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Enhancement of Quantum Yield and Lifetime of Photoinduced Charge-Separation for Cyclometallated Platinum(Ii) Complex/Ferricyanide System Via Nafion Membrane-Solution Interface

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The photoinduced electron transfer from the excited state of cyclometallated platinum(II) complex PtL1L22+ (L1 = 4-methoxyphenyl-6-phenyl-2,2'-bibyridine, L2 = pyridine) incorporated into Nafion membranes to Fe(CN)63- in the surrounding solution has been examined. N,N'-tetramethylene-2,2'-bipyridinium (DQ2+) entrapped in the Nafion membranes is used as an electron relay. Luminescence quenching studies indicate that the quenching reaction of the excited PtL1L22+ with DQ2+ is static in nature. PtL1L23+ generated from the luminescence quenching remains in the Nafion matrix, while DQ+. migrates by an electron hopping mechanism to the Nafion-water interface, where transfers an electron to Fe(CN)63- to produce Fe(CN)64-. The negatively charged Fe(CN)64- is repelled into the bulk solution by the anionic Nafion surface. The isolation of the photoinduced oxidized species PtL1L23+ in Nafion from the ultimate reduced species Fe(CN)64- in solution prevents them from undergoing back electron transfer. Thus, an extremely long-lived charge separation state is achieved in a high quantum yield.

Affiliations: 1: Institute of Photographic Chemistry, the Chinese Academy of Sciences, Beijing 100101, China; 2: Center for Molecular Science, Institute of Chemistry, the Chinese Academy of Sciences, Beijing 100080, CHINA


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