2026/07/20 by 家祺, Nie Fang, W M Zhu +1 · 1 voice
Chemistry · Materials Science · #Crystallography and molecular interactions #Nanoporous metals and alloys #X-ray Diffraction in Crystallography
paper · doi:10.1021/acs.cgd.6c00275
openalex publication_date 2026/07/20 · openalex created_date 2026/07/21 · openalex updated_date 2026/07/22
Noncovalent interactions are the fundamental forces governing crystal packing and the generation of intrinsic porosity in noncovalent porous crystals (NPCs); however, the comparative efficacy of distinct interaction types remains insufficiently characterized. This study presents a systematic, direct comparison between hydrogen bonding and halogen bonding within single-component NPCs, utilizing triptycene-based molecular scaffolds with identical geometric parameters. By selectively incorporating hydrogen-bonding (H···N) or halogen-bonding (X···N) motifs, we observe strikingly divergent crystallization behaviors. The hydrogen-bonded system displays pronounced polymorphism, yielding multiple crystal forms due to competing, nonspecific interaction modes. Conversely, the halogen-bonded analogue crystallizes exclusively into a single, highly porous structure. This sharp contrast is attributed to the unique nature of halogen bonding, which enforces highly directional and specific intermolecular interactions. This specificity enhances porosity, suppresses polymorphism, and significantly improves structural predictability. Consequently, these findings establish halogen bonding as an advantageous supramolecular design element within specific molecular scaffolds for constructing single-component NPCs.