Docking Strategy To Construct Thermostable, Single‐Crystalline, Hydrogen‐Bonded Organic Framework with High Surface Area

Abstract Enhancing thermal and chemical durability and increasing surface area are two main directions for the construction and improvement of the performance of porous hydrogen‐bonded organic frameworks (HOFs). Herein, a hexaazatriphenylene (HAT) derivative that possesses six carboxyaryl groups serves as a suitable building block for the systematic construction of thermally and chemically durable HOFs with high surface area through shape‐fitted docking between the HAT cores and interpenetrated three‐dimensional network. A HAT derivative with carboxybiphenyl groups forms a stable single‐crystalline porous HOF that displays protic solvent durability, even in concentrated HCl, heat resistance up to 305 °C, and a high Brunauer–Emmett–Teller surface area SA (BET) of 1288 m 2 g −1 . A single crystal of this HOF displays anisotropic fluorescence, which suggests that it would be applicable to polarized emitters based on robust functional porous materials.