A Dual-Pathway Responsive Mechanophore for Intelligent Luminescent Polymer Materials

Abstract

Mechanoluminescent units, when integrated into polymer matrices, undergo structural transformations in response to mechanical force, resulting in changes in fluorescence. This phenomenon holds considerable promise for the development of stress-sensing materials. Despite the high demand for robust, tunable mechanoluminescent mechanophores for force assessment and smart force-responsive materials, strategies for their design and synthesis remain underdeveloped. In an attempt to address this challenge, we have introduced a novel dual-pathway responsive mechanophore, bis(2-(2-( tert -butyldimethylsilanyloxy)benzylidene)amino)aryl disulfides ( SSTBS ), which, when incorporated into polymer chains, exhibits fluorescence upon the combined application of force and chemical stimulus, irrespective of their sequence. This property is facilitated by the disulfide bond’s sensitivity to mechanical force and the fluoride anion-induced desilylation and deprotonation. Notably, the force-responsive threshold of the SSTBS mechanophore can be finely tuned by TBAF treatment, as supported by both experimental and computational studies, providing a simple, yet effective means, to regulate polymer force responsiveness on demand. We believe that the strategy developed in this investigation will shed light on the design of mechanophores for the fabrication of intelligent luminescent polymer materials and advance the development of smart force-reporting systems.