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Allosteric control of reaction thermodynamics is well understood, but the mechanisms by which changes in local geometries of receptor sites lower activation reaction barriers in electronically uncoupled, remote reaction moieties remain relatively unexplored. Here we report a molecular scaffold in which the rate of thermal E-to-Z isomerization of an alkene increases by a factor of as much as 10⁴in response to fast binding of a metal ion to a remote receptor site. A mechanochemical model of the olefin coupled to a compressive harmonic spring reproduces the observed acceleration quantitatively, adding the studied isomerization to the very few reactions demonstrated to be sensitive to extrinsic compressive force. The work validates experimentally the generalization of mechanochemical kinetics to compressive loads and demonstrates that the formalism of force-coupled reactivity offers a productive framework for the quantitative analysis of the molecular basis of allosteric control of reaction kinetics. Important differences in the effects of compressive vs. tensile force on the kinetic stabilities of molecules are discussed.

 

The mechanical degradation of polymers is typically limited to a single chain scission per triggering chain stretching event, and the loss of stress transfer that results from the scission limits the extent of degradation that can be achieved. Here, we report that the mechanically triggered ring-opening of a [4.2.0]bicyclooctene (BCOE) mechanophore sets up a delayed, force-free cascade lactonization that results in chain scission. Delayed chain scission allows many eventual scission events to be initiated within a single polymer chain. Ultrasonication of a 120 kDa BCOE copolymer mechanically remodels the polymer backbone, and subsequent lactonization slowly (~days) degrades the molecular weight to 4.4 kDa, > 10× smaller than control polymers in which lactonization is blocked. The force-coupled kinetics of ring-opening are probed by single molecule force spectroscopy, and mechanical degradation in the bulk is demonstrated. Delayed scission offers a strategy to enhanced mechanical degradation and programmed obsolescence in structural polymeric materials.

 

Molecular force probes that generate optical responses to critical levels of mechanical stress (mechanochromophores) are increasingly attractive tools for identifying molecular sites that are most prone to failure. Here, a coumarin dimer mechanophore whose mechanical strength is comparable to that of the sulfur–sulfur bonds found in vulcanized rubbers is reported. It is further shown that the strain‐induced scission of the coumarin dimer within the matrix of a particle‐reinforced polybutadiene‐based co‐polymer can be detected and quantified by fluorescence spectroscopy, when cylinders of the nanocomposite are subjected to unconstrained uniaxial stress. The extent of the scission suggests that the coumarin dimers are molecular “weak links” within the matrix, and, by analogy, sulfur bridges are likely to be the same in vulcanized rubbers. The mechanophore is embedded in polymer main chains, grafting agent, and cross‐linker positions in a polymer composite in order to generate experimental data to understand how macroscopic mechanical stress is transferred at the molecular scale especially in highly entangled cross‐linked polymer nanocomposite. Finally, the extent of activation is enhanced by approximately an order of magnitude by changing the regiochemistry and stereochemistry of the coumarin dimer and embedding the mechanophore at the heterointerface of the particle‐reinforced elastomer.

 

Mechanochemical response is the result of a complex integration of many factors, but methods for disentangling the various contributions are emerging.

 

Abstract The mechanically induced symmetry-allowed disrotatory ring openings of cis- and trans-gem-dichlorocyclopropane (gDCC) diesters are demonstrated through sonication and single-molecule force spectroscopy (SMFS) studies. In contrast to the previously reported symmetry-forbidden conrotatory ring opening of alkyl-tethered trans-gDCC, we show that the diester-tethered trans-gDCC primarily undergoes a symmetry-allowed disrotatory pathway even at the high forces (>2 nN) and short-time scales (ms or less) of sonication and SMFS experiments. The quantitative force-rate data obtained from SMFS data is consistent with computational models of transition-state geometry for the symmetry-allowed process, and activation lengths of 1.41 ± 0.02 Å and 1.08 ± 0.03 Å are inferred for the cis-gDCC diester and trans-gDCC diester, respectively. The strong mechanochemical coupling in the trans-gDCC is notable, given that the directionality of the applied force may appear initially to oppose the disrotatory motion associated with the reaction. The stereochemical perturbations of mechanical coupling created by the ester attachments reinforce the complexity that is possible in covalent polymer mechanochemistry and illustrate the breadth of reactivity outcomes that are available through judicious mechanophore design. 

The mechanical strength of individual polymer chains is believed to underlie a number of performance metrics in bulk materials, including adhesion and fracture toughness. Methods by which the intrinsic molecular strength of the constituents of a given polymeric material might be switched are therefore potentially useful both for applications in which triggered property changes are desirable, and as tests of molecular theories for bulk behaviors. Here we report that the sequential oxidation of sulfide containing polyesters ( PE-S ) to the corresponding sulfoxide ( PE-SO ) and then sulfone ( PE-SO2 ) first weakens (sulfoxide), and then enhances (sulfone), the effective mechanical integrity of the polymer backbone; PE-S ∼ PE-SO2 > PE-SO . The relative mechanical strength as a function of oxidation state is revealed through the use of gem -dichlorocyclopropane nonscissile mechanophores as an internal standard, and the observed order agrees well with the reported bond dissociation energies of C–S bonds in each species and with the results of CoGEF modeling.