Activation of a Copper Biscarbene Mechano-Catalyst Using Single-Molecule Force Spectroscopy Supported by Quantum Chemical Calculations

Single-molecule force spectroscopy allows investigation of the effect of mechanical force on individual bonds. By determining the forces necessary to sufficiently activate bonds to trigger dissociation, it is possible to predict the behavior of mechanophores. The force necessary to activate a copper biscarbene mechano-catalyst intended for self-healing materials was measured. By using a safety line bypassing the mechanophore, it was possible to pinpoint the dissociation of the investigated bond and determine rupture forces to range from 1.6 to 2.6 nN at room temperature in dimethyl sulfoxide. The average length-increase upon rupture of the Cu−C bond, due to the stretching of the safety line, agrees with quantum chemical calculations, but the values exhibit an unusual scattering. This scattering was assigned to the conformational flexibility of the mechanophore, which includes formation of a threaded structure and recoiling of the safety line.     

Structure-mechanochemical activity relationships for cyclobutane mechanophores

Ultrasound activation of mechanophores embedded in polymer backbones has been extensively studied of late as a method for realizing chemical reactions using force. To date, however, there have been few attempts at systematically investigating the effects of mechanophore structure upon rates of activation by an acoustic field. Herein, we develop a method for comparing the relative reactivities of various cyclobutane mechanophores. Through the synthesis and ultrasonic irradiation of a molecular weight series of poly(methyl acrylate) polymers in which each macromolecule has a single chain-centered mechanophore, we find measurable and statistically significant shifts in molecular weight thresholds for mechanochemical activation that depend on the structure of the mechanophore. We also show that calculations based on the constrained geometries simulate external force method reliably predict the trends in mechanophore reactivity. These straightforward calculations and the experimental methods described herein may be useful in guiding the design and the development of new mechanophores for targeted applications.     

Mechanical Force Induces Ylide-Free Cycloaddition of Nonscissible Aziridines

The application of aziridines as nonvulnerable mechanophores is reported. Upon exposure to a mechanical force, stereochemically pure nonactivated aziridines incorporated into the backbone of a macromolecule do not undergo cis–trans isomerization, thus suggesting retention of the ring structure under force. Nonetheless, aziridines react with a dipolarophile and seem not to obey conventional reaction pathways that involve C−C or C−N bond cleavage prior to the cycloaddition. Our work demonstrates that a nonvulnerable chemical structure can be a mechanophore.     

Mechanical Force Induces Ylide‐Free Cycloaddition of Nonscissible Aziridines

The application of aziridines as nonvulnerable mechanophores is reported. Upon exposure to a mechanical force, stereochemically pure nonactivated aziridines incorporated into the backbone of a macromolecule do not undergo cis–trans isomerization, thus suggesting retention of the ring structure under force. Nonetheless, aziridines react with a dipolarophile and seem not to obey conventional reaction pathways that involve C?C or C?N bond cleavage prior to the cycloaddition. Our work demonstrates that a nonvulnerable chemical structure can be a mechanophore.     

Mechanochemical Release of Fluorophores from a “Flex-activated” Mechanophore

Optical force probes that can release force-dependent and visualized signals with minimal changes in the polymer main chains under mechanical load are highly sought after but currently limited. In this study, we introduce a flex-activated mechanophore (FA) based on the Diels–Alder adduct of anthracene and dimethyl acetylenedicarboxylatea that exhibits turn-on mechanofluorescence. We demonstrate that when FA is incorporated into polymer networks or in its crystalline state, it can release fluorescent anthracenes through a retro-Diels–Alder mechanochemical reaction under compression or hydrostatic high pressure, respectively. The flex-activated mechanism of FA is successfully confirmed. Furthermore, we systematically modulate the force delivered to the mechanophore by varying the crosslinking density of the networks and the applied macroscopic pressures. This modulation leads to incremental increases in mechanophore activation, successive release of anthracenes, and quantitative enhancement of fluorescence intensity. The exceptional potential of FA as a sensitive force probe in different bulk states is highlighted, benefiting from its unique flex-activated mode with highly emissive fluorophore releasing. Overall, this report enriches our understanding of the structures and functions of flex-activated mechanophores and polymeric materials.     

Mechanochemical Cycloreversion of Cyclobutane Observed at the Single Molecule Level

Mechanochemical cycloreversion of cyclobutane is known from ultrasound experiments. It is, however, not clear which forces are required to induce the cycloreversion. In atomic force microscopy (AFM) experiments, on the other hand, it is notoriously difficult to assign the ruptured bond. We have solved this problem through the synthesis of tailored macrocycles, in which the cyclobutane mechanophore is bypassed by an ethylene glycol chain of specific length. This macrocycle is covalently anchored between a glass substrate and an AFM cantilever by polyethylene glycol linkers. Upon mechanical stretching of the macrocycle, cycloreversion occurs, which is identified by a defined length increase of the stretched polymer. The measured length change agrees with the value calculated with the external force explicitly included (EFEI) method. By using two different lengths for the ethylene glycol safety line, the assignment becomes unambiguous. Mechanochemical cycloreversion of cyclobutane is observed at forces above 1.7 nN.     

Comparison of the reactivity of isomeric 2H- and 3H-naphthopyran mechanophores

Naphthopyrans are molecular switches that produce highly colored merocyanine dyes upon photochemical or mechanochemical activation in polymers. The mechanochromic behavior of these molecular force probes enables the straightforward visualization of stress and/or strain in materials. To date, research on the mechanochemistry of naphthopyran has largely focused on the 3H-naphtho[2,1-b]pyran (3H) scaffold, whereas isomeric 2H-naphtho[1,2-b]pyrans (2H) exhibit complementary properties as suggested from their photochemical reactivity. Here we directly compare the reactivity of two isomeric 2H- and 3H-naphthopyran mechanophores in solution-phase ultrasonication experiments and in crosslinked polydimethylsiloxane elastomers subjected to uniaxial tensile deformation. The prototypical 3H-naphthopyran mechanophore produces a yellow merocyanine dye that reverts quickly, while the 2H-naphthopyran mechanophore generates a red merocyanine dye that reverts significantly slower. The trends in absorption and reversion measured in solution are also reflected in solid polymeric materials activated in tension. Building on recent research into substituent effects, this study identifies naphthopyran isomerism as a simple lever for modulating the mechanochromic properties of the naphthopyran mechanophore used in the development of force-responsive polymers.     

Mechanical Reversibility of Strain‐Promoted Azide–Alkyne Cycloaddition Reactions

Mechanophores, that is, molecules that show a defined response to force, are crucial building blocks of mechanoresponsive materials. The possibility of mechanically induced cycloreversion for a series of triazoles formed via strain‐promoted azide–alkyne cycloaddition reactions was investigated by density functional theory calculations, and these triazoles were compared to the 1,4‐ and 1,5‐regioisomers formed in the reaction of an azide with a terminal alkyne. We show that cycloreversion is in principal possible and that the pulling geometry is the most important parameter that determines the probability of cycloreversion. We further compared triazole stability to the mechanical stability of polymers that are frequently used as force transducers in mechanochemical experiments and identified DIBAC (azadibenzylcyclooctyne) as a promising mechanophore for future applications.     

Designing naphthopyran mechanophores with tunable mechanochromic behavior

Mechanochromic molecular force probes conveniently report on stress and strain in polymeric materials through straightforward visual cues. We capitalize on the versatility of the naphthopyran framework to design a series of mechanochromic mechanophores that exhibit highly tunable color and fading kinetics after mechanochemical activation. Structurally diverse naphthopyran crosslinkers are synthesized and covalently incorporated into silicone elastomers, where the mechanochemical ring–opening reactions are achieved under tension to generate the merocyanine dyes. Strategic structural modifications to the naphthopyran mechanophore scaffold produce dramatic differences in the color and thermal electrocyclization behavior of the corresponding merocyanine dyes. The color of the merocyanines varies from orange-yellow to purple upon the introduction of an electron donating pyrrolidine substituent, while the rate of thermal electrocyclization is controlled through electronic and steric factors, enabling access to derivatives that display both fast-fading and persistent coloration after mechanical activation and subsequent stress relaxation. In addition to identifying key structure–property relationships for tuning the behavior of the naphthopyran mechanophore, the modularity of the naphthopyran platform is demonstrated by leveraging blends of structurally distinct mechanophores to create materials with desirable multicolor mechanochromic and complex stimuli-responsive behavior, expanding the scope and accessibility of force-responsive materials for applications such as multimodal sensing.

Structure–activity relationships for strategic substitution of the naphthopyran mechanophore scaffold enable polymeric materials with tunable mechanochromic behavior.     

Carbon Dots Intensified Mechanochemiluminescence from Waterborne Polyurethanes as Tunable Force Sensing Materials

1,2-Dioxetane is a well-known chemiluminescent mechanophore allowing real-time monitoring of polymer chain scission, but usually suffers from fluorescence quenching in polar environments. Herein, a series of mechanochemiluminescent waterborne polyurethanes/carbon dots composites(WPU-CDs) have been synthesized by incorporating fluorescent CDs to promote the energy transfer process in different environments. The resulting bulk WPUs, and in particular, their swollen films filled with a large amount...     

Off-center Mechanophore Activation in Block Copolymers

Block copolymers (BCPs) are used in numerous applications in modern materials science. Yet, like homopolymers, BCPs can undergo covalent bond scission when mechanically stressed (mechanochemistry), which could lead to unexpected consequences in such applications. BCPs’ heterogeneity may affect force transduction, perhaps changing force distribution and localization. To verify this, a gem-dichlorocyclopropane (gDCC) embedded linear chain is prepared and extended with a poly(methyl methacrylate) block. When stressed in solution, the mechanochemical ring-opening of gDCC is accelerated compared to homopolymers, even though the mechanophores are at the chain ends. Moreover, a higher mechanophore activation selectivity is obtained. These results indicate that mechanochemical response outside, and even far from the chain center is quite prominent in BCPs, and that forces along the polymer chain can efficiently activate multi-mechanophores regions, even when far from the polymer midchain.     

Mechanophores with a Reversible Radical System and Freezing‐Induced Mechanochemistry in Polymer Solutions and Gels

Visualization and quantitative evaluation of covalent bond scission in polymeric materials are highly important for understanding failure, fatigue, and deterioration mechanisms and improving the lifetime, durability, toughness, and reliability of the materials. The diarylbibenzofuranone‐based mechanophore radical system enabled, through electron paramagnetic resonance spectroscopy, in situ quantitative evaluation of scission of the mechanophores and estimation of mechanical energy induced along polymer chains by external forces. The coagulation of polymer solutions by freezing probably generated force but did not cleave the mechanophores. On the other hand, cross‐linking led to efficient propagation of the force of more than 80 kJ mol^?1 to some mechanophores, resulting their cleavage and generation of colored stable radicals. This mechanoprobe concept has the potential to elucidate other debated issues in the polymer field as well.     

Rhodamine Mechanophore Functionalized Mechanochromic Double Network Hydrogels with High Sensitivity to Stress

Mechanochromic hydrogels, a new class of stimuli-responsive soft materials, have potential applications in a number of fields such as damage reporting and stress/strain sensing. We prepared a novel mechanochromic hydrogel using a strategy that has been developed to prepare dual-network(DN) hydrogels. A hydrophobic rhodamine derivative(Rh mechanophore) was covalently incorporated into a first network as a cross-linker. This first network embedded with Rh mechanophore within the DN hydrogel was pre-stretched. This guaranteed that the stress could be transferred extensively to the Rh-crosslinked first network once the hydrogel was under an applied force. Interestingly, we found that the threshold stress required to activate the mechanochromism of the hydrogel was less than 200 kPa, and much less than those in previous reports. Moreover, because of the excellent sensitivity of the hydrogel to stress, the DN hydrogel exhibited reversible freezing-induced mechanochromism. Benefiting from the sensitivity of Rh mechanophore to both p H and force, the DN hydrogel showed p H-regulated mechanochromic behavior. Our experimental results indicate that the preparation strategy we used introduces sensitive mechanochromism into the hydrogel and preserves the advantageous mechanical properties of the DN hydrogel. These results will be beneficial to the design and preparation of mechanochromic hydrogels with high stress sensitivity, and foster their practical applications in a number of fields such as damage reporting and stress/strain sensing.     

Proton-coupled mechanochemical transduction: a mechanogenerated Acid

A novel mechanophore with acid-releasing capability is designed to produce a simple catalyst for chemical change in materials under mechanical stress. The mechanophore, based on a gem-dichlorocyclopropanated indene, is synthesized and used as a cross-linker in poly(methyl acrylate). Force-dependent rearrangement is demonstrated for cross-linked mechanophore samples loaded in compression, while the control shows no significant response. The availability of the released acid is confirmed by exposing a piece of insoluble compressed polymer to a pH indicator solution. The development of this new mechanophore is the first step toward force-induced remodeling of stressed polymeric materials utilizing acid-catalyzed cross-linking reactions.     

Force-induced redistribution of a chemical equilibrium

Spiropyran (SP) mechanophores (mechanochemically reactive units) can impart the unique functionality of visual stress detection to polymers and have potential for use in smart materials with self-sensing capabilities. These color-generating mechanophores were incorporated into polyurethane via step growth polymerization. Polyurethane, which is inherently a versatile engineering polymer, possesses an optimized balance of mechanical toughness and elasticity to allow for investigation of the kinetics of the mechanochemical response of the SP mechanophore in the bulk polymer via fluorescence and absorbance measurements. The stress-induced 6-π electrocyclic ring-opening to the colored merocyanine (MC) form of the mechanophore was quantified by measuring the change in absorbance of the polymer, while it was held at constant strain. The closing kinetics of the mechanophore was also studied by fluorescence imaging. Finally, the effects of mechanical strain on the equilibrium between the SP and MC forms are reported and discussed.     

Mechanochemical generation of acid-degradable poly(enol ether)s

In an effort to develop polymers that can undergo extensive backbone degradation in response to mechanical stress, we report a polymer system that is hydrolytically stable but unmasks easily hydrolysable enol ether backbone linkages when force is applied. These polymers were synthesized by ring-opening metathesis polymerization (ROMP) of a novel mechanophore monomer consisting of cyclic ether fused bicyclohexene. Hydrogenation of the resulting polymers led to significantly enhanced thermal stability (T_d > 400 °C) and excellent resistance toward acidic or basic conditions. Solution ultrasonication of the polymers resulted in up to 65% activation of the mechanophore units and conversion to backbone enol ether linkages, which then allowed facile degradation of the polymers to generate small molecule or oligomeric species under mildly acidic conditions. We also achieved solid-state mechano-activation and polymer degradation via grinding the solid polymer. Force-induced hydrolytic polymer degradability can enable materials that are stable under force-free conditions but readily degrade under stress. Facile degradation of mechanically activated polymechanophores also facilitates the analysis of mechanochemical products.

A mechanically responsive polymer system that is hydrolytically stable without stress, but unmasks enol ether backbone linkages under force to allow facile hydrolytic degradation.     

Molecular engineering of mechanophore activity for stress-responsive polymeric materials

Force reactive functional groups, or mechanophores, have emerged as the basis of a potential strategy for sensing and countering stress-induced material failure. The general utility of this strategy is limited, however, because the levels of mechanophore activation in the bulk are typically low and observed only under large, typically irreversible strains. Strategies that enhance activation are therefore quite useful. Molecular-level design principles by which to engineer enhanced mechanophore activity are reviewed, with an emphasis on quantitative structure–activity studies determined for a family of gem-dihalocyclopropane mechanophores.     

A modular approach to mechanically gated photoswitching with color-tunable molecular force probes

Molecular force probes conveniently report on mechanical stress and/or strain in polymers through straightforward visual cues. Unlike conventional mechanochromic mechanophores, the mechanically gated photoswitching strategy decouples mechanochemical activation from the ultimate chromogenic response, enabling the mechanical history of a material to be recorded and read on-demand using light. Here we report a completely redesigned, highly modular mechanophore platform for mechanically gated photoswitching that offers a robust, accessible synthesis and late stage diversification through Pd-catalyzed cross-coupling reactions to precisely tune the photophysical properties of the masked diarylethene (DAE) photoswitch. Using solution-phase ultrasonication, the reactivity of a small library of functionally diverse mechanophores is demonstrated to be exceptionally selective, producing a chromogenic response under UV irradiation only after mechanochemical activation, revealing colored DAE isomers with absorption spectra that span the visible region of the electromagnetic spectrum. Notably, mechanically gated photoswitching is successfully translated to solid polymeric materials for the first time, demonstrating the potential of the masked diarylethene mechanophore for a variety of applications in force-responsive polymeric materials.

A highly modular and synthetically accessible mechanophore platform enables mechanically gated photoswitching in solution and in solid polymeric materials.     

High strain‐rate response of spiropyran mechanophores in PMMA

We report the high strain‐rate response of a spiropyran (SP) mechanophore in poly(methylmethacrylate). Previous work on this system has demonstrated a reversible bond scission in the SP under local tensile force, converting it to a fluorescent merocyanine form. A Hopkinson bar was used to apply fast compressive loads at rates from 10² to 10⁴ s^?1, resulting in significant activation of the SP near fracture surfaces. However, comparison with a similar thermochromic SP reveals that much of the observed activation likely arises from thermal effects during high‐rate fracture. These results show the importance of a thermally active control system in distinguishing mechanochromic response during high‐rate loading. Microscale fluorescence mapping of the fracture surfaces using a confocal Raman microspectrometer suggests that some distinct mechanical activation may be occurring in craze‐like regions during fibril rupture. The thermal response of the SP is useful in its own right for characterizing plastic heating regions during dynamic fracture. Published 2014. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1347–1356     

Swelling-induced Mechanochromism in Multinetwork Polymers

We report a novel and versatile approach to achieving swelling-induced mechanochemistry using a multinetwork (MN) strategy that enables polymer networks to repeatedly swell with monomers and solvents. The isotropic expansion of the first network (FN) provides sufficient force to drive the mechanochemical scission of a radical-based mechanophore, difluorenylsuccinonitrile (DFSN). Although prompt recombination generally occurs in such highly mobile environments, the resulting pink radicals are kinetically stabilized in the gels, probably due to limited diffusion in the extended polymer chains. Moreover, the DFSN embedded in the isotropically strained chain exhibits increased thermal reactivity, which can be reasonably explained by an entropic contribution of the FN to the dissociation. The utility of the MN polymers is demonstrated not only in terms of swelling-force-induced network modification, but also in the context of tunable reactivity of the dissociative unit through proper design of the hierarchical network architecture.