Cooperative and Geometry-Dependent Mechanochromic Reactivity through Aromatic Fusion of Two Rhodamines in Polymers

Abstract

The unique topological features of Piezo proteins underlie the lever-like cellular mechanotransduction mechanism. This knowledge inspires us to seek topological/geometric control of mechanochromophores with unprecedentedly amplified, synergistic changes in polymers to serve as ideal stress probes. Here, by judicious placement of two spirolactam rings into aminobenzopyranoxanthene, a series of stereo- and regio-isomeric rhodamine-like mechanophores are developed. With two labile bonds closely coupled into one rigidified scaffold, these π-fused bis-mechanophores enable mechanochromic polymers, featuring cooperative bond scission, low rupture force (lower than rhodamine), and geometry-controlled ring-opening reactivity. Sonication, single-molecule force spectroscopy experiments, and density functional theory calculations provide insight into the force-color relationship and rationalize how the difference in reactivity of the four isomeric mechanophores is affected by their molecular geometry and thermodynamic equilibrium. Our strategy based on the aromatic fusion of bis-mechanophore promises a modular approach to isomeric mechanophores for cooperative bond scission. Also, important insights into internal and external factors governing tandem mechanochemical reactions are gained.