Solving the Azobenzene Entropy Puzzle: Direct Evidence for Multi-State Reactivity.

A solution to the azobenzene "entropy puzzle" [ J. Phys.: Condens. Matter, 2017, 29, 314002] is provided. Previous computational studies of the thermal Z → E (back-)isomerization of azobenzene could not describe the experimentally observed large negative activation entropies. Here it is shown that the experimental results are only compatible with a more complicated multistate rotation mechanism that involves a triplet excited state. Using nonadiabatic transition state theory, close to perfect agreement is achieved between all calculated and experimental Eyring parameters. We also provide new experiments that indicate the presence of a noticeable external heavy-atom effect, which is a direct result of spin-orbit coupling effects being important in the proposed mechanism. These results suggest a reexamination of the mechanisms of related thermal double bond isomerizations in other systems in cases when an excited state of triplet (or other) multiplicity becomes thermally accessible during a rotation process.