Extended Data Fig. 1: The electron as an efficient catalyst for both covalent reactions and molecular recognition.
a, Electron-catalysed covalent reactions are well established in synthetic covalent chemistry, particularly for radical-mediated photoredox catalysis and organic electrosynthesis. Consider a reaction A + B → A–B, where a high energy barrier causes the reaction to be very slow. Injection of an electron reduces one of the substrates (A) to a highly reactive radical species (A•−), which can rapidly form a covalent bond with the other substrate (B). The resulting intermediate (A•−–B) releases the electron to afford the final product (A–B). Whereas the overall process is redox neutral, i.e., the redox state remains the same during the transformation from the substrates to product, the catalytic pathway, which involves the temporary addition of an electron, leads to a substantially lower energy barrier, thereby expediting the formation of the covalent bond. In this process, the electron has acted as an effective catalyst. b, The research reported in this article aims to extend the paradigm of electron catalysis to promoting and controlling molecular recognition. The trajectory for this noncovalent process is similar to that for electron-catalysed covalent reactions, except that the product is a supramolecular complex wherein molecular components are assembled courtesy of noncovalent bonding interaction(s), rather than a molecule whose atoms are connected by covalent bond(s).
