Louis Kahn, architect of the Salk Institute in La Jolla, said1 “even a common, ordinary brick wants to be something more than it is.” Suppose that were also true of molecules. We know that they can and do aggregate; they give complex structures, and by doing so they acquire new properties—functions that may not be apparent from a study of the individual components. This review is about molecular aggregates of a certain sort, namely, those that assemble and more or less completely surround other molecules. Taking part in this intimacy imparts unique properties to the participants, and new functions emerge from the aggregate as a whole. For the most part, we emphasize self‐complementary structures. Their ability to assemble—an expression of the molecule's desire to be something more than it is—results from instructions engineered into the molecules during their creation.
Covalent mechanochemistry within bulk polymers typically occurs with irreversible deformation of the parent material. Here we show that embedding mechanophores into an elastomeric poly(dimethylsiloxane) (PDMS) network allows for covalent bond activation under macroscopically reversible deformations. Using the colorimetric mechanophore spiropyran, we show that bond activation can be repeated over multiple cycles of tensile elongation with full shape recovery. Further, localized compression can be used to pattern strain-induced chemistry. The platform enables the reversibility of a secondary strain-induced color change to be characterized. We also observe mechanical acceleration of a flex-activated retro-Diels–Alder reaction, allowing a chemical signal to be released in response to a fully reversible deformation.
Specific metal-ligand coordination between bis-Pd(II) and Pt(II) organometallic cross-linkers and poly(4-vinylpyridine) in DMSO defines a three-dimensional associative polymer network. Frequency-dependent dynamic mechanical moduli of a series of four different bulk materials, measured across several decades of oscillatory strain rates, are found to be quantitatively related through the pyridine exchange rates measured on model Pd(II) and Pt(II) complexes. Importantly, the mechanism of ligand exchange in the networks is found to be the same solvent-assisted pathway observed in the model complexes, and so the bulk mechanical properties are determined by relaxations that occur when the cross-links are dissociated from the polymer backbone. It is how often the cross-links dissociate, independently of how long they remain dissociated, that determines the bulk mechanical properties. The quantitative relationship between bulk materials properties and the kinetics and mechanisms observed in model compounds holds promise for the rational, molecular design of materials with tailored mechanical properties.
Transition state structures are central to the rates and outcomes of chemical reactions, but their fleeting existence often leaves their properties to be inferred rather than observed. By treating polybutadiene with a difluorocarbene source, we embedded gem-difluorocyclopropanes (gDFCs) along the polymer backbone. We report that mechanochemical activation of the polymer under tension opens the gDFCs and traps a 1,3-diradical that is formally a transition state in their stress-free electrocyclic isomerization. The trapped diradical lives long enough that we can observe its noncanonical participation in bimolecular addition reactions. Furthermore, the application of a transient tensile force induces a net isomerization of the trans-gDFC into its less-stable cis isomer, leading to the counterintuitive result that the gDFC contracts in response to a transient force of extension.
Current activity in, and future prospects for, the incorporation of mechanochemically active functional groups (''mechanophores'') into polymers is reviewed. This area of research is treated in the context of two categories. The first category is the development of new chemistry in the service of material science, through the design and synthesis of mechanophores to provide stress-sensing and/or stress-responsive elements in materials. The second category is the reverse-the development of new material architectures that efficiently transmit macroscopic forces to targeted molecules in order to generate chemical reactivity that is inaccessible by other means. IntroductionThe mechanical forces typical of daily life have the potential to induce dramatic reactivity at the molecular level. The force between an infant's clenched finger and thumb, for example, is more than ten billion times that of the force between atoms in a carbon-carbon bond. Not only are macroscopic forces many orders of magnitude greater than atomic forces, they are also directional, and therefore differ from conventional forms of energy input such as heat and light. In the past four years, several studies have demonstrated that macroscopic mechanical forces can be harnessed at the molecular level, creating a new tool for the organic and materials chemist alike. Broadly, the opportunities in this area can be divided into two categories. First, there is the opportunity to develop new chemistry in the service of material science by designing and synthesizing mechanically activated functional groups (''mechanophores'') and incorporating them as stress-sensing and/or stress-responsive elements in materials. The second opportunity is the complement of the first-the development of new material architectures that efficiently transmit macroscopic forces to targeted molecules and, in so doing, open up a world of chemical reactivity that is inaccessible by other means. We will refer to these as ''chem / mat'' and ''mat / chem'' mechanochemistry, respectively (Fig. 1). The field of mechanochemistry therefore touches on materials chemistry from the point of view of each of its principle progenitors with potential utility in areas ranging from stoichiometric reactivity and catalysis to stress-responsive and selfhealing polymers.We see the greatest opportunities in mechanochemistry arising from situations in which the mechanical force is directly applied to the mechanophore, so that a directional coupling between the vector of applied force and the reaction of interest is possible. The focus of this paper, then, will be on the mechanochemistry of polymers under tension, where the mechanical coupling is most obvious and, therefore, most amenable to the chemist's intuition. Other aspects of mechanochemistry, such as those involved in the milling of crystals, metals, and alloys, 1 are well known and important fields, but they will not be discussed here. A comprehensive review of mechanochemistry in polymers has been published recently by Caruso et al., 2 and it is ...
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