Nonporous Adaptive Crystals Based on Pillararene/Calixarene‐Inspired Novel Macrocyclic Arenes

Nonporous adaptive crystals (NACs) represent a unique class of supramolecular macrocycle-based crystalline organic materials that have garnered significant attention in supramolecular chemistry and beyond over the past decade. Unlike traditional porous materials, NACs are initially nonporous but can induce porosity through host-guest interactions in the solid-state, enabling exceptional performance in hydrocarbon separation. This review surveys the development of NACs based on novel macrocyclic arenes inspired by pillararene and calixarene structures, encompassing biphen[n]arene, tiara[n]arene, leaning pillararene, hybrid[n]arene, leggero pillararene, geminiarene, bowtiearene, rhombicarene, and other derivatives. Emphasizing their preparation, structural characteristics, and mechanisms of adsorptive selectivity, this comprehensive overview highlights their contributions to advancing supramolecular chemistry, functional materials, and beyond. Finally, the remaining challenges and perspectives are outlined. It is anticipated that this review will serve as a timely and valuable reference for researchers interested in NACs and related materials, stimulating further impactful studies in related fields.