Cascade Fluorescence Modulation in Photochromic Microcapsules

Certain derivatives of terarylene are able to undergo a highly efficient oxidative cycloreversion cascade effect, a ring opening reaction with quantum yields above unity, resulting in a colored-to-colorless transition in solution. In the presence of chloroform, high-energy UV and X-rays can trigger this phenomenon, potentially acting as a visual detection system for ionizing radiation. However, chloroform is sensitive to different irradiation wavelengths without distinction, making it difficult to adapt to a reusable device. Chlorobenzene was chosen as an alternative halogenated solvent, as it offers wavelength selectivity between photocyclization and cascade effect cycloreversion. Nile Red was also incorporated into the system with the aim of improving the sensitivity of the visual detection via fluorescence photoswitching. Finally, microencapsulation of both terarylene and Nile Red was targeted to obtain both the cascade effect and photoswitching in a single system. In microcapsules made from a Pickering emulsion, this terarylene−Nile Red system showed high fatigue resistance to repeated photocyclization and cycloreversion irradiation, giving access to repeated ON/OFF fluorescence photoswitching. The cascade effect was also successfully demonstrated along with fluorescence recovery, showing the versatility of the two phenomena in different media.