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.

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 (lambda(CT) = 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: [TTF(q+),CA(q-)] with high degree of charge-transfer (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.