To Isomerize or not to Isomerize? <i>E</i>/<i>Z</i> Isomers of Cyclic Azobenzene Derivatives and Their Reactivity Upon One‐Electron Reduction
Gabriel Glotz, Konstantin Knaipp, Martin S. Maier, Katharina Hüll, A. Novák, Anne‐Marie Kelterer, Thomas Griebenow, Rainer Herges, Dirk Trauner, Georg Gescheidt
Abstract
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.
Topics & Concepts
IsomerizationAzobenzeneMoietyReactivity (psychology)ChemistryRing (chemistry)Medicinal chemistryElectronStereochemistryPhotochemistryOrganic chemistryMoleculeCatalysisQuantum mechanicsAlternative medicineMedicinePathologyPhysicsPhotochromic and Fluorescence ChemistryRadical Photochemical ReactionsLuminescence and Fluorescent Materials