Mechanofluorochromic polymers, which can indicate damage or excessive stress in highly polarized environments with a clearly perceptible optical signal, are potentially useful in a variety of exciting applications. However, most reported fluorochromic mechanophores exhibit poor color contrast and fluorescence penetration, or are irreversible in polarized phase after mechanical activation. Here, this challenge is tackled by designing and engineering a novel near‐infrared (NIR) emissive, rhodanmin derived mechanophore (Rh‐Co) in a kind of hydrogel composites. The ring‐opened Rh‐Co is unique in high molar extinction coefficient and bright NIR emission with such optical transition under force directly corresponding to covalent bond scission and reversibly switchable in an aqueous environment. The hydrogel composites thus can sensitively change their color from yellow to green and emit highly penetrated NIR fluorescence when different types of forces (tension, compression, and friction force) are applied, highlighting the potential applications of Rh‐Co in biocompatible environments as a “force meter.”

A Chromic and Near‐Infrared Emissive Mechanophore Serving as a Versatile Force Meter in Micelle–Hydrogel Composites

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.

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

Large steric hindrance amide modified benzothiadiazole: High contrast mechanochromic luminescence and volatile acid vapor response

Mechanochromophores based on conformational changes of donor-acceptor-donor (DAD) springs allow sensing of forces acting on polymer chains by monotonic changes of absorbance or photoluminescence (PL) wavelength. Here, we identify a series of thiophene (D)-flanked quinoxalines (A) as molecular torsional springs for force sensing in bulk polymers at room temperature. The mode of DAD linkage to the polymer matrix and linker rigidity are key parameters that influence the efficacy of force transduction to the DAD spring and thus mechanochromic response, as probed by in situ PL spectroscopy of bulk films during stress-strain experiments. The largest shift of the PL maximum, and thus the highest sensitivity, is obtained from an ansa-DAD spring exhibiting bridged D units and a stiff A linker. Using detailed spectroscopy and density functional theory calculations, we reveal conformer redistribution in the form of a thiophene ring flip as the major part of the overall mechanochromic response. At forces as low as 27 pN at early stages of deformation, the ring flip precedes mechanically induced planarization of the ansa-DAD spring, the latter process producing a PL shift of 21 nm nN-1. Within the stress-strain diagram, the thiophene ring flip and DAD planarization are thus two separated processes that also cause irreversible and reversible mechanochromic responses, respectively, upon sample failure. As the thiophene ring flip requires much smaller forces than planarization of the DAD spring, such micromechanical motion gives access to sensing of tiny forces and expands both sensitivity and the force range of conformational mechanochromophores.

Conformer Ring Flip Enhances Mechanochromic Performance of ansa-Donor-Acceptor-Donor Mechanochromic Torsional Springs.

Abstract Force-reversible C-N bonds, resulting from the click chemistry reaction between triazolinedione (TAD) and indole derivatives, offer exciting opportunities for molecular-level engineering to design materials that respond to mechanical loads. Here, we displayed that TAD-indole adducts, acting as crosslink points in dry-state covalently crosslinked polymers, enable materials to display reversible stress-responsiveness in real time already at ambient temperature. Whereas the exergonic TAD-indole reaction results in the formation of bench-stable adducts, they were shown to dissociate at ambient temperature when embedded in a polymer network and subjected to a stretching force to recover the original products. Moreover, the nascent TAD moiety can spontaneously and immediately be recombined after dissociation with an indole reaction partners at ambient temperature, thus allowing for the adjustment of the polymer segment conformation and the maintenance of the network integrity by force-reversible behaviors. Overall, our strategy represents a general method to create toughened covalently crosslinked polymer materials with simultaneous enhancement of mechanical strength and ductility, which is quite challenging to achieve by conventional chemical methods. 

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Force–reversible chemical reaction at ambient temperature for designing toughened dynamic covalent polymer networks

A near-infrared (NIR) mechanophore was developed and incorporated into a poly(methyl acrylate) chain to showcase the first force-induced NIR chromism in polymeric materials. This mechanophore, based on benzo[1,3]oxazine (OX) fused with a heptamethine cyanine moiety, exhibited NIR mechanochromism in solution, thin-film, and bulk states. The mechanochemical activity was validated using UV-vis-NIR absorption/fluorescence spectroscopies, gel permeation chromatography (GPC), NMR, and DFT simulations. Our work demonstrates that NIR mechanochromic polymers have considerable potential in mechanical force sensing, damage detection, bioimaging, and biomechanics.

Nnamdi M. Ofodum

Papers

Force-Induced Near-Infrared Chromism of Mechanophore-Linked Polymers.