ABSTRACT
Diarylethenes belong to the most eminent photoswitches and have been studied for many decades. They are found in virtually every field of application and have become highly valuable molecular tools for instilling light-responsiveness into materials, catalysts, biological systems, or pharmacology. In this work, we present a novel and distinct type of pyrimidine-based aza-diarylethene, which undergoes a highly unusual zwitterion-forming photoreaction. During this fully reversible process, a CN double bond is established under concomitant aromatization and thiophene-ring opening. The metastable zwitterion thus possesses a positively charged extended aromatic structure and an independent conjugated thiolate function. It can further photoisomerize between a more stable Z and a less stable E isomer, resulting in effective four-state photoswitching. Unusual for diarylethenes, the metastable isomers show negative solvatochromism and red-shifted absorption in apolar solvents. With this behavior, aza-diarylethenes effectively bridge the properties of merocyanines and diarylethenes. Thermal stability of the zwitterions can be modulated from very labile to highly stable behavior in response to pH, again in a fully reversible manner. Pyrimidine-based aza-diarylethene thus establishes a unique photoreaction mechanism for diarylethenes, allowing control of charge separation, thermal stability, and color generation in a different way than hitherto possible.
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.
