Microporosity of a Guanidinium Organodisulfonate Hydrogen‐Bonded Framework

Brekalo, Ivana; Deliz, David E.; Barbour, Leonard J.; Ward, Michael D.; Friščić, Tomislav; Holman, K. Travis

doi:10.1002/ange.201911861

Cited by 15 publications

(3 citation statements)

References 45 publications

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“…In this seminal study, the bowl-shaped molecule p-tert-butylcalix [4]arene was shown to include a guest molecule in discrete cavities despite the absence of channels. Subsequently, other non-porous molecular materials exhibiting dynamic and cooperative guest transport were reported [38][39][40][41][42][43][44][45] .…”

Section: Preparation and Characterization Of 1 Dmfmentioning

confidence: 99%

Reversible transformations between the non-porous phases of a flexible coordination network enabled by transient porosity

et al. 2023

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Flexible metal–organic materials that exhibit stimulus-responsive switching between closed (non-porous) and open (porous) structures induced by gas molecules are of potential utility in gas storage and separation. Such behaviour is currently limited to a few dozen physisorbents that typically switch through a breathing mechanism requiring structural contortions. Here we show a clathrate (non-porous) coordination network that undergoes gas-induced switching between multiple non-porous phases through transient porosity, which involves the diffusion of guests between discrete voids through intra-network distortions. This material is synthesized as a clathrate phase with solvent-filled cavities; evacuation affords a single-crystal to single-crystal transformation to a phase with smaller cavities. At 298 K, carbon dioxide, acetylene, ethylene and ethane induce reversible switching between guest-free and gas-loaded clathrate phases. For carbon dioxide and acetylene at cryogenic temperatures, phases showing progressively higher loadings were observed and characterized using in situ X-ray diffraction, and the mechanism of diffusion was computationally elucidated.

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Section: Preparation and Characterization Of 1 Dmfmentioning

confidence: 99%

Reversible transformations between the non-porous phases of a flexible coordination network enabled by transient porosity

et al. 2023

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“…KUF‐1, self‐assembled from tetra‐sulfonate anions and guanidinium cation is also thermally stable in the range of 298–573 K. It can keep high crystallinity in the range of 298–423 K. The unique S‐shape NH 3 adsorption behavior and good reusability make it a promising adsorbent for effective NH 3 capture [42] . Recent research discovered that gas pressure imposition could regenerate porous structures from collapsed nonporous GS frameworks [43] . That paves a fresh avenue for the permanent porosity establishment and functional application of GS frameworks.…”

Section: Rational Design Of Hybrid Hofsmentioning

confidence: 99%

Hybrid Hydrogen‐Bonded Organic Frameworks: Structures and Functional Applications

Liu

Chang

Fang

et al. 2023

Chemistry A European J

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As a new class of porous crystalline materials, hydrogen-bonded organic frameworks (HOFs) assembled from building blocks by hydrogen bonds have gained increasing attention. HOFs benefit from advantages including mild synthesis, easy purification, and good recyclability. However, some HOFs transform into unstable frameworks after desolvation, which hinders their further applications. Nowadays, the main challenges of developing HOFs lie in stability improvement, porosity establishment, and functionalization. Recently, more and more stable and permanently porous HOFs have been reported. Of all these design strategies, stronger charge-assisted hydrogen bonds and coordination bonds have been proven to be effective for developing stable, porous, and functional solids called hybrid HOFs, including ionic and metallized HOFs. This Review discusses the rational design synthesis principles of hybrid HOFs and their cutting-edge applications in selective inclusion, proton conduction, gas separation, catalysis and so forth.

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“…In hydrogen‐bonded sulfonate frameworks, with guanidinium, [19] hexaaqua, [20] or hexaammine metal cations, [21] the flexibility of the charge‐assisted hydrogen‐bonding with larger cations enables the inclusion of a diverse range of guests. Unfortunately, both classes of material often lack structural stability upon removal of guest compounds, although some exceptions have been reported [21,22] …”

Section: Introductionmentioning

confidence: 99%

Microporous Metal‐Phosphonates with a Novel Orthogonalized Linker and Complementary Guests: Insights for Trivalent Metal Complexes from Divalent Metal Complexes

Glavinović

Perras

Gelfand

et al. 2023

Chemistry A European J

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The reliable self‐assembly of microporous metal‐phosphonate materials remains a longstanding challenge. This stems from, generally, more coordination modes for the functional group allowing more dense structures, and stronger bonding driving less crystalline products. Here, a novel orthogonalized aryl‐phosphonate linker, 1,3,5‐tris(4’‐phosphono‐2’,6’‐dimethylphenyl) benzene (H6L3) has been used to direct formation of open frameworks. The peripheral aryl rings of H6L3 are orthogonalized relative to the central aromatic ring giving a tri‐cleft conformation of the linker in which small aromatic molecules can readily associate. When coordinated to magnesium ions, a series of porous crystalline metal‐organic, and hydrogen‐bonded metal‐organic frameworks (MOFs, HMOFs) are formed (CALF‐41 (Mg), HCALF‐42 (Mg), ‐43 (Mg)). While most metal‐organic frameworks are tailored based on choice of metal and linker, here, the network structures are highly dependent on the inclusion and structure of the guest aromatic compounds. Larger guests, and a higher stoichiometry of metal, result in increased solvation of the metal ion, resulting in networks with connectivities increasingly involving hydrogen‐bonds rather than direct phosphonate coordination. Upon thermal activation and aromatic template removal, the materials exhibit surface areas ranging from 400–600 m2/g. Self‐assembly in the absence of aromatic guests yields mixtures of phases, frequently co‐producing a dense 3‐fold interpenetrated structure (1). Interestingly, a series of both more porous (530–900 m2/g), and more robust solids is formed by complexing with trivalent metal ions (Al, Ga, In) with aromatic guest; however, these are only attainable as microcrystalline powders. The polyprotic nature of phosphonate linkers enables structural analogy to the divalent analogues and these are identified as CALF‐41 analogues. Finally, insights to the structural transformations during metal ion desolvation in this family are gained by considering a pair of structurally related Co materials, whose hydrogen‐bonded (HCALF‐44 (Co)) and desolvated (CALF‐44 (Co)) coordination bonded networks were fully structurally characterized.

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Microporosity of a Guanidinium Organodisulfonate Hydrogen‐Bonded Framework

Cited by 15 publications

References 45 publications

Reversible transformations between the non-porous phases of a flexible coordination network enabled by transient porosity

Reversible transformations between the non-porous phases of a flexible coordination network enabled by transient porosity

Hybrid Hydrogen‐Bonded Organic Frameworks: Structures and Functional Applications

Microporous Metal‐Phosphonates with a Novel Orthogonalized Linker and Complementary Guests: Insights for Trivalent Metal Complexes from Divalent Metal Complexes

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