A two-step MM and QM/MM approach to model AIEE of aryloxy benzothiadiazole derivatives for optoelectronic applications.

Aryloxy-benzothiadiazole (ArO-Btz) derivatives show aggregation-induced enhanced emission (AIEE) in the solid-state and are promising candidates for optoelectronic applications. However, understanding the AIEE is a challenging task and is necessary for the rational molecular design of emitters. Therefore, in the present study, electron acceptors (-F, -CN, -NO2, and -COOH) on the benzothiadiazole ring have been screened for emission in solution and aggregated phases. Herein, we report QM (DFT/TDDFT) and ONIOM (QM/MM) studies on the four ArO-Btz derivatives in comparison with the parent molecule with typical characteristics of AIEE, optoelectronic and non-linear optical properties. Starting from the optimized crystal structure of the parent compound, the structures of the designed clusters have been pre-optimized with MM and then with QM/MM to explore their absorption and emission in the solid phase. The results indicate that in the aggregated phase, the surrounding environment reduces intra-molecular rotations and molecular motion that lead to enhanced emission. Natural bond orbital (NBO) analyses reveal that the ground state structure is stabilized from electron delocalization and operative push-pull effects. Interestingly, nitro-benzothiadiazole exhibits prominent AIEE phenomena, with an emission wavelength beyond 700 nm in solution and in the cluster, reinforced by the magnification of its oscillatory strength by 100 times when aggregated. This dinitro-aryloxy-benzothiadiazole derivative is proposed as a near-infrared emitter for dye-sensitized solar cell, optoelectronic, and non-linear optical applications.