Abstract
Time-resolved fluorescence studies on 4-dimethylamino-4′-cyano-stilbene (DCS) and on the laser dye DCM in homologous solvent series of differing polarity reveal a strong polarity control of the temperature-dependent nonradiative decay rate k nr. This rate is faster for DCS than for DCM by a factor of about 10 and is accelerated for low-polarity solvents. This is rationalized by a stepwise relaxation model which involves a TICT state (twisted single-bond conformation) as the main fluorescent species and temperature-activated nonradiative decay via a photochemical funnel with twisted double-bond conformation. CNDO/S calculations support this assignment.
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