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 pi-pi* 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.