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• W2096602008 abstract "Tetrathiafulvalene (TTF) spontaneously forms a series of unusual charge-transfer complexes with various quinonoid acceptors such as o-chloranil (CA) that show pronounced near-IR absorption (λCT = 1100 nm). The successful isolation of the corresponding [1: 1] donor–acceptor complex from solution and X-ray crystallographic analysis at low temperatures reveal the polarized charge-transfer state: [TTFq+,CAq−] with high degree of charge-tranfer (q = 0.6), which is spectrally and crystallographically distinguished from the separate redox (ion-pair) state: [TTF+˙ + CA−˙]. The unique interconversion of charge-transfer and electron-transfer states is theoretically well-accommodated by Mulliken theory using semi-empirical valence-bond and molecular-orbital methodologies. Mechanistic implications are discussed of both the thermally activated and the photochemically promoted processes via fast (intracomplex) electron transfer followed by collapse of the adiabatic and the non-adiabatic (vibrationally-excited) ion-pairs, respectively, to the [2 + 4] cycloadduct of tetrathiafulvalene and o-chloranil." @default.
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• W2096602008 date "2006-10-01" @default.
• W2096602008 modified "2023-10-10" @default.
• W2096602008 title "Electronic structures of intermolecular charge-transfer states in fast electron transfers with tetrathiafulvalene donor. Thermal and photoactivation of [2 + 4] cycloaddition to o-chloranil acceptor" @default.
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• W2096602008 doi "https://doi.org/10.1039/b607431f" @default.
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