Molecular components are vital to introduce and manipulate quantum interference (QI) in charge transport through molecular electronic devices. Up to now, the functional molecular units that show QI are mostly found in conventional π‐ and σ‐bond‐based systems; it is thus intriguing to study QI in multicenter bonding systems without both π‐ and σ‐conjugations. Now the presence of QI in multicenter‐bond‐based systems is demonstrated for the first time, through the single‐molecule conductance investigation of carborane junctions. We find that all the three connectivities in carborane frameworks show different levels of destructive QI, which leads to highly suppressed single‐molecule conductance in para‐ and meta‐connected carboranes. The investigation of QI into carboranes provides a promising platform to fabricate molecular electronic devices based on multicenter bonds.

Quantum interference (QI) plays an imperative role in the operation of molecular devices within the phase-coherent length, and it is vital to harness the patterns of QI, i.e., constructive and destructive interference. However, the size of the single-molecule device is too small compared to most gate electrodes. Those gates act like a backgate to affect the molecular component uniformly. Switching the patterns of QI in the same molecular skeleton remains challenging. Here, we develop the atomically precise gating strategy that manipulates the frontier orbitals of molecular components, achieving the complete switching of QI patterns between destructive to constructive QI and leading to a significant conductance modulation at room temperature. The chemical gating effect is exerted locally on the pyridine nitrogen through the selective interaction to cationic reagents, with which we can also control the switching reversibility as desired. We demonstrate the unique effect of atomically precise gating to modulate the quantum interference at the single-molecule scale, opening an avenue to develop new-conceptual electronic devices.

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