Benzophenone[3]arene: Supramolecular Modulation of Semi-crystalline toward Crystalline Transformation

Host–guest intermolecular interactions have emerged as pivotal strategies to suppress material architecture relaxation and drive amorphous–crystalline phase transitions. In this work, we designed and synthesized a novel macrocyclic arene (BP[3]) incorporating a benzophenone motif, which exhibits remarkable solvent-dependent self-assembly behaviors across different solvent environments. Due to the conformational locking effect induced by host–guest recognition, BP[3] exhibited excellent adsorption performance against five benzene vapors, especially for benzene and toluene, with molar host–guest adsorption capacities of 1:4 and 1:5, respectively. More importantly, the dynamic bonding network reconstruction initiated by the embedding of guest molecules can effectively inhibit the structural relaxation process of the BP[3]α phase and finally realize the solid-state phase transition from amorphous to crystalline.