Insights into the Structural Modification of Selenium-Doped Derivatives with Narrowband Emissions: A Theory Study.

The research on boron/nitrogen (B/N)-based multiresonance thermally activated delayed fluorescence (MR-TADF) emitters has been a prominent topic due to their narrowband emission and high luminous efficiency. However, devices derived from the common types of narrowband TADF materials often experience an efficiency roll-off, which could be ascribed to their relatively slow triplet-singlet exciton interconversion. Since inserting the heavy Se atom into the B/N scheme has been a proven strategy to address the abovementioned issues, herein, extensive density functional theory (DFT) and time-dependent DFT (TD-DFT) simulations have been employed to explore the effects of the structural modification on a series of structurally modified selenium-doped derivatives. Furthermore, the two-layered ONIOM (QM/MM) model has been employed to study the pressure effects on the crystal structure and photophysical properties of the pristine CzBSe. The theoretical results found that the introduced tert-butyl units in Cz-BSeN could result in a shorter charge transfer distance and smaller reorganization energy than the parent CzBSe. In contrast to directly incorporating the