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Increasing Cage Escape Yields for Halide Oxidation in Aqueous Solutions Using Ir(III) Photosensitizers with π-Extended Aromatic Ligands
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DOI：10.1021/acs.inorgchem.5c05414.png)
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Abstract
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A series of five Ir(III) photosensitizers featuring π-extended aromatic ligands is reported for iodide, bromide, and chloride photo-oxidation in acetonitrile/water (50:50) mixtures. All photosensitizers exhibited excited-state reactivity toward iodide, bromide, and chloride, with quenching rate constants in the (1.2–2.1) 1010 M–1s–1, (0.8–4.8) 109 M–1s–1, and (0.049–1.3) 108 M–1s–1 range, respectively. Nanosecond transient absorption spectroscopy confirmed electron transfer from the halides to the excited photosensitizers, with cage escape yields (ΦCE) that were significantly higher in acetonitrile than in acetonitrile/water mixtures. In acetonitrile, up to unitary cage escape yields were obtained for iodide, bromide, and chloride oxidation. In water-enriched conditions, those yields decreased drastically, but the introduction of π-extended aromatic ligands allowed to maintain appreciable cage escape yields (ΦCE = 0.02–0.32).
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4.7
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10.5W