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

Zhou, Yue; Kan, Liang; Eubank, Jarrod F.; Li, Guanghua; Zhang, Lirong; Liu, Yunling

doi:10.1039/c9sc00290a

Cited by 32 publications

(21 citation statements)

References 64 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Slow evaporation of an ethyl ether solution into a THF solution of TMBTI in two weeks afforded the colorless stick‐like crystals. During our exploration of the activated ZJU‐HOF‐1, the structure of the as‐synthesized HOF (JLU‐SOF3) was independently reported for different properties [13c] . Single crystal X‐ray diffraction analysis revealed that JLU‐SOF3 crystallizes in a hexagonal P

\overset{6}{true}

2 c space group with a hydrogen‐bonded 3D network (Figure 1).…”

Section: Resultsmentioning

confidence: 99%

A Rod‐Packing Hydrogen‐Bonded Organic Framework with Suitable Pore Confinement for Benchmark Ethane/Ethylene Separation

et al. 2021

View full text Add to dashboard Cite

Fort he separation of ethane from ethylene,i t remains challenging to target both high C 2 H 6 adsorption and selectivity in aC 2 H 6 -selective material. Herein, we report ar eversible solid-state transformation in al abile hydrogenbonded organic framework to generate an ew rod-packing desolvated framework (ZJU-HOF-1) with suitable cavity spaces and functional surfaces to optimally interact with C 2 H 6 .Z JU-HOF-1 thus exhibits simultaneously high C 2 H 6 uptake (88 cm 3 g À1 at 0.5 bar and 298 K) and C 2 H 6 /C 2 H 4 selectivity (2.25), which are significantly higher than those of most top-performing materials.T heoretical calculations revealed that the cage-like cavities and functional sites synergistically "match" better with C 2 H 6 to provides tronger multipoint interactions with C 2 H 6 than C 2 H 4 .Incombination with its high stability and ultralow water uptake,this material can efficiently capture C 2 H 6 from 50/50 C 2 H 6 /C 2 H 4 mixtures in ambient conditions under 60 %RH, providing arecordpolymer-grade C 2 H 4 productivity of 0.98 mmol g À1 .

show abstract

\overset{6}{true}

2 c space group with a hydrogen‐bonded 3D network (Figure 1).…”

Section: Resultsmentioning

confidence: 99%

A Rod‐Packing Hydrogen‐Bonded Organic Framework with Suitable Pore Confinement for Benchmark Ethane/Ethylene Separation

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Recently, new supramolecular porous materials named hydrogen-bonded organic frameworks (HOFs) or supramolecular organic frameworks (SOFs) have been developed [25][26][27][28][29][30][31][32][33][34][35][36]. Usually, a HOF is built from multitopic tectons that interact with their neighbors by directional hydrogen bonds, disfavoring close packing, and thus generating significant pore volumes within the crystal [25][26][27][28]. These heterogeneous, crys-talline, supramolecular frameworks may be neutral, for example, those built by mutual interactions of multitopic carboxylic acids [25][26][27][28][29].…”

Section: Introductionmentioning

confidence: 99%

“…Usually, a HOF is built from multitopic tectons that interact with their neighbors by directional hydrogen bonds, disfavoring close packing, and thus generating significant pore volumes within the crystal [25][26][27][28]. These heterogeneous, crys-talline, supramolecular frameworks may be neutral, for example, those built by mutual interactions of multitopic carboxylic acids [25][26][27][28][29]. Alternatively, they can be constructed from components possessing oppositely charged multitopic tectons, in which case the framework becomes a charge-assisted hydrogenbonded framework (CAHOF), as was the case when multitopic guanidinium or amidinium cations were combined with polycarboxylates, polysulfonates, or polyphosphonates [30][31][32][33].…”

Section: Introductionmentioning

confidence: 99%

“…Although the field of HOF and CAHOF applications is still in its infancy, there are some promising advances in proton conductivity [30,31], gas separation and absorption [28,29], enzyme encapsulation [36], and even asymmetric synthesis (albeit with a framework that contained a transition metal ion) [37]. However, for the HOF and CAHOF catalysts to have a similar appeal to other regular active site distribution materials, such as zeolites, MOFs, or COFs, a broader scope of applications has to be investigated.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The charge-assisted hydrogen-bonded organic framework (CAHOF) self-assembled from the conjugated acid of tetrakis(4-aminophenyl)methane and 2,6-naphthalenedisulfonate as a new class of recyclable Brønsted acid catalysts

Kuznetsova¹,

Gak²,

Nelyubina³

et al. 2020

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

The acid–base neutralization reaction of commercially available disodium 2,6-naphthalenedisulfonate (NDS, 2 equivalents) and the tetrahydrochloride salt of tetrakis(4-aminophenyl)methane (TAPM, 1 equivalent) in water gave a novel three-dimensional charge-assisted hydrogen-bonded framework (CAHOF, F-1). The framework F-1 was characterized by X-ray diffraction, TGA, elemental analysis, and 1H NMR spectroscopy. The framework was supported by hydrogen bonds between the sulfonate anions and the ammonium cations of NDS and protonated TAPM moieties, respectively. The CAHOF material functioned as a new type of catalytically active Brønsted acid in a series of reactions, including the ring opening of epoxides by water and alcohols. A Diels–Alder reaction between cyclopentadiene and methyl vinyl ketone was also catalyzed by F-1 in heptane. Depending on the polarity of the solvent mixture, the CAHOF F-1 could function as a purely heterogeneous catalyst or partly dissociate, providing some dissolved F-1 as the real catalyst. In all cases, the catalyst could easily be recovered and recycled.

show abstract

“…We and others − have contributed to the design of 3D HOFs using geometrically well-defined trigonal prismatic carboxyl building blocks. Our molecular design is based on the use of triptycene as the backbone in order to take advantage of (1) its rigid bicyclic structure that prevents close packing in the solid state for the introduction of porosity and (2) the ease of its peripheral functionalization that allows the installation of six aryl-carboxyl groups, affording a highly modulable trigonal prismatic scaffold.…”

Section: D Hofs With Trigonal Prismatic Building Blocksmentioning

confidence: 99%

Hydrogen-Bonded Organic Frameworks: A Rising Class of Porous Molecular Materials

2020

View full text Add to dashboard Cite

Metrics & MoreArticle Recommendations CONSPECTUS: Hydrogen-bonded organic frameworks (HOFs) are a class of porous molecular materials that rely on the assembly of organic building blocks by means of hydrogen-bonding interactions to form two-dimensional (2D) and three-dimensional (3D) crystalline networks. The reversible nature of the hydrogenbond formation endows HOFs with the attributes of solution processability and simple regeneration. High-quality single crystals of HOFs can be grown easily for unambiguous superstructure determination by single-crystal X-ray diffraction, which is crucial for the elucidation of superstructure−property relationships.During the past decade, considerable progress has been achieved in realizing stable HOFs with permanent porosities by focusing on the design of molecular building blocks in order to introduce rigidity, auxiliary [π•••π] interactions, and interpenetration of their frameworks to sustain the extended networks. The applications of HOFs are far-reaching, spanning catalysis, energy, and biomedical products as well as the storage and separation of fine chemicals.In this Account, we, first of all, provide an overview of the chronological development of HOFs, starting from the seminal work by Marsh and Duchamp in 1969 on the crystal superstructure of the hydrogen-bonded networks of trimesic acid. We identify the development of novel hydrogen-bonding motifs such as diaminotriazine (DTA), the introduction of the concept of molecular tectonics, and the establishment of permanent porosity in HOFs as being some of the milestones, which incentivized the current burgeoning research endeavors on developing HOFs as multifunctional materials. This Account is focused primarily on surveying the strategies for constructing porous 3D HOFs based on organic building blocks with peripheral carboxyl groups. These strategies are presented in the following categories: (1) the polycatenation of 2D networks by trigonal building blocks to form global 3D frameworks, (2) the utilization of building blocks with 3D geometriestetrahedral and trigonal prismaticthat are predisposed to form 3D networks, and (3) the docking by shape-fitting of geometrically labile building blocks. We emphasize how the molecular geometry of the building blocks plays an important role in modulating the superstructures of extended frameworks so as to address specific applications. Recognizing that the in silico design of HOFs is the ultimate goal of researchers in this field, we also discuss the recent advances in superstructure prediction that lead to the formation of porous supramolecular crystals and assess the complications in implementing computational methods for HOFs with complex superstructures. We hope this Account will inspire the development of new supramolecular designs and creative approaches to crystal engineering that aid and abet the assembly of multifunctional HOFs with customizable properties.

show abstract

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

Abstract: Two 3D SOFs were synthesized based on a ‘direction-oriented’ strategy. The unique and permanent porosity structures exhibit remarkable ability to separate CO2 from N2 and light hydrocarbons.

Cited by 32 publications

References 64 publications

A Rod‐Packing Hydrogen‐Bonded Organic Framework with Suitable Pore Confinement for Benchmark Ethane/Ethylene Separation

A Rod‐Packing Hydrogen‐Bonded Organic Framework with Suitable Pore Confinement for Benchmark Ethane/Ethylene Separation

The charge-assisted hydrogen-bonded organic framework (CAHOF) self-assembled from the conjugated acid of tetrakis(4-aminophenyl)methane and 2,6-naphthalenedisulfonate as a new class of recyclable Brønsted acid catalysts

Hydrogen-Bonded Organic Frameworks: A Rising Class of Porous Molecular Materials

Contact Info

Product

Resources

About