Phys Chem Chem Phys. 2022 Nov 1. doi: 10.1039/d2cp03948f. Online ahead of print.
The emergence and development of radical luminescent materials is a huge breakthrough toward high-performance organic light-emitting diodes (OLEDs) without spin-statistical limits. Herein, we design a series of radicals based on tris(2,4,6-trichlorophenyl)methyl (TTM) by combining skeleton-engineering and periphery-engineering strategies, and present some insights into how different chemical modifications can modulate the chemical stability and luminescence properties of radicals by quantum chemistry methods. Firstly, through the analysis of the geometric structure changes from the lowest doublet excited state (D1) to the doublet ground state (D0) states, the emission energy differences between the BN orientation isomers are explained, and it is revealed that the radical with a smaller dihedral angle difference can more effectively suppress the geometric relaxation of the excited states and bring a higher emission energy. Meanwhile, a comparison of the excited state properties in different radicals can help us to disclose the luminescence behavior, that is, the enhanced luminescent intensity of the radical is caused by the intensity borrowing between the charge transfer (CT) state and the dark locally excited (LE) state. In addition, an efficient algorithm for calculating the internal conversion rate (kIC) is introduced and implemented, and the differences in kIC values between designed radicals are explained. More specifically, the delocalization of hole and electron wave functions can reduce nonadiabatic coupling matrix elements (NACMEs), thus hindering the non-radiative decay process. Finally, the double-regulation of chemical stability and luminescence properties was realized through the synergistic effect of skeleton-engineering and periphery-engineering, and to screen the excellent doublet emitter (BN-41-MPTTM) theoretically.