The experimental methods used to study mechanochemical reactions are only semi-quantitative, and therefore preclude the derivation of rate constants and the development of predictive models of these reactions. As a consequence, open questions remain related to how reaction mechanisms and potential energy surfaces change under compressive force, and how to determine <i>a priori</i> the relative mechanical reactivity of a molecule. The result is that the role of force on surface reactions remains controversial, and disagreement exists as to whether force can alter reaction kinetics on surfaces. Here we report an experimental approach for quantifying the kinetics of surface reactions under applied force by using massively parallel elastomeric arrays to push a reactive species into an appropriately functionlized surfaces. Activation volumes for the Husigen reaction between an azide and alkyne was measured, and it was found that reaction yield was dependent upon force, time, and monolayer chain length. Subsequently, the same method was used to functionalize the basal plane of graphene by force-accelerated Diels-Alder reactions. Force-induced <i>bond forming</i> reactions remain grossly unexplored, and a deeper understanding of the underlying mechanisms could provide new opportunities in coatings, sensors, and electronics.

Interrogating force-induced reaction acceleration on bond-forming surface reactions

255th National Meeting (2018)

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