Role of exciton delocalization in chiroptical properties of benzothiadiazole carbon nanohoops†

Abstract

Development of chiral organic materials with a strong chiroptical response is crucial to advance technologies based on circularly polarized luminescence, enantioselective sensing, or unique optical signatures in anti-counterfeiting. The progress in the field is hampered by the lack of structure–property relationships that would help designing new chiral molecules. Here, we address this challenge by synthesis and investigation of two chiral macrocycles that integrate in their structure a pseudo-meta [2.2]paracyclophane with planar chirality and a highly fluorescent benzothiadiazole. Both compounds display remarkably red-shifted fluorescence with high quantum yields and large Stokes shifts. They differ in the extent of p-electron conjugation that allowed, for the first time, systematic examination of the effect of exciton delocalization on the absorption and luminescence of circularly polarized light. By a combination of steady-state spectroscopy and quantum chemical calculations, we constructed a unique structure–property relationship offering critical insights that will aid and abet the development of robust design guidelines for materials with strong electronic circular dichroism or circularly polarized luminescence of exceptional brightness.