<p>Material failure is a ubiquitous problem, and it is known that materials fail at much lower stresses than the theoretical maximum calculated from the number and strength of the individual bonds along the material cross-section. The decreased strength is attributed to inhomogeneous stress distributions under load, thus causing the stress to accumulate at localized regions, initiating microcrack formation and subsequent propagation. In many cases, these initiation and propagation steps involve covalent bond scission. </p><p>Over the past decade there has been increased interest in channeling the mechanical forces that typically trigger destructive processes (e.g., chain scission) during use into constructive chemical transformations. In an ideal system, these stress-induced chemical transformations would redistribute load prior to material failure, thus extending material lifetime. In this Dissertation, the work of developing constructive transformations through the response of a small molecule "mechanophore" is discussed. </p><p>The gem-dihalocyclopropane mechanophore is capable of undergoing a non-scissile electrocyclic ring opening reaction under molecular scale tensile load. The mechanochemistry is demonstrated both in solution via pulsed ultrasound (Chapter 2) and in the bulk via extrusion and uniaxial tension (Chapter 3). In solution, dramatic remodeling at the molecular level occurs under the elongational flow experienced during pulsed ultrasound. Because elongational flow results in regiospecific stress distributions along a polymer main chain, this remodeling converts a gem-dichlorocyclopropane-laden homopolymer into phase separating diblock-copolymers. In the bulk, it is shown that the increased reactivity of an activated gem-dibromocyclopropane mechanophore towards nucleophilic displacement reactions leads to more non-destructive intermolecular bond-forming reactions than chain scissions, indicating the potential of the gem-dibromocyclopropane mechanophore as a self-strengthening platform. </p><p>Coupling the idea of mechanophore activation under high forces and covalent bond formation, an autonomous remodeling platform is developed, utilizing the gem-dibromocyclopropane mechanophore and a carboxylate nucleophile (Chapter 4). The system can be either two components, with a mechanophore-based polymer and a small molecule cross-linker, or a one-component system in which the mechanophore and nucleophile are embedded within the same polymer backbone. Both in the bulk and in solution, the autonomous remodeling polymer undergoes mechanophore activation followed by covalent bond formation, creating a cross-linked network in response to high shear forces. This form of remodeling leads to orders of magnitude increases in elastic modulus in response to forces that otherwise degrade polymer molecular weight and material properties. In all cases, the covalent bond formation through nucleophilic displacement of the allylic bromine by a carboxylate is confirmed as the source of polymer remodeling by FTIR as well as numerous control studies. </p><p>Together, these studies show that covalent polymer mechanochemistry can be used as a constructive tool for polymer chemistry (the direct conversion of homopolymers into well-ordered diblock copolymers) and materials science (polymers that self-strengthen in response to an applied force). This work paves the way for the future development of new mechanophores that will optimize the proof-of-principle behaviors demonstrated here.</p> / Dissertation

<p>Just as heat, light and electricity do, mechanical forces can also stimulate reactions. Conventionally, these processes - known as mechanochemistry - were viewed as comprising only destructive events, such as bond scission and material failure. Recently, Moore and coworkers demonstrated that the incorporation of mechanophores, i.e., mechanochemically active moieties, can bring new types of chemistry. This demonstration has inspired a series of fruitful works, at both the molecular and material levels, in both theoretical and experimental aspects, for both fundamental research and applications. This dissertation evaluates mechanochemical behavior in all of these contexts. </p><p>At the level of fundamental reactivity, forbidden reactions, such as those that violate orbital symmetry effects as captured in the Woodward-Hoffman rules, remain an ongoing challenge for experimental characterization, because when the competing allowed pathway is available, the reactions are intrinsically difficult to trigger. Recent developments in covalent mechanochemistry have opened the door to activating otherwise inaccessible reactions. This dissertation describes the first real-time observation and quantified measurement of four mechanically activated forbidden reactions. The results provide the experimental benchmarks for mechanically induced forbidden reactions, including those that violate the Woodward-Hoffmann and Woodward-Hoffmann-DePuy rules, and in some cases suggest revisions to prior computational predictions. The single-molecule measurement also captured competing reactions between isomerization and bimolecular reaction, which to the best of our knowledge, is the first time that competing reactions are probed by force spectroscopy. </p><p> Most characterization for mechanochemistry has been focused on the reactivity of mechanophores, and investigations of the force coupling efficiency are much less reported. We discovered that the stereochemistry of a non-reactive alkene pendant to a reacting mechanophore has a dramatic effect on the magnitude of the force required to trigger reactivity on a given timescale (here, a 400 pN difference for reactivity on the timescale of 100 ms). The stereochemical perturbation has essentially no measurable effect on the force-free reactivity, providing an almost perfectly orthogonal handle for tuning mechanochemical reactivity independently of intrinsic reactivity. </p><p>Mechanochemical coupling is also applied here to the study of reaction dynamics. The dynamics of reactions at or in the immediate vicinity of transition states are critical to reaction rates and product distributions, but direct experimental probes of those dynamics are rare. The s-trans, s-trans 1,3-diradicaloid transition states are trapped by tension along the backbone of purely cis-substituted gem-difluorocyclopropanated polybutadiene using the extensional forces generated by pulsed sonication of dilute polymer solutions. Once released, the branching ratio between symmetry-allowed disrotatory ring closing (of which the trapped diradicaloid structure is the transition state) and symmetry-forbidden conrotatory ring closing (whose transition state is nearby) can be inferred. Net conrotatory ring closing occurred in 5.0 ± 0.5% of the released transition states, as compared to 19 out of 400 such events in molecular dynamics simulations.</p><p>On the materials level, the inevitable stress in materials during usage causes bond breakage, materials aging and failure. A strategy for solving this problem is to learn from biological materials, which are capable to remodel and become stronger in response to the otherwise destructive forces. Benzocyclobutene has been demonstrated to mechanically active to ortho-quinodimethide, an intermediate capable for [4+4] dimerization and [4+2] cycloaddition. These features make it an excellent candidate for and synthesis of mechanochemical remodeling. A polymer containing hundreds of benzocyclobutene on the backbone was synthesized. When the polymer was exposed to otherwise destructive shear forces generated by pulsed ultrasound, its molecular weight increased as oppose to other mechanophore-containing polymers. When a solution of the polymer with bismaleimide was subjected to pulsed ultrasonication, crosslink occurred and the modulus increased by two orders of magnitude.</p> / Dissertation