Ir3, each bearing a unique anchoring moiety (diethyl [2,2'-bipyridine]-4,4'-dicarboxylate, tetraethyl [2,2'-bipyridine]-4,4'-diylbis(phosphonate), or [2,2'-biquinoline]-4,4'-dicarboxylic acid), were synthesized to serve as photosensitizers. Their electrochemical and photophysical characteristics were systematically investigated. ERP measurements were employed to elucidate the impact of the anchoring groups on the photocatalytic hydrogen generation performance of the complexes. The novel iridium(III) complexes were integrated with platinized TiO2 (Pt-TiO2) nanoparticles and tested for their ability to catalyze hydrogen production under visible light. A H2 turnover number (TON) of up to 3670 was obtained upon irradiation for 120 h. The complexes with tetraethyl [2,2'-bipyridine]-4,4'-diylbis(phosphonate) anchoring groups were found to outperform those bearing other moieties, which may be one of the important steps in the development of high-efficiency iridium(III) photosensitizers for hydrogen generation by water splitting. Additionally, toxicological analyses found no significant difference in the toxicity to luminescent bacteria of any of the present iridium(III) complexes compared with that of TiO2, which implies that the complexes investigated in this study do not pose a high risk to the aquatic environment compared to TiO2.
