To Isomerize or not to Isomerize? E/Z Isomers of Cyclic Azobenzene Derivatives and Their Reactivity Upon One-Electron Reduction

Azo compounds are efficient electron acceptors. Upon one-electron reduction they generally isomerize forming the thermodynamically most stable radical anion. Herein we show that the size of the central ring in 1,2-diazocines and diazonines has a ruling influence on the configuration of the one-electron reduced species. Markedly, diazonines, which bear a central nine membered heterocycle, show light-induced E/Z isomerization, but retain the configuration of the diazene N=N moiety upon one-electron reduction. Accordingly, E/Z isomerization is not induced by reduction.

Automated summary

The size of the central ring in 1,2-diazocines and diazonines influences the configuration of the one-electron reduced species. Diazonines with a central nine-membered heterocycle exhibit light-induced E/Z isomerization, while retaining the configuration of the diazene N=N moiety upon one-electron reduction. Therefore, E/Z isomerization is not induced by reduction.