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- W2032028131 abstract "A study of laser kinetic spectroscopy on [RuII(tpy)(BL)CoIII(tpy)]5+ (BL: 1,4-bis[2,2‘:6‘,2‘ ‘-terpyridine-4‘-yl]benzene (btbz) and 6‘,6‘ ‘-bis(2-pyridyl)- 2,2‘:4‘,4‘ ‘:2‘ ‘,2‘ ‘‘-quarter-pyridine (bpqp)) revealed rise-and-decay of a triplet Ru-to-ligand charge-transfer state, 3CT(Ru), and an electron-transfer product of [(tpy)RuIII(BL)CoII(tpy)]5+. 3CT(Ru) underwent electron-transfer with a rate constant of 0.3 × 1012 and 1 × 1012 s-1 to produce [(tpy)RuIII(BL)CoII(tpy)]5+ with a doublet electronic configuration dπ6dσ* of cobalt(II). The return electron transfer (RET) of [RuIII(tpy)(BL)CoII(tpy)]5+ (BL:btbz and bpqp) in acetonitrile occurred with a rate constant of 1 × 1010 and 6 × 1010 s-1 at 298 K, respectively, which are much faster than intramolecular RET of [(bpy)2Ru(BL)Co(bpy)2]5+ from cobalt(II) with a quartet electronic configuration of dπ5dσ*2. The magnitude of reorganization energy (0.95 ± 0.15 eV) and electronic coupling matrix element (0.8 and 2 meV) are evaluated from the independence of RET rate on the temperature by using a small entropy change of RET. The small intramolecular reorganization energy (0−0.3 eV) for 2Co(II)/1Co(III) redox process of [(tpy)RuII(BL)CoIII(tpy)]5+ (BL: btbz and bpqp) are responsible for the fast RET. The magnitude of the intramolecular reorganization energy is in agreement with those (0.27−0.29 eV) calculated by using a density functional theory." @default.
- W2032028131 created "2016-06-24" @default.
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- W2032028131 date "2002-10-26" @default.
- W2032028131 modified "2023-09-23" @default.
- W2032028131 title "Temperature-Independent Rate of Electron-Transfer between a Cobalt(II) and a Ruthenium(III) of Doublet Electronic Configuration" @default.
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- W2032028131 doi "https://doi.org/10.1021/jp021257h" @default.
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