Arylazoindazole Photoswitches: Facile Synthesis and Functionalization via S_NAr Substitution

A straightforward synthetic route to arylazoindazoles via nucleophilic aromatic substitution is presented. Upon deprotonation of the NH group, a C₆F₅-substituted formazan undergoes facile cyclization as a result of intermolecular nucleophilic substitution (S_NAr). This new class of azo photoswitches containing an indazole five-membered heterocycle shows photochemical isomerization with high fatigue resistance. In addition, the Z-isomers have long thermal half-lives in the dark of up to several days at room temperature. The fluorinated indazole group offers a handle for further functionalization and tuning of its properties, as it is shown to be susceptible to a subsequent, highly selective nucleophilic displacement reaction.