Geometry-Induced Oligomerization of Fluorine-Substituted Phenylazothiazole Photoswitches

Photoswitches are molecules that can absorb light of specific wavelengths and undergo a reversible transformation between their trans and cis isomeric forms. In phenylazo photoswitches, it is common for the less stable cis (Z) isomer to convert back to the more stable trans (E) isomer either through photochemical or thermal means. In this research, we designed new derivatives of phenylazothiazole (PAT) photoswitches, PAT-Fn, which feature fluorine substituents on their phenyl component. These derivatives can reversibly isomerize under visible light exposure with the enrichment of E and Z isomers at photostationary state (PSS). Surprisingly, we observed an unconventional phenomenon when these PAT-Fn (n >= 2) photoswitches were in their cis isomeric state in the absence of light. Instead of the anticipated transformation from cis to trans isomer, these compounds converted to an oligomeric compound. Our detailed experimental investigation and theoretical calculations, indicated the crucial role of fluorine substituents and the distinctive geometric arrangement of the cis isomer in driving the unexpected oligomerization process originating from the cis isomeric state. Geometry of the molecules plays important role in various chemical and physical properties. Photoswitches are molecules that undergo structural changes from a stable isomer (trans) to a geometrically different less stable structure (cis) by light irradiation through isomerization. Here an unconventional phenomenon is reported where a cis isomer undergo oligomerization in the absence of light, however, behave as typical photoswitches in the presence of light irradiation. image