A rigid phenyl-based covalently interlocked macrocycle with inherent porosity

Abstract

The precise construction of three-dimensional (3D) carbon networks consisting solely of sp² hybridized atoms has long been pursued in carbon nanoscience. Herein, we report the bottom-up synthesis of a covalently interlocked macrocycle ([2]CIM) featuring a molecular core of 31 benzene units. X-ray crystallography unambiguously confirmed the covalently interlocked structure of [2]CIM, revealing a rigid 3D architecture with inherent porosity. Its configurational rigidity and unique solidstate packing enable it as a promising molecular porous material, exhibiting a specific surface area (SABET) of 507 m 2 g -1 .Comprehensive gas absorption studies demonstrated its selective uptake of ethane (C2H6) over ethylene (C2H4), marking the first such observation for phenyl-based molecular macrocycles. This work not only enables in-depth solid-state investigations of novel rigid 3D conjugated molecules, but also paves the way for the precise synthesis of 3D carbon networks at the molecular level.