Crystalline Naphthylene Macrocycles Capturing Gaseous Small Molecules in Chiral Nanopores.

ABSTRACT

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 N2 molecules in chiral C2 arrangements. With macrocycles as basic frameworks, functional nanopores may be exploited for chiral small-molecule alignments.