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• W2058100980 endingPage "6808" @default.
• W2058100980 startingPage "6800" @default.
• W2058100980 abstract "The photophysics and photochemistry of the salt [(bpy)Re(CO)(3)(py)(+)][BzBPh(3)(-)] (ReBo, where bpy = 2,2'-bipyridine, py = pyridine, Bz = C(6)H(5)CH(2) and Ph = C(6)H(5)) has been investigated in THF and CH(3)CN solutions. UV-visible absorption and steady-state emission spectroscopy indicates that in THF ReBo exists primairly as an ion-pair. A weak absorption band is observed for the salt in THF solution that is assigned to an optical ion-pair charge transfer transition. Stern-Volmer emission quenching studies indicate that BzBPh(3)(-) quenches the luminescent dpi (Re) --> pi (bpy) metal-to-ligand charge transfer excited state of the (bpy)Re(CO)(3)(py)(+) chromophore. The quenching is attributed to electron transfer from the benzylborate anion to the photoexcited Re(I) complex, (bpy(-)(*))Re(II)(CO)(3)(py)(+) + BzBPh(3)(-) --> (bpy(-)(*))Re(I)(CO)(3)(py) + BzBPh(3)(*). Laser flash photolysis studies reveal that electron transfer quenching leads to irreversible reduction of the Re(I) cation to (bpy(-)(*))Re(I)(CO)(3)(py). Photoinduced electron transfer is irreversible owing to rapid C-B bond fragmentation in the benzylboranyl radical, PhCH(2)BPh(3)(*) --> PhCH(2)(*) + BPh(3)(*). Quantitative laser flash photolysis experiments show that the quantum efficiency for production of the reduced complex (bpy(-)(*))Re(I)(CO)(3)(py) is unity, suggesting that C-B bond fragmentation in the benzylboranyl radical occurs more rapidly than return electron transfer within the geminate radical pair that is formed by photoinduced electron transfer." @default.
• W2058100980 created "2016-06-24" @default.
• W2058100980 creator A5025436588 @default.
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• W2058100980 date "1996-01-01" @default.
• W2058100980 modified "2023-09-23" @default.
• W2058100980 title "Ion-Pair Charge Transfer Photochemistry in Rhenium(I) Borate Salts" @default.
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• W2058100980 doi "https://doi.org/10.1021/ic9605074" @default.
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• W2058100980 hasPublicationYear "1996" @default.
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