Tuning of the Optical Properties of Cis ‐ and Trans ‐Bis‐Tetrazo1,2‐bindazoles Guided by Predictive DFT: An Isomer Story

ABSTRACT We report the synthesis and structure‐property relationships of a new family of nitrogen‐rich polyaromatic derivatives, namely cis ‐ and trans ‐tetrazo1,2‐ b indazoles. Through density functional theory (DFT)‐guided molecular engineering, substituents were introduced at selected positions on the polyaromatic scaffold via a modular strategy. The spectroscopic (absorption and emission) and redox (cyclic voltammetry) properties of these derivatives, though occasionally counterintuitive, were accurately predicted by DFT calculations and rationalized through molecular orbital interactions. Depending on the isomer ( cis / trans ), the nature of the substituents and their position, we achieved either intense luminescence in the visible range or near infrared (NIR) absorption up to 1050 nm, while maintaining an excellent electron affinity. This work highlights the versatility of the tetrazo1,2‐ b indazole scaffold and its potential for precise fine‐tuning of the electronic properties of advanced functional materials.