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

Computational studies on trans & RARR; cis and cis & RARR; trans isomerizations of photoresponsive azobis(benzo-15-crown-5) havebeen reported in this work. The photoexcited & pi;& pi;* state(S-2) of the trans isomer relaxes throughthe planar S-2 minimum and the planar S-2/S-1 conical intersection (both situated around 9 kcal/mol belowthe vertically excited S-2 state) arising along the N UNstretching coordinate. The n & pi;* state (S-1) of thisisomer has both planar and rotated (clockwise and anticlockwise) minima,which may lead to a torsional conical intersection (S-0/S-1) geometry having a 更多