Bhattacharjee Indranil, Wang Liangxuan, Gonzalez-Sanchis Nerea, Milián-Medina Begoña, Ballesteros Rafael, Wannemacher Reinhold, Ballesteros-Garrido Rafael, Gierschner Johannes
Madrid Institute for Advanced Studies, IMDEA Nanoscience, C/Faraday 9, Ciudad Universitaria de Cantoblanco, Madrid 28049, Spain.
Institute of Physical and Theoretical Chemistry, Eberhard Karls University Tübingen, Tübingen 72076, Germany.
J Phys Chem A. 2025 May 22;129(20):4471-4479. doi: 10.1021/acs.jpca.5c01474. Epub 2025 May 12.
The quest for nitrogen-doped (N-doped) polycyclic aromatic hydrocarbons (PAHs) requires well-defined prototype systems to understand the relationship between the structure and the resulting photophysical and photochemical properties. To this end, a novel, simple, and small compound, 1,6-diazapyrene, was synthesized. In-depth analysis, employing optical spectroscopy and (time-dependent) density functional theory, (TD-)DFT, elucidates the optical excitations on the basis of MO symmetry, energy, and topology considerations; the study further unveils the photophysical and photochemical deactivation kinetics after photoexcitation, revealing extreme changes against pyrene as well as against the well-known 2,7-diazapyrene isomer. The high sensitivity of the aza-substitution position to generate such changes is considered as highly relevant for the targeted design of N-doped PAHs in general.
对氮掺杂（N掺杂）多环芳烃（PAHs）的探索需要明确的原型系统，以了解结构与所得光物理和光化学性质之间的关系。为此，合成了一种新型、简单的小化合物1,6-二氮芘。通过光谱学和（含时）密度泛函理论（TD-DFT）进行的深入分析，基于分子轨道对称性、能量和拓扑考虑阐明了光学激发；该研究进一步揭示了光激发后的光物理和光化学失活动力学，揭示了与芘以及著名的2,7-二氮芘异构体相比的极端变化。一般而言，氮杂取代位置对产生此类变化的高敏感性被认为与N掺杂PAHs的靶向设计高度相关。
