Cyclometalated iridium and platinum complexes as singlet oxygen photosensitizers: quantum yields, quenching rates and correlation with electronic structures

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Abstract
Photophysical properties are reported for a series of cyclometalated platinum and iridium complexes that can serve as photosensitizers for singlet oxygen. The complexes have the formula (C^N)2Ir(O^O) or (C^N)Pt(O^O) where C^N is a monoanionic cyclometalating ligand such as 2-(phenyl)pyridyl and 2-(phenyl)quinolyl, and O^O is the ancillary ligand acetylacetonate (acac) or dipivaloylmethane (dpm). Also examined were a series of (N^N)PtMe2 complexes where N^N is a diimine such as 2,2′-bipyridyl. In general, the cyclometalated complexes are excellent photosensitizers for the production of singlet oxygen, while the (N^N)PtMe2 complexes were ineffective at this reaction. Quantum yields of singlet oxygen production range from 0.9–1.0 for the cyclometalated Pt complexes and 0.5–0.9 for Ir complexes. Luminescence quenching and singlet oxygen formation of the Ir complexes occurs from a combination of electron and energy transfer processes, whereas the Pt complexes only react by energy transfer. For Ir complexes with low emission energy, physical deactivation of the triplet excited state becomes competitive with energy transfer to ground state dioxygen. The rates of singlet oxygen quenching for the complexes presented here are in the range 6 × 106–2 × 107 M−1 s−1 for Pt complexes and 2 × 105–2 × 107 M−1 s−1 for Ir complexes, respectively. Differences in the efficiency of both forming and quenching singlet oxygen between the Ir and Pt cyclometalates are believed to come about from the more exposed coordination geometry in the latter species.