Surface Tension Manipulation with Visible Light through Sensitized Disequilibration of Photoswitchable Amphiphiles.

Abstract

Azoarene isomerization lies at the heart of numerous applications from catalysis or energy storage to photopharmacology. While efficient switching between their E and Z isomers predominantly relies on UV light, a recent study by Klajn and co-workers introduced visible light sensitization of E azoarenes and subsequent isomerization as a tool coined disequilibration by sensitization under confinement (DESC) to obtain high yields of the Z isomer. This host-guest approach is, however, still constrained to minimally substituted azoarenes with limited applicability in advanced molecular systems. Herein, we expand DESC for the assembly of surfactants at the air-water interface. Leveraging our expertise with photoswitchable amphiphiles, we induce substantial alterations of water's surface tension through reversible arylazopyrazole isomerization. After studying the binding of charged surfactants to the host, we find that the surface activity differences upon visible light irradiation for both isomers are comparable to those obtained by UV light excitation. The method is demonstrated on a large concentration range and can be activated using green or red light, depending on the sensitizer chosen. The straightforward implementation of photoswitch sensitization in a complex molecular network showcases how DESC enables the improvement of existing systems and the development of novel applications driven by visible light.