Photoisomerization mechanism of 1,1'-dimethyl-2,2'-pyridocyanine in the gas phase and in solution.

The trans→cis and cis→trans photoisomerization mechanisms of 1,1'-dimethyl-2,2'-pyridocyanine have been investigated theoretically in the gas phase and in methanol. Two-dimensional potential energy surfaces were computed for the ground and first excited singlet states of the isolated molecule using complete active space self-consistent field method. Our computations suggest that the torsion around the central C-C bonds with carbon-out-of-plane motion is the preferred photoisomerization mechanism. In the gas phase, conical intersections were found near the minima of excited state. The excited-state decay follows a barrierless minimum-energy pathway before the molecule moves to the excited-state global minimum (minS1) and the system relaxes to the ground state through a conical intersection. In methanol, the system would first reach a stationary structure of C2 symmetry after the trans form is electronically excited. Solvent polarity effects were investigated in chloroform, dichloromethane, 1-propanol, ethanol, methanol, and water. There is a significant barrier between the stationary structure of C2 symmetry and minS1 in the excited state in high polarity solvents. Thus, Me-1122P has a much longer lifetime of the excited state in solvents of high polarity.