Stereoselective Excited-State Isomerization and Decay Paths in cis-Cyclobiazobenzene

Herein, we have employed OM2/MRCI-based full-dimensional nonadiabatic dynamics simulations to explore the photoisomerization and subsequent excited-state decay of a macrocyclic cyclobiazobenzene molecule. Two S1/S0 conical intersection structures are found to be responsible for the excited-state decay. Related to these two conical intersections, we found two stereoselective photoisomerization and excited-state decay pathways, which correspond to the clockwise and counterclockwise rotation motions with respect to the N═N bond of the azo group. In both pathways, the excited-state isomerization is ultrafast and finishes within ca. 69 fs, but the clockwise isomerization channel is much more favorable than the counterclockwise one with a ratio of 74% versus 26%. Importantly, the present work demonstrates that stereoselective pathways exist not only in the photoisomerization of isolated azobenzene (AB)-like systems but also in macrocyclic systems with multiple ABs. This finding could provide useful insights for...