Preparation, structure and optical properties of TCNB-based charge-transfer cocrystals

• Three typical types of luminescent organic cocrystals were synthesized by a simple supramolecular assembly strategy. • The cocrystals exhibit interesting optical properties for its charge transfer (CT) interactions. • DFT calculations were used to predict the CT interactions and the binding patterns. Organic charge transfer cocrystals exhibit interesting properties due to their multi-components synergistic and collective effect. Herein, using 1,2,4,5-tetracyanobenzene (TCNB) as electron acceptor, carbazole (CARB), dibenzothiophene (DBZP) and dibenzofuran (DBZF) as electron donors, three charge transfer cocrystals of CARB-TCNB, DBZP-TCNB and DBZF-TCNB were synthesized by solvent evaporation method and solvent-assisted grinding method. These cocrystals were constructed based on the π–π stacking interactions and C H…N hydrogen bonds and confirmed by the SXRD analysis. The stacking modes are consistent with the model that predicted by molecular electrostatic potential analysis (ESP). The IGM and AIM analyses suggested that the π-π stacking and C H…N hydrogen bonds are weak in nature. The purity and homogeneity of cocrystals and grinding products were verified by PXRD analysis. In addition, the IR, UV–vis absorption and luminescent properties were investigated, and the cocrystals and grinding products exhibited different behaviors from that of their precures. In short, this work not only reports the CT complexes synthesized by liquid- and solid- strategies, but also provides an in-depth understanding of the spectral changes caused by the CT interactions.