Adaptive Assembly of Dative B←N Frameworks for Dimension‐Controlled Hetero‐Engineering

ABSTRACT Luminescent heterostructures with spatially resolved emission hold great promise for optoelectronic applications, yet dimension‐controlled hetero‐assembly for stimuli‐responsive heterostructures remains a significant challenge owing to the uncertain integration of distinct components. Herein, we reported an adaptive assembly strategy in dative B←N framework, enabling dimension‐controlled synthesis of luminescent heterostructures with stimuli‐responsive properties. The conformational flexibility of boroxine units permit the epitaxial ligand to form the similar conformation as the seed ligand, triggering the adaptive hetero‐assembly between different frameworks. Moreover, the structural similarity on side chains of seed and epitaxial ligands determines the spatial matching degree at heterointerface, and thus adjusting the structural types of ligand side chains enables precise regulation of both the interfacial lattice matching and assembly orientation, thereby constructing one‐dimensional and two‐dimensional B←N framework heterostructures. The resulting heterostructures exhibit spatially‐resolved stimuli‐responsive emission by inheriting intramolecular charge transfer of ligands, functioning as photonic barcode labels with multi‐level authentication capability. These findings provide insights into optical heterostructures that combine tunable dimensionality with responsive functionality.