Tunable B←N Lewis pairs enabling dative organic frameworks with intrinsic stimuli-responsiveness

B←N Lewis pairs have emerged as a highly versatile platform for modulating molecular electronics and constructing adaptive functional materials, owing to their tunable coordination strength and optoelectronic properties. Nevertheless, precise control over their bonding characteristics and the achievement of reversible stimuli-responsiveness at the framework-level remain formidable challenges. Herein, we present a supramolecular design strategy for tuning B←N Lewis acid-base pairs with distinct electronic characteristics by employing a π-conjugated planar boron compound as Lewis acid and three nitrogen-containing Lewis bases with different electronic properties. This approach enables a systematic exploration of their binding strength, directionality, and optical behaviors. Furthermore, a series of B←N dative-bonded organic frameworks (DOFs) is constructed by integrating a C₂-symmetric boron monomer with C₃-symmetric nitrogen monomers. The resultant DOFs exhibit reversible fluorescence color transitions and structural recovery upon alternating stimuli of trifluoroacetic acid and triethylamine, demonstrating their potential for dynamic response in the development of advanced functional materials.