The photoswitching behaviors of heteroaryl azos and azobenzenes have attracted considerable interest due to their applications from material science to pharmacology. However, the use of UV light limits their application, especially in biomedicine and photopharmacology. In this work, using several aromaticity descriptors, including anisotropy of the induced current density analysis and nucleus-independent chemical shifts, we systematically investigate the relationship between anti-aromaticity and the absorption of a series of heterocyclic azos. We have demonstrated that the antiaromatic heterocycles substituted with diazenes enable the significant red shifts of the n → π* and π → π* transition bands of E and Z isomers via density functional theory calculations. Moreover, introducing substituents into heterocycles could further tune the absorption. Finally, the λmax of the first transition bands of the E (ca. 1026 nm) and Z isomers (ca. 1167 nm) of azos is achieved in the near-infrared region.

https://doi.org/10.1021/acs.joc.3c00010