Aryl Azocyclopropeniums: Minimalist, Visible-Light Photoswitches.

We report convenient syntheses of aryl azocyclopropeniums and a study of their photochemical properties. Incorporation of the smallest arene leads to pronounced redshift of the π-π* absorbance band, compared to azobenzenes. Photoisomerization under purple or green light irradiation affords Z- or E-isomers in ratios up to 94% Z or 90% E, and the switches proved stable over multiple irradiation cycles. Thermal half-lives of metastable Z-isomers range from minutes to hours in acetonitrile and water. These properties together with the concise, versatile syntheses render aryl azocyclopropeniums exciting additions to the tool kit of readily available molecular photoswitches for wide ranging applications.

Azoacetylenes for the Synthesis of Arylazotriazole Photoswitches.

We report a modular approach toward novel arylazotriazole photoswitches and their photophysical characterization. Addition of lithiated TIPS-acetylene to aryldiazonium tetrafluoroborate salts gives a wide range of azoacetylenes, constituting an underexplored class of stable intermediates. In situ desilylation transiently leads to terminal arylazoacetylenes that undergo copper-catalyzed cycloadditions (CuAAC) with a diverse collection of organoazides. These include complex molecules derived from natural products or drugs, such as colchicine, taxol, tamiflu, and arachidonic acid. The arylazotriazoles display near-quantitative photoisomerization and long thermal Z-half-lives. Using the method, we introduce for the first time the design and synthesis of a diacetylene platform. It permits implementation of consecutive and diversity-oriented approaches linking two different conjugants to independently addressable acetylenes within a common photoswitchable azotriazole. This is showcased in the synthesis of several photoswitchable conjugates, with potential applications as photoPROTACs and biotin conjugates.