Journal
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES
Volume 10, Issue 6, Pages 895-903Publisher
SPRINGERNATURE
DOI: 10.1039/c0pp00265h
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Photooxidation reactions of 1,5-dihydroxynaphthalene (DHN) have been carried out in the presence of cyclometalated neutral and cationic iridium (Ir) complexes 1-6 as singlet oxygen (O-1(2)) sensitizers in order to investigate the O-1(2) generation quantum yield and photosensitizing durability of the complexes. The reactions allowed a successful kinetic study to provide the pseudo-first-order rate constants and the initial rates of DHN consumption, which in turn led to the O-1(2) generation quantum yields. The results revealed that cationic Ir complexes [Ir(ppy)(2)(phen)(+) (4) and Ir(ppy)(2)(bpy)(+) (5), where ppy = 2-phenylpyridine, phen = 1,10-phenanthroline, bpy = 2,2'-bipyridyl] have high O-1(2) generation quantum yields (Phi(Delta) = 0.93, 0.97). On the other hand, neutral complexes with lower oxidation potentials were considered to have a more efficient charge-transfer (CT) interaction with molecular oxygen, which decreased the efficiency of singlet oxygen formation. Additionally, a steric factor of the ligands was reflected in O-1(2) generation quantum yield. High yields of the oxidized product for the photoreactions using the cationic complexes indicated their excellent photosensitizing durability, originating from the high photochemical stability upon irradiation.
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