Fluorescent Dye-Based Chiral Crystalline Organic Salt Networks for Circularly Polarized Luminescence.

Abstract

A facile and general strategy is developed herein for the construction of circularly polarized luminescence (CPL) materials with simultaneously high fluorescence quantum efficiency (Φ) and large luminescence dissymmetry factor (glum). The self-assembly of fluorescent dye, disodium 4,4'-bis(2-sulfonatostyryl)biphenyl (CBS), with chiral diamines such as (R,R)/(S,S)-1,2-diaminocyclohexane (R/S-DACH) and R/S-1,2-diaminopropane (R/S-DAP), produces four chiral crystalline organic salt networks (COSNs). These as-synthesized organic salts emit strong blue-color CPL upon excitation, with both high Φ and glum values of up to 79% and 0.022. The well-defined molecular structures and arrangements of CBS are directly observed through single crystal X-ray analysis, offering crucial information regarding the origins of high-efficiency CPL performance. The chirality of amine is effectively transferred to CBS and further amplified to the supramolecular structure by multiple hydrogen bonding and π-π stacking interactions, giving rise to the large glum factors; meanwhile, the fixation and the ordered arrangement of CBS by these multiple interactions empower efficient suppression of molecular motions, facilitating strong fluorescence. This work can inspire the assembly of CPL organic materials with high Φ and glum via charge-assisted hydrogen bonds between fluorescent dyes and chiral inducers. It also offers important insight into the structural origins of supramolecular chirality and CPL performance.