Department of Chemistry, The University of Tokyo, Hongo, Bunkyu-ku, Tokyo, 113-0033, Japan.
Department of Chemistry and Advanced Institute for Materials Research, Tohoku University, Aoba-ku, Sendai, 980-8578, Japan.
Chem Asian J. 2020 Nov 16;15(22):3829-3835. doi: 10.1002/asia.202000876. Epub 2020 Sep 28.
A series of chiral naphthylene macrocycles, [n]cyclo-epi-naphthylenes ([n]CeNAPs), possessing epi-linkages were synthesized by one-pot macrocyclization. With chiral (R)- or (S)-1,1'-linkages embedded in binaphthyl precursors, the macrocycles were assembled in polygonal structures possessing chiral hinges as corners. Among four chiral [n]CeNAP variants, [8]CeNAP with eight naphthylene panels formed robust columnar assemblies in crystals. The nanoporous crystals maintained a columnar assembly structure even after the removal of encapsulated solvent molecules, and their gas adsorption behavior was thoroughly investigated. Gas adsorption, including state-of-the-art in situ crystallographic analyses, revealed accurate atomic-level structures of the nanopores trapping gaseous N molecules in chiral C arrangements. With macrocycles as basic frameworks, functional nanopores may be exploited for chiral small-molecule alignments.
一系列手性萘大环，[n]环-桥萘（[n]CeNAPs），通过一锅法大环化合成，具有桥接键。在联萘前体中嵌入手性（R）-或（S）-1,1'-键，大环以具有手性铰链作为角的多边形结构组装。在四个手性[n]CeNAP 变体中，具有八个萘环的[8]CeNAP 在晶体中形成了稳定的柱状组装体。纳米多孔晶体在除去包裹的溶剂分子后仍然保持柱状组装结构，并且对其气体吸附行为进行了彻底的研究。气体吸附，包括最先进的原位晶体学分析，揭示了纳米孔中捕获气态 N 分子的手性 C 排列的精确原子级结构。以大环为基本框架，可以开发功能性纳米孔，以实现手性小分子的排列。
