Intense Circularly Polarized Luminescence Induced by Chiral Supramolecular Assembly: The Importance of Intermolecular Electronic Coupling

Herein we report on circularly polarized luminescence (CPL) emission originating from supramolecular chirality of organic microcrystals with a | g lum | value up to 0.11. The microcrystals were prepared from highly emissive difluoroboron β‐diketonate (BF 2 dbk) dyes R ‐ 1 or S ‐ 1 with chiral binaphthol (BINOL) skeletons. R ‐ 1 and S ‐ 1 exhibit undetectable CPL signals in solution but manifest intense CPL emission in their chiral microcrystals. The chiral superstructures induced by BINOL skeletons were confirmed by single‐crystal XRD analysis. Spectral analysis and theoretical calculations indicate that intermolecular electronic coupling, mediated by the asymmetric stacking in the chiral superstructures, effectively alters excited‐state electronic structures and facilitates electron transitions perpendicular to BF 2 bdk planes. The coupling increases cos θ μ , m from 0.05 (monomer) to 0.86 (tetramer) and triggers intense optical activity of BF 2 bdk. The results demonstrate that optical activity of chromophores within assemblies can be regulated by both orientation and extent of intermolecular electronic couplings.