A Dynamic 3D Hydrogen‐Bonded Organic Frameworks with Highly Water Affinity

Abstract

Owing to the critical roles it plays for both structure and functionality, hydrogen bonding has high hopes for the orientated applications in hydrogen-bonded organic frameworks (HOFs). Here in this work, a hydrogenbonding strategy is performed for adjusting the structure and functionality of a heme-like ligand meso-tetra(carboxy-phenyl)-porphyrin (TCPP) with co-former 1,3-di(4-pyridyl) propane (1,3-DPP). A 3D dynamic HOF TCPP-1,3-DPP, with permanent porosity is obtained. For this HOF, the two components form novel robust 1D porous stripes, with the 1,3-DPP molecules acting as the lining for the pores that are confined within the region between adjacent carboxyphenyl moieties of TCPP. This confinement has tuned the affinities of TCPP from hydrophobic into hydrophilic. Interestingly, the 1D stripes are further stacked by weak π…π interactions into a 3D framework, the latter is highly dynamic with 1D stripes sliding back and forth, upon pressurized and water adsorption in the solid-state under ambient conditions, respectively. The activated TCPP-1,3-DPP has a Brunauer-Emmett-Teller surface area of 258 m 2 g −1 , and shows a maximum adsorption capacity about 9.8% for water during the adsorption-desorption cycles, demonstrating a promising candidate for the real-world application in effective dehydration of industrial gases under ambient conditions.

New Cobalt(II) and Copper(II) Thiocyanate Complexes of 2,5‐Bis(pyridin‐2‐yl)‐1,3,4‐oxadiazole Ligand: Synthesis, Crystal Structures, Spectral Properties and Hirshfeld Surface Analysis

“…These complexes showed intermolecular π – π interactions between pyridine rings and intermolecular C–H⋯N bonds. Owing to the critical roles it plays for both structure and functionality, the intermolecular interactions including hydrogen bonding, π – π stacking, and halogen bonding can be decisive for the orientated applications in molecular recognition, self‐organization, and hydrogen‐bonded organic frameworks (HOFs) …”

Selective separation of Xe/Kr and adsorption of water in a microporous hydrogen-bonded organic framework

“…Similarly, the adsorption amount of water vapor is negligible less than P/P 0 z 0.40 at 308 K. At P/P 0 ¼ 0.9, HOF-BTB adsorbed 304.6 mg g À1 of water vapor at 298 K and 252.2 mg g À1 at 308 K. These water vapor uptakes of HOF-BTB is much higher than that of the recently reported porphyrin based HOF, TCPP-1,3-DPP (91 mg g À1 at 298 K). 40 Though its uptake is smaller than that of representative porous materials such as MOF-808, Cr-MIL-101, MCM-41, TpBpy, and CPOP-9, it is comparable to materials with similar surface areas. [54][55][56][57] For example, NU-POP-1, CE-1, and MOF-801 P (with the surface area of 950 cm 3 g À1 , 960 cm 3 g À1 , and 990 cm 3 g À1 , respectively) showed uptakes of 230 mg g À1 , 220 mg g À1 , and 362 mg g À1 , respectively.…”

“…Some HOF materials have been reported to have higher stability under exposure to moisture or in water. [38][39][40] To evaluate the stability of HOF-BTB in the presence of water, we immersed as-prepared HOF-BTB crystals, as well as thermally activated crystals, into distilled water for a month. All observed PXRD patterns of both HOF-BTB crystals are in good agreement with the simulated PXRD pattern (Fig.…”

“…16,21,23,36 Interestingly, several HOFs are known to be more durable than MOFs and COFs in a humid environment or even in water. 7,10,[37][38][39][40] However, the study on water vapor adsorption in HOFs remains rare.…”

Self-assembly of two robust 3D supramolecular organic frameworks from a geometrically non-planar molecule for high gas selectivity performance

“…Supramolecular organic frameworks (SOFs, also called HOFs, abbreviation of hydrogen-bonded organic frameworks) constructed by hydrogen-bonding and p-p interactions are attractive gas adsorbents thanks mainly to their low framework density and regeneration by simple recrystallization. 10,[13][14][15][16][17][18][19] However, the stability of SOFs is still a challenge although a number of SOFs with permanent porosity have been reported. [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] Considering their highly predictable hydrogenbonding motif, some (carboxylic acid)-containing organic units were selected to construct SOF materials by the groups of Zentner, Moorthy, Hisaki and others.…”