Fluorescence of Trans-4-Cyano-4′-dimethylaminostilbene; No Evidence for a TICT State

Abstract

Abstract The fluorescence properties of trans-4-cyano-4′-dimethylaminostilbene (trans-1) and a rigid analogue, in which the dimethylaminophenyl group is replaced by an indoline ring, trans-l-(4-cyanophenyl)-2-(5-[2,3-dihydro]N-methylindolyl)ethylene (trans-2) were studied in 20 solvents. The quantum yields of fluorescence (Φf) and of trans→cis photoisomerization (Φt→c) as well as the fluorescence maximum (ν̃f) and the bandwidth (⊿ν̃f) were examined. The activation energies (range: 3.5-7.8 kcal/mol) obtained from <2>f and <£t_c measurements are nearly the same for 1 and 2 in a given solvent. Φf , ν̃f and ⊿ν̃f as a function of solvent polarity and temperature show similar trends for 1 and 2. No dual emission was observed for either of the cyanostilbenes. These findings indicate that a twisted intramolecular charge transfer (TICT) state is not involved in the relaxation process of the first excited trans singlet state (1t*). The main deactivation pathway of 1t* competing with fluorescence is trans→cis photoisomerization by twisting about the C = C double bond in the first excited singlet state for both.