Unexplored Isomerization Pathways of Azobis(benzo-15-crown-5): Computational Studies on a Butterfly Crown Ether

Computational studies on trans → cis and cis → trans isomerizations of photoresponsive azobis­(benzo-15-crown-5) have been reported in this work. The photoexcited ππ* state (S2) of the trans isomer relaxes through the planar S2 minimum and the planar S2/S1 conical intersection (both situated around 9 kcal/mol below the vertically excited S2 state) arising along the NN stretching coordinate. The nπ* state (S1) of this isomer has both planar and rotated (clockwise and anticlockwise) minima, which may lead to a torsional conical intersection (S0/S1) geometry having a