Twist and Return-Induced Ring Strain Triggers Quick Relaxation of a ( Z)-Stabilized Cyclobisazobenzene.

Continuous irradiation of the thermodynamically stable ( Z, Z)-cyclobisazobenzene does not lead to accumulation of a ( Z, E) or ( E, E) isomer as one might expect. Our combined experimental and computational investigation reveals that Z → E photoisomerization still takes place on an ultrafast time scale but induces large ring strain in the macrocycle, which leads to a very fast thermal back-isomerization, preventing photostationary accumulation of ( E)-isomers.