Resolving photo-induced twisted intramolecular charge transfer with vibrational anisotropy and TDDFT.

The interplay between reaction environment and photochemical outcome has wide ranging implications for designing and directing light driven chemical conversions. We present a detailed mechanistic description of photoisomerization in julolidine malononitrile (JDMN) as the first step to characterizing this interplay between reaction pathways and reaction environment. We have used polarization resolved UV pump-mid-IR probe spectroscopy and time dependent DFT calculations to investigate the dynamics of charge transfer induced intramolecular rotation in JDMN. We have probed the mechanism and dynamics of photoisomerization with the symmetric and antisymmetric CN-stretch of the malononitrile group. These measurements show the S1 electronic excited state relaxes with a 12.3 ps time constant by isomerizing around both the C-C single and C-C double bond of the malononitrile group with a branching ratio of 1:5. Isomerization around the single bond leads to the formation of a metastable twisted excited state, while isomerization around the double bond leads to excited state quenching via a conical intersection between the S1 and S0 electronic states. We have characterized the electronic and nuclear structure of the long-lived excited state with pump-probe anisotropy measurements and time dependent DFT calculations using the CAM-B3LYP functional and the 6-31G(d,p) basis set. These calculations further confirm that isomerization around the malononitrile single bond forms a twisted intermolecular charge transfer excited state.