Symmetry control of radiative decay in linear polyenes: low barriers for isomerization in the S1 state of hexadecaheptaene.

The room temperature absorption and emission spectra of the 4-cis and all-trans isomers of 2,4,6,8,10,12,14-hexadecaheptaene are almost identical, exhibiting the characteristic dual emissions S1-->S0 (21Ag- --> 11Ag-) and S2-->S0 (11Bu+ --> 11Ag-) noted in previous studies of intermediate length polyenes and carotenoids. The ratio of the S1-->S0 and S2-->S0 emission yields for the cis isomer increases by a factor of approximately 15 upon cooling to 77 K in n-pentadecane. In contrast, for the trans isomer this ratio shows a 2-fold decrease with decreasing temperature. These results suggest a low barrier for conversion between the 4-cis and all-trans isomers in the S1 state. At 77 K, the cis isomer cannot convert to the more stable all-trans isomer in the 21Ag- state, resulting in the striking increase in its S1-->S0 fluorescence. These experiments imply that the S1 states of longer polyenes have local energy minima, corresponding to a range of conformations and isomers, separated by relatively low (2-4 kcal) barriers. Steady state and time-resolved optical measurements on the S1 states in solution thus may sample a distribution of conformers and geometric isomers, even for samples represented by a single, dominant ground state structure. Complex S1 potential energy surfaces may help explain the complicated S2-->S1 relaxation kinetics of many carotenoids. The finding that fluorescence from linear polyenes is so strongly dependent on molecular symmetry requires a reevaluation of the literature on the radiative properties of all-trans polyenes and carotenoids.