Exploring the Theoretical Foundations of Thermally Activated Delayed Fluorescence (TADF) Emission: A Comprehensive TD-DFT Study on Phenothiazine Systems

This study conducts a thorough theoretical investigation of Thermally Activated Delayed Fluorescence (TADF) in phenothiazine-based systems, examining ten molecular configurations recognized experimentally as TADF-active. Employing Time-Dependent Density Functional Theory (TD-DFT), our analysis spans the investigation of singlet-triplet energy gaps (Delta EST), spin-orbit coupling, and excitation characteristics using Multiwfn. This approach not only validates the adherence to El Sayed's rule across these systems but also provides a detailed understanding of charge transfer dynamics, as visualized through heat maps. A significant aspect of our study is the exploration of different oxidation states of sulfur and site substitutions on phenothiazine. This systematic variation aims to identify additional TADF-active compounds, drawing parallels with properties characterizing other known TADF emitters. Our investigation into Reverse Intersystem Crossing (rISC) rates and the analysis of dihedral angles in relation to Delta EST values offer nuanced insights into the TADF behaviours of these molecules. By integrating rigorous computational analysis with practical implications, we provide a foundational understanding that enhances the design and optimization of phenothiazine-based materials for optoelectronic applications. This work not only advances our theoretical understanding of TADF in phenothiazine derivatives but also serves as a guide for experimentalists and industry professionals in the strategic design of new TADF materials. Exploring Thermally Activated Delayed Fluorescence (TADF) in phenothiazine-based systems, through this study, we analyse ten recognized TADF-active configurations using TD-DFT and Multiwfn. It validates El Sayed ' s rule and visualizes charge transfer dynamics, exploring diverse sulfur oxidation states and phenothiazine substitutions to identify additional TADF-active compounds. Insights into rISC rates and dihedral angles contribute to a comprehensive understanding, guiding phenothiazine material design for experimentalists. image