Simultaneous Detection of Circularly Polarized Luminescence and Raman Optical Activity in an Organic Molecular Lemniscate

Angew Chem Int Ed Engl. 2022 Aug 22;61(34):e202206976. doi: 10.1002/anie.202206976. Epub 2022 Jul 14.

Abstract

Circularly polarized luminescence (CPL) and Raman optical activity (ROA) were observed in a single spectroscopic experiment for a purely organic molecule, an event that had so far been limited to lanthanide-based complexes. The present observation was achieved for [16]cycloparaphenylene lemniscate, a double macrocycle constrained by a rigid 9,9'-bicarbazole subunit, which introduces a chirality source and allows the molecule to be resolved into two configurationally stable enantiomers. Distortion of oligophenylene loops in this lemniscular structure produces a large magnetic transition dipole moment while maintaining the π-conjugation-induced enhancement of the Raman signal, causing the appearance of the CPL/ROA couple. A two-photon mechanism is proposed to explain the population of the lowest-energy excited electronic state prior to the simultaneous emission-scattering event.

Keywords: Circularly Polarized Luminescence; Cycloparaphenylene; Lemniscular; Magnetic Moments; Raman Optical Activity.