A Hydrogen-Bonded, Hexagonally Networked, Layered Framework with Large Aperture Designed by Structural Synchronization of a Macrocycle and Supramolecular Synthon.

To develop porous organic frameworks, precise control of the stacking manner of two-dimensional porous motifs and structural characterization of the resultant framework are important. From these points of view, porous molecular crystals formed through reversible intermolecular hydrogen bonds, such as hydrogen-bonded organic frameworks (HOFs), can provide deep insight because of their high crystallinity, affording single-crystalline X-ray diffraction analysis. In this study, we demonstrate that the stacking manner of hydrogen-bonded hexagonal network (HexNet) sheets can be controlled by synchronizing a homological triangular macrocyclic tecton and a hydrogen-bonded cyclic supramolecular synthon called the phenylene triangle. A structure of the resultant HOF was crystallographically characterized and revealed to have a large channel aperture of 2.4 nm. The HOF also shows thermal stability up to 290 °C, which is higher than that of the conventional HexNet frameworks.