Hydrogen‐Bonded Framework With Low‐Density Hexagonal Network Structure Formed by Diethynylterphenyl‐Bridged Macrocyclic Hexacarboxylic Acid

Abstract Macrocyclic π‐conjugated molecules are attractive building block molecules for porous molecular crystals because of their shape‐persistent cyclic structures and rich electronic properties. Herein, we report a single‐crystalline layered framework formed with a low‐density hydrogen‐bonded hexagonal network (HexNet) sheet. The sheet is composed of a C 3 ‐symmetric π‐conjugated building block molecule possessing a macrocyclic core expanded by diethynylterphenyl linkers and peripheral six 4‐carboxyphenyl groups. The sheet has three types of vacancies, of which the largest hexagonal void has a size of 30 Å × 34 Å. The present system is the framework with the largest crystalline periodicity among the reported single‐crystalline HexNet frameworks.