Dynamic Regulation of Adaptive Butterfly‐Shaped Molecules via B←N Coordination

Abstract Achieving dynamic control over stereostructures and electronic properties of rigid molecules remains a significant challenge due to the delicate balance between stability and flexibility. Here, the construction of butterfly‐shaped molecular junctions stabilized by moderate‐strength boron‐nitrogen (B←N) coordination between boraacenes and pyridines is reported. By leveraging the pivot‐like flexibility of B←N bonds, molecular conductance switching with on/off ratios exceeding 100 is achieved through force‐driven dynamic transitions between distinct stacking conformations. Single‐molecule electrical measurements combined with first‐principle calculations identify distinct charge transport mechanisms—through‐space and through‐bond—associated with the butterfly‐wing open and closed configurations. Furthermore, external factors like electric fields and substituent effects modulate π – π interactions and charge transport properties. The introduction of destructive quantum interference effects can be achieved by replacing molecular units. The findings demonstrate that B←N coordination serves as a dynamically tunable linkage, offering a pathway to design molecular platforms with multifunctional units, customized stereo‐conformations, and quantum effects.