Stoichiometric and Chiral Stacking Tailoring of Dibenzocarbazole Analog–TCNB Charge‐Transfer Cocrystals via Supramolecular Assembly for Variable Optical Behaviors

Abstract In this paper, three new donor–acceptor complex forms (zBC) containing a helical‐shape dibenzocarbazole analog (DBCz) as the electron donor and 1,2,4,5‐tetracyanobenzene (TCNB) as the electron acceptor via a simple solution‐processing strategy are reported. The beginning components self‐assembled into supramolecular frameworks with glamorous alignment modes and different molar ratios: ≈1:1 P or M‐enantiomer for α‐cocrystal, alternated P/M‐column stacking in mesmeric 2:3 β‐cocrystal, and segregated stacking of γ‐cocrystal. As a result, α‐cocrystal exhibits bright solid‐state red fluorescent, β‐cocrystal shows significant optical waveguide behavior with a low optical loss coefficient of ≈0.018 dB µm −1 , and no visual light emission is observed for γ‐cocrystal under ultraviolet radiation. Interestingly, the α‐zBC crystal is not only emissive but also chiroptically active with dissymmetry factor ( g lum ) of 0.004. This study on chiral stacking tailoring paves a way for functional design of organic charge‐transfer complex toward application in high‐performance organic optoelectronics.