Breaking Interference‐Driven Reversal Currents to Boost Single‐Molecule Conductance

Controlling charge transport in single‐molecule junctions is essential for advancing molecular electronics. This study demonstrates a novel strategy to dramatically enhance conductance in cross‐conjugated systems by preventing reversal current formation in destructive quantum interference (DQI) regimes. We design four molecules with meta‐substituted phenyl rings replaced by hydrogen‐bonded diketone (OHO) or boron‐coordinated rings (NBN, NBO, OBO), all maintaining hexagonal cross‐conjugated topology. Experimental and theoretical analyses reveal a counterintuitive conductance enhancement arising from suppressed reversal currents. Replacing the prototype m‐phenyl ring (mPh) with diketone (OHO) elevates conductance by one order of magnitude. Further boron coordination synergistically modulates quantum interference and energy levels, achieving an unprecedented two orders of magnitude increase in conductance in OBO (from 10−5.39 G0 to 10−3.41 G0). This work establishes a paradigm for efficient conductance modulation via targeted reversal current suppression, enabling rationally designed quantum‐interference molecular devices.