Mechanochemical Activation of Polymer-Embedded Photoluminescent Benzoxazole Moieties

Despite an increasing number of studies that have investigated mechanochemical effects in polymers, the number of polymers whose fluorescence characteristics change upon exposure to mechanical stress is still limited. We here report the investigation of a mechanofluorophore based on an aliphatic ester of 2-(2′-hydroxyphenyl)­benzoxazole. The free benzoxazole displays green photoluminescence, which is associated with an excited state intramolecular proton transfer (ESIPT) process, whereas aliphatic esters of this compound emit blue light. When poly­(methyl acrylate) containing an esterified benzoxazole mechanophore at the center of each chain molecule was exposed to ultrasound, a significant reduction of the molecular weight and pronounced changes of the photoluminescence emission and UV–vis absorption spectra were observed. The optical changes and the fact that the time-traces for molecular weight decrease and formation of the ESIPT capable species mirror each other indicate that the mechanophore is preferentially cleaved upon sonication and that such cleavage restores the 2-(2′-hydroxyphenyl)­benzoxazole motif. The concept of mechanical activation of ester-protected ESIPT dyes, and more broadly of other hydroxyl group carrying fluorophores that change their emission properties upon ester formation and cleavage, should be general and allow access to a range of other mechanofluorophores.