Diaryl-hemiindigos as visible light, pH, and heat responsive four-state switches and application in photochromic transparent polymers

Abstract

Abstract Photoswitches are indispensable tools for responsive chemical nanosystems and are used today in almost all areas of the natural sciences. Hemiindigo (HI) derivatives have recently been introduced as potent photoswitches, but their full applicability has been hampered by the limited possibilities of their functionalization and structural modification. Here we report on a short and easy to diversify synthesis yielding diaryl-HIs bearing one additional aromatic residue at the central double bond. The resulting chromophores offer an advantageous property profile combining red-light responsiveness, high thermal bistability, strong isomer accumulations in both switching directions, strong photochromism, tunable acid responsiveness, and acid gating. With this progress, a broader structural realm becomes accessible for HI photoswitches, which can now be synthetically tailored for advanced future applications, e.g., in research on molecular machines and switches, in studies of photoisomerization mechanisms, or in the generation of smart and addressable materials. To showcase the potential of these distinct light-responsive molecular tools, we demonstrate four-state switching, chemical fueling, and reversible inscription into transparent polymers using green and red light as well as acid/base stimuli, in addition to a comprehensive photochemical study of all compounds.