Tetrathiafulvalene-Fused Heterabuckybowl: Protonation-Induced Electron Transfer and Self-Sensitized Photooxidation.

The electron donor tetrathiafulvalene (D1 ) was fused onto the electron-rich heterabuckybowl trichalcogenasumanene (D2 ) through an electron-deficient pyrazine unit (A) to give 1 c, 1 d, 2 c, and 2 d, featuring the D1 -A-D2 structure. Both D1 and D2 play a pivotal role in intramolecular charge-transfer (ICT) transitions, consequently 1 c, 2 d, 2 c, and 2 d show a broad ICT band at 450-720 nm in steady state. They exhibit two charge-separated transient states, CS1 and CS2 , that appear in sequence. CS1 has a short lifetime (542 fs), and the D1 moiety on CS1 is in the radical cation state with an absorption maximum (λmax ) at 889 nm. CS1 then converts into CS2 (λmax , 1105 nm) through an ICT between D1 .+ and D2 , affording D1 (1-δ).+ and D2 δ.+ . Compounds 1 c, 1 d, 2 c, and 2 d show protonation-induced intramolecular electron transfer that leads to absorption at λ=700-1300 nm. Owing to the existence of an electron-rich C=C bond on the D1 moiety and in situ generation of 1 O2 by the pyrazine-fused D2 moiety, compounds 1 c, 1 d, 2 c, and 2 d display self-sensitized photooxidation in 50 s.