BN Dative Bonds in Self‐Assembly: From Discrete Supramolecular Architectures to Porous Functional Frameworks

BN dative bonds, derived from Lewis acid–base interactions, have emerged as versatile motifs for self‐assembly because they combine directionality, reversibility, and coordination‐induced geometric adaptability. These features support the formation of architectures ranging from macrocycles and cages to interlocked systems, crystalline polymers, and boron–nitrogen organic frameworks. This review surveys the development of BN‐bond‐driven self‐assembly in both discrete and extended systems, with emphasis on how Lewis acidity/basicity, steric effects, linker geometry, secondary interactions, and activation conditions govern structure and function. Representative studies show that B–N self‐assembly enables host–guest recognition, switching, separation, sensing, photocatalysis, and robust porous materials. Persistent challenges, however, include bond lability, competing cyclization and polymerization pathways, framework collapse, interpenetration, and the difficulty of achieving stable three‐dimensional porous architectures. Overall, this review provides a unified perspective on the design principles, functional scope, and future development of B–N‐based self‐assembled materials.