Excited-State Proton Transfer of Phenol Cyanine Picolinium Photoacid

[Image: see text] Steady-state and time-resolved fluorescence techniques as well as quantum-mechanical calculations were used to study the photophysics and photochemistry of a newly synthesized photoacid—the phenol cyanine picolinium salt. We found that the nonradiative rate constant k(nr) of the excited protonated form of the photoacid is larger than that of the excited-state proton transfer (ESPT) to the solvent, k(ESPT). We estimate that the quantum efficiency of the ESPT process is about 0.16. The nonradiative process is explained by a partial trans–cis isomerization reaction, which leads to the formation of a “dark” excited state that can cross to the ground state by nonadiabatic coupling. Moreover, the ESPT process is coupled to the photo-isomerization reaction, as this latter reaction enhances the photoacidity of the studied compound, as a result of photoinduced charge transfer. To prevent trans–cis isomerization of the cyanine bridge, we conducted experiments of PCyP adsorbed on cellulose in the presence of water. We found that the steady-state fluorescence intensity increased by about a factor of 50 and the lifetime of the ROH band increased by the same factor. The fluorescence intensity of the RO(–) band with respect to that of the ROH band was the same as in aqueous solution. This explains why inhibiting the photo-isomerization reaction by adsorbing the PCyP on cellulose does not lead to a higher ESPT rate.