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 m2 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.

Supramolecular Metal–Organic Framework for CO2/CH4 and CO2/N2 Separation

“…Compared with the traditional cryogenics distillation and amine solvent-based absorption, adsorbent separation technologies with porous materials toward CO 2 separation and capture is an alternative method for its lower energy/cost and mild operation conditions. Hence, the diversity of porous materials have been explored, such as carbon-based materials, − zeolites, − porous polymers, − metal–organic frameworks (MOFs), − hydrogen–organic frameworks (HOFs), − and so forth. MOFs are assembled by coordination bonding of their corresponding building units, which have attracted tremendous interest because of their diversiform variety, pore functionality, − and tailorable pore size. − Compared to MOFs, HOFs are linked by weaker hydrogen-bond interactions, which are less stable and usually undergo structure collapse upon guest removal. − However, HOFs are of mild synthetic conditions, easy purification, and regeneration by recrystallization. − …”

Hydrogen-bonded porous frameworks constructed by rigid π-conjugated molecules with carboxy groups

“…To date, two HAT-based HOFs (CPHAT-1a and CBPHAT-1a), which have phenylene and biphenylene arms, were reported [92,112]. A preliminary crystal structure of one solvated HOF composed of a HAT derivative possessing diphenylacetylene arms (CTolHAT-1) was also revealed by the author's group as shown in Fig.…”

Self-Recognizing π-π Stacking Interactions Designed for the Generation of Ultrastable Mesoporous Hydrogen-Bonded Organic Frameworks

“…Such tectons usually form 2D layers by H-bonding while cooperative π-π stacking interactions exist between 2D layers, which has proven to be a reliable approach to stabilize HOF materials. 8,11,[29][30][31][32] For example, a series of HOFs with isostructural or quasi-isostructural honeycomb frameworks has been prepared by assembling tectons with C 3 -or C 6 -symmetries. 29,33 However, as the length of tectons increases, the π-π stacking between 2D layers tends to be in a staggered manner rather than eclipsed, which leads to a decrease in the pore size of these HOFs.…”