Photochemistry Driven by Excited‐State Aromaticity Gain or Antiaromaticity Relief

• Published in: Chemistry : a European journal 2023-04, Vol.29 (19), p.e202203748-n/a
• Main Authors: Yan, Jiajie, Slanina, Tomáš, Bergman, Joakim, Ottosson, Henrik
• Format: Article
• Language: English
• Subjects: antiaromaticity; Aromaticity; Baird's rule; Chemistry; Electrons; Excitation; excited states; Mathematical analysis; Photochemistry; photoreactivity; Physicochemical properties; Potential energy; Quantum chemistry
• ISSN: 0947-6539; 1521-3765; 1521-3765
• DOI: 10.1002/chem.202203748

Gain of aromaticity or relief of antiaromaticity along a reaction path are important factors to consider in mechanism studies. Analysis of such changes along potential energy surfaces has historically focused on reactions in the electronic ground state (S0), but can also be used for excited states. In the lowest ππ* states, the electron counts for aromaticity and antiaromaticity follow Baird's rule where 4n π‐electrons indicate aromaticity and 4n+2 π‐electrons antiaromaticity. Yet, there are also cases where Hückel's rule plays a role in the excited state. The electron count reversals of Baird's rule compared to Hückel's rule explain many altered physicochemical properties upon excitation of (hetero)annulene derivatives. Here we illustrate how the gain of excited‐state aromaticity (ESA) and relief of excited‐state antiaromaticity (ESAA) have an impact on photoreactivity and photostability. Emphasis is placed on recent findings supported by the results of quantum chemical calculations, and photoreactions in a wide variety of areas are covered. Aromatic and antiaromatic molecules are light‐switched yin‐yang entities flipping aromaticity into antiaromaticity, and vice versa, upon excitation to the lowest ππ* state. This key feature has an impact on the photoreactivity and photostability of molecules in a variety of areas, and can serve as a compass for excursions in electronically excited states.