Thermally Activated Delayed Fluorescence in B,N-Substituted Tetracene Derivatives: A Theoretical Pathway to Enhanced OLED Materials.

Polycyclic aromatic hydrocarbons (PAHs) exhibit intriguing characteristics that position them as promising candidates for advancements in organic semiconductor technologies. Notably, tetracene finds substantial utility in Electronics due to its application in organic light-emitting diodes (OLEDs) and organic field-effect transistors (OFETs). The strategic introduction of an isoelectronic boron-nitrogen (B,N) pair to replace a carbon-carbon pair in acenes introduces changes in the electronic structure, allowing for the controlled modulation of diradical characteristics. Consequently, this B,N substitution enables precise adjustments in chemical, optical, and electronic attributes. In this work, we undertook a systematic exploration of thermally activated delayed fluorescence (TADF) phenomena within a set of 77 B,N-substituted derivatives of tetracene. The primary objective was to identify and select prospective molecules for the fabrication of OLEDs. Employing multiconfigurational methods of computational quantum chemistry, we conducted an extensive investigation to unravel the potential candidates. As a result, we identified molecules that might exhibit the sought-after TADF behavior. Descriptors such as excitation energies, harmonic oscillator model of aromaticity (HOMA) and fractional occupation number weighted density (FOD) were assessed and indicated five candidates with stability comparable to that of pristine tetracene. This research not only contributes to a deeper understanding of the influence of B,N substitution on acene derivatives but also opens doors for the development of organic electronics by harnessing the properties of these selected molecules.