Interface Phenomena in Molecular Junctions through Noncovalent Interactions

Noncovalent interactions, both between molecules and at the molecule-electrode interfaces, play essential roles in enabling dynamic and reversible molecular behaviors, including self-assembly, recognition, and various functional properties. In macroscopic ensemble systems, these interfacial phenomena often exhibit emergent properties that arise from the synergistic interplay of multiple noncovalent interactions. However, at the single-molecule scale, precisely distinguishing, characterizing, and controlling individual noncovalent interactions remains a significant challenge. Molecular electronics offers a unique platform for constructing and characterizing both intermolecular and molecule-electrode interfaces governed by noncovalent interactions, enabling the isolated study of these fundamental interactions. Furthermore, precise control over these interfaces through noncovalent interactions facilitates the development of enhanced molecular devices. This review examines the characterization of interfacial phenomena arising from noncovalent interactions through single-molecule electrical measurements and explores their applications in molecular devices. We begin by discussing the construction of stable molecular junctions through intermolecular and molecule-electrode interfaces, followed by an analysis of electron tunneling mechanisms mediated by key noncovalent interactions and their modulation methods. We then investigate how noncovalent interactions enhance device sensitivity, stability, and functionality, establishing design principles for next-generation molecular electronics. We have also explored the potential of noncovalent interactions for bottom-up self-assembled molecular devices. The review concludes by addressing the opportunities and challenges in scaling up molecular electronics through noncovalent interactions.