Interlocking Organic Nanotubes into a Three‐Dimensional Framework: Synthesis, Crystal Structure with Dual‐Buckle Configuration, and Application in Stabilizing Lithium Metal Anode

Abstract Single‐crystalline organic nanotubes (ONTs) are very important to help us deeply understand the structure‐property relationship, however, their preparation remains challenging. In this study, we propose a “B←N coordination‐directed self‐locking” strategy to construct robust single‐crystalline ONTs (named as CityU‐56 ). Single crystals of CityU‐56 are assembled via the formation of dynamic B←N bonds between 2,2′,7,7′‐tetra(4‐pyridyl)‐9,9′‐spirobifluorene (SPFPY) and 1,4‐bis(benzodioxaborole)benzene (BACT). Single‐crystal X‐ray diffraction analysis indicates that CityU‐56 possesses a well‐defined prismatic nanotube structure with highly ordered arrays. Importantly, the dual buckle‐tongue‐latch interlocking mechanism between adjacent nanotubes stabilizes the ordered arrangement of the nanotubes through synergistic B←N coordination and π–π stacking. Given these advantages, CityU‐56 has been demonstrated to serve as an artificial solid electrolyte interphase (ASEI) layer for lithium metal anodes, which significantly enhanced the stability and long‐term cycling performance of the as‐fabricated batteries.