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Stretching a segment of a polymer beyond its contour length makes its (primarily backbone) bonds more dissociatively labile, which enables polymer mechanochemistry. Integrating some backbone bonds into suitably designed molecular moieties yields mechanistically and kinetically diverse chemistry, which is becoming increasingly exploitable. Examples include, most prominently, attempts to improve mechanical properties of bulk polymers, as well as prospective applications in drug delivery and synthesis. This review aims to highlight an emerging effort to apply the concepts and experimental tools of mechanochemistry to fundamental physical questions in soft matter. A succinct summary of the state-of-the-knowledge of the field, with emphasis on foundational concepts and generalizable observations, is followed by analysis of 3 recent examples of mechanochemistry yielding molecular-level details of elastomer failure, macromolecular chain dynamics in elongational flows and kinetic allostery. We conclude with reasons to assume that the highlighted approaches are generalizable to a broader range of physical problems than considered to date., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

We demonstrate an intermolecular reaction cascade to control the force which triggers crosslinking of a mechanochromic polymer of spirothiopyran (STP). Mechanochromism arises from rapid reversible force-sensitive isomerization of STP to a merocyanine, which reacts rapidly with activated C=C bonds. The concentration of such bonds, and hence the crosslinking rate, is controlled by force-dependent dissociation of a Diels-Alder adduct of anthracene and maleimide. Because the adduct requires ca. 1 nN higher force to dissociate at the same rate as that of STP isomerization, the cascade limits crosslinking to overstressed regions of the material, which are at the highest rate of material damage. Using comb polymers decreased the minimum concentration of mechanophores required to crosslinking by about 100-fold compared to previous examples of load-strengthening materials. The approach described has potential for controlling a broad range of reaction sequences triggered by mechanical load., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

Incorporation of small reactive moieties, the reactivity of which depends on externally imposed load (so-called mechanophores) into polymer chains offers access to a broad range of stress-responsive materials. Here, we report that polymers incorporating spirothiopyran (STP) manifest both green mechanochromism and load-induced addition reactions in solution and solid. Stretching a macromolecule containing colorless STP converts it into green thiomerocyanine (TMC), the mechanically activated thiolate moiety of which undergoes rapid thiol-ene click reactions with certain reactive C=C bonds to form a graft or a cross-link. The unique dual mechanochemical response of STP makes it of potentially great utility both for the design of new stress-responsive materials and for fundamental studies in polymer physics, for example, the dynamics of physical and mechanochemical remodeling of loaded materials., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A catalyst that couples a photoswitch to the biaryl backbone of a chiral bis(phosphine) ligand, thus allowing photochemical manipulation of ligand geometry without perturbing the electronic structure is reported. The changes in catalyst activity and selectivity upon switching can be attributed to intramolecular mechanical forces, thus laying the foundation for a new class of catalysts whose selectivity can be varied smoothly and in situ over a useful range by controlling molecular stress experienced by the catalyst during turnover. Forces on the order of 100 pN are generated, thus leading to measurable changes in the enantioselectivities of asymmetric Heck arylations and Trost allylic alkylations. The differential coupling between applied force and competing stereochemical pathways is quantified and found to be more efficient for the Heck arylations., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Sensitized photolysis: We describe a series of macrocyclic disulfides containing stiff stilbene (see scheme) as the intramolecular photosensitizer designed for fundamental mechanistic studies of sensitized photolysis of the S-S bond. Preliminary studies revealed weak temperature dependence of the quantum yields, which decreased exponentially with Boltzmann-weighted average separation between the S-S bond and stiff stilbene.

Interactions between a pair of transition-metals can range from weak antiferromagnetic coupling to bonds of the highest multiplicity known in chemistry, for example, quadruple in isolatable compounds. Tremendous effort has been invested in studying homodinuclear transition-metal-metal bonds. In contrast, relatively little attention has been devoted to heterodinuclear analogues, as it is substantially more challenging to prepare and handle such entities. Yet, in this largely unexplored area of transition-metal chemistry, novel chemical interactions with unprecedented reactivities are likely to be found. Heterodinuclear analogues of diatomic transition-metal dimers being yet inaccessible, dinuclear complexes with Werner-type ligands provide examples of high-multiplicity bonds between different d elements in their least-perturbed form. Such compounds provide an opportunity to probe fundamental issues of chemical bonding between transition-metals, by revealing how and to what extent such bonds are affected by differences in the two metals. Complexes wherein electronically unsaturated heterodinuclear cores are stabilized by pi-acidic ligands (such as CO) hold the potential of new chemical reactions (including catalytic) that capitalize on the synergetic effect of two transition-metal centers.