Azoheteroarene and Diazocine Molecular Photoswitches: Self‐Assembly, Responsive Materials and Photopharmacology

Abstract Aromatic units tethered with an azo (−N=N−) functionality comprise a unique class of compounds, known as molecular photoswitches, exhibiting a reversible transformation between their E ‐ and Z ‐isomers in response to photo‐irradiation. Photoswitches have been explored extensively in the recent past to prepare dynamic self‐assembled materials, optoelectronic devices, responsive biomaterials, and more. Most of such materials involve azobenzenes as the molecular photoswitch and to date, SciFinder lists more than 7000 articles and 1000 patents. Subsequently, a great deal of effort has been invested to improve the photo‐isomerization efficiency and related mesoscopic properties of azobenzenes. Recently, azoheteroarenes and cyclic azobenzenes, such as arylazopyrazoles, arylazoisoxazoles, arylazopyridines, and diazocines, have emerged as second generation molecular photoswitches beyond conventional azobenzenes. These photoswitches offer distinct photoswitching behavior and responsive properties which make them highly promising candidates for multifaceted applications ranging from photoresponsive materials to photopharmacophores. In this minireview, we introduce the structural refinement and photoresponsive properties of azoheteroarenes and diazocines and summarize the state‐of‐the‐art on utilizing these photoswitches as responsive building blocks in supramolecular assembly, material science and photopharmacology, highlighting their versatile photochemical behavior, enhanced functionality, and latest applications.