Modulating excited state properties of thermally activated delayed fluorescence molecules by hybrid long-range and short-range charge transfer strategy

Balancing the rapid radiative decay process and the fast reverse intersystem crossing (RISC) process of thermally activated delayed fluorescence (TADF) molecule remains a great challenge and efficient molecular design stra-tegies are highly desired. Herein, from a theoretical perspective, excited state properties of three reported TADF molecules (1TICz, 1BOICz and 2BOICz) are investigated based on density functional theory (DFT) and time -dependent density functional theory (TD-DFT) calculations coupled with the thermal vibration correlation function (TVCF) method. Results indicate that, by introducing the multi-resonance (MR) acceptor, 1BOICz possesses hybrid long-range and short-range charge transfer features, balanced small energy gap (Delta EST) and large oscillator strength (f) is obtained. Furthermore, by incorporating double equivalent MR acceptors in 2BOICz, largely enhanced f with slightly changed Delta EST is achieved, inner mechanism for remarkable photophysical property is illustrated. Keep this strategy, seven new TADF molecules (2pDBA-bICz-1, 2pDBA-bICz-2, 2OSBA-bICz, 2DQAO-bICz, 2QAO-bICz, 2SQAO-bICz and 2OQAO-bICz) are theoretically designed, detailed physical parameters are analyzed and excited state energy consumption process is studied. Strong electrophilicity on acceptor is determined and the strength of nucleophilic sites on the bridge-phenyl of 2DQAO-bICz, 2QAO-bICz, 2SQAO-bICz and 2OQAO-bICz is increased, this promotes the short-range charge transfer property. In addition, the excitation processes for all studied molecules are dominated by long-range charge transfer from donor to acceptors, and supplemented by the short-range charge transfer on the bridge-phenyl with MR effect. Compromise energy gap and oscillator strength as well as large spin orbit coupling (SOC) constant are obtained for designed molecules. Thus, by regulating the long-range and short-range charge transfer ratios, excited state properties are successfully modulated and new efficient TADF molecules are proposed. Our research aims to provide deeper insight into long-range and short-range charge transfer features in balancing small Delta EST and large f, which could facilitate the development of novel efficient TADF molecules.