Influence of Solvent Polarity and Viscosity on Nonradiative Processes in Oligothiophenes with Intramolecular Charge Transfer

By the methods of luminescence, picosecond spectroscopy, and quantumchemical calculations the mechanisms of electron excitation energy deactivation in some oligothiophenes with intramolecular charge transfer depending on the solvent polarity and viscosity have been investigated. While for 2Npiperidino5(2,2dicyanovinyl)thiophene (PDCVT) the main channel of nonradiative deactivation is the transition to a lower intermediate state with a twisted double bond controlled by the medium viscosity, in the case of (E){225piperidino2thienyl]6(trifluoridemethyl)4H4pyranylidene}propanedinitryl (PTFDN) fluorescence quenching is initiated by the solvent polarity. For two other oligothiophenes, 2Npiperidino5cyanothiophene (PCT) and 2Npiperidino5cyanoterthiophene (PCTT), differing in the length of the thiophene chain, we have revealed, along with the effective quenching of fluorescence in shortchain PCT (independent of the solvent polarity and viscosity), an increase in the radiation capacity in PCTT with increasing polarity of the solvent. The possible mechanisms of nonradiative deactivation in the investigated oligothiophenes are discussed.