Supramolecular Diodeswith Donor–Acceptor Interactions

Inspired by the initial proposal of σ-bridged donor–acceptor (D-σ-A) single-molecule diodes in 1974, extensive studies over the past 50 years have explored various designs for π-conjugated D-π–A single-molecule diodes due to their feasible chemical synthesis and effective charge transfer. However, the rectification ratio of π-conjugated single-molecule diodes has been long-term limited by the challenge of asymmetric electronic coupling to induce the rectification effect. Here, we present a supramolecular diode constructed through an intramolecular π–π interaction-driven assembly strategy. The asymmetric transmission in this system is tunable via subangström mechanical control, resulting in a rectification ratio of up to 16. Electron transport studies reveal that this through-space D-π–π–A system constructed by the π–π stacking between pyrene (<b>Py</b>) and naphthalenediimide (<b>NDI</b>) is crucial for achieving asymmetric currents under different bias polarization. Theoretical calculations suggest that the intermolecular destructive quantum interference not only enables a sharp variation in electron transmission but also facilitates asymmetric electronic energy shifts through mechanical stretching, significantly improving the rectification ratio. Our work provides a general approach to fabricating and modulating asymmetric molecular architectures through noncovalent supramolecular interactions, showcasing the potential of high-performance single-molecule rectifiers.