Radical cations of twisted acenes: chiroptical properties and spin delocalization

Abstract

We introduce the first series of enantiopure twistacene radical cations, which form reversibly upon chemical or electrochemical oxidation. Their vis-NIR chiroptical properties (Cotton effect and anisotropy factor) increase systematically with the backbone twist. The hyperfine constants observed by EPR demonstrate significant spin delocalization even for large backbone twist angles.