Polymers that release small molecules in response to mechanical force are promising materials for a variety of applications ranging from sensing and catalysis to targeted drug delivery. Within the rapidly growing field of polymer mechanochemistry, stress-sensitive molecules known as mechanophores are particularly attractive for enabling the release of covalently bound payloads with excellent selectivity and control. Here, we review recent progress in the development of mechanophore-based molecular release platforms and provide an optimistic, yet critical perspective on the fundamental and technological advancements that are still required for this promising research area to achieve significant impact.
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 stimuliresponsive behavior, expanding the scope and accessibility of force-responsive materials for applications such as multimodal sensing.Scheme 1 Reaction of naphthopyran in PDMS materials generates colored merocyanine dyes with substituent-dependent mechanochromic properties.
Vulcanization of silicone networks from commercially available linear poly(dimethyl-co-methylhydro)siloxane (PMHS) and α-diketones was achieved using metal-free borane hydrosilylation at room temperature. The Lewis acid catalyst, tris(pentafluorophenyl)borane (B(C6F5)3), efficiently cross-linked PMHS at minimal catalyst loadings (200–1000 ppm) to produce polymer networks with mechanical properties, thermal stability, and optical clarity rivaling that achieved from traditional platinum catalysis. Variation of the starting PMHS structure is shown to influence the final characteristics of the network. Increasing molar mass of the PMHS chain results in a higher thermal decomposition temperature, while increasing mole fractions of Si–H moieties along the backbone increase the cross-linking density and the attendant Shore hardness. The degradation behavior of the networks was investigated, with the borane-vulcanized samples showing rapid dissolution upon exposure to acid and high stability to neutral and basic conditions. Functional networks bearing halide and vinyl groups could also be prepared via a preliminary reaction of PMHS with an appropriate monoketone, providing a general and versatile strategy for network derivatization with the potential for postvulcanization functionalization being subsequently demonstrated via thiol–ene click chemistry.
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