Isoreticular expansion of polyMOFs achieves high surface area materials

Schukraft, Giulia E. M.; Ayala, Sergio; Dick, B.L.; Cohen, Seth M.

doi:10.1039/c7cc04222a

Cited by 59 publications

(41 citation statements)

References 36 publications

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“…In contrast with other polymer‐MOF hybrid systems, polyMOFs use pre‐synthesized organic polymers containing H 2 bdc units that act as ligands for MOF preparation. In a series of reports, a variety of polyMOF structures, including IRMOFs, UiO‐66, pillared‐MOFs, and isoreticular structures with laterally extended linkers have been described ,. All polyMOFs to date are synthesized from ligands connected through para ‐substituted terephthalic acid (H 2 bdc) with alkoxy linkages of various lengths (Figure ).…”

Section: Figurementioning

confidence: 99%

polyMOF Formation from Kinked Polymer Ligands via ortho‐Substitution

Palomba

Ayala

Cohen

2018

Israel Journal of Chemistry

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Reticular chemistry is an important tool in the crystal engineering of metal-organic frameworks (MOFs). Isoreticular chemistry allows for the preparation of MOFs of the same topology from ligands with related geometries. In this work, reticular chemistry is used to explore the scope of polyMOFs, which are frameworks synthesized from polymer ligands. "Linked" ortho-substituted benzene dicarboxylate polymer ligands with varying length alkyl spacers were used to synthesize polyMOFs and elucidate the effects of polymer architecture on resulting crystal formation. It was found that these "kinked" polymer ligands were able to form polyIRMOF architectures, but did not readily form polyUiO-66 topologies. CommunicationFigure 3. SEM images of o-polyIRMOFs synthesized with: a) o-pbdc-8a-u, and b) o-pbdc-10a-u.Figure 4. N 2 sorption isotherms for o-polyIRMOF synthesized with two polymer-ligands: o-pbdc-8a-u in red and o-pbdc-10a-u in blue.

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Section: Figurementioning

confidence: 99%

polyMOF Formation from Kinked Polymer Ligands via ortho‐Substitution

Palomba

Ayala

Cohen

2018

Israel Journal of Chemistry

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“…[40b] In addition, polyMOFs conform to the principle of isoreticular chemistry,allowing for linear extension of the organic linker groupts to obtain polyMOFs with even greater surface areas (> 1500 m 2 g À1 ). [41] Recently MacLeod and Johnson reported on as eries of block co-polyMOFs,where uniform benzene-1,4-dicarboxylic acid dimers or tetramers were attached as endgroups to ap olystyrene polymer. [42] These block copolymers were treated with Zn 2+ under solvothermal conditions.Copolymers containing benzene-1,4-dicarboxylic acid dimers did not form polyMOFs,suggesting alower limit on block size required to obtain crystalline phases.H owever,t he tetramer-terminated copolymers formed ab lock co-polyMOF (BCPMOF) that displayed distinct phase separation between the "hard" polyMOF block and the "soft" polystyrene block (when imaged by TEM).…”

Section: Methodsmentioning

confidence: 99%

Supramolecular Metallopolymers: From Linear Materials to Infinite Networks

2018

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The fields of coordination polymers (CPs) and supramolecular metallopolymers (SMPs) have been extensively studied for decades. Spectacular recent advances in both fields have created new compounds that lie at the interface between these two classes of organic-inorganic hybrid materials. At this interface, materials based on molecular weaving, supramolecular clusters, and metal-organic framework-polymer hybrids have emerged. This minireview provides a perspective on the intellectual emergence and connection between different supramolecular constructs and the state of the art with respect to this new materials interface.

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“…Recently, Cohen and co-workers demonstrated that certain linear organic polymers with aromatic dicarboxylic acids in their backbones could be used as ligands to synthesize highly crystalline and porous MOFs, called polyMOFs. [129,[168][169][170] A series of polymer ligands were synthesized ( to prepare polyMOFs with crystalline structures isostructural to MOF-5, [Zn 2 (bdc) 2 (dabco)], [Zn 2 (bdc) 2 (4,4′-bpy)], UiO-66, UiO-67, and UiO-68, respectively. The polyMOFs showed a permanent porosity, as their parent MOF structures do, and some of these polyMOFs inherited the hydrophobicity of their polymer ligands.…”

Section: Maf-x12mentioning

confidence: 99%

Hydrophobic Metal–Organic Frameworks: Assessment, Construction, and Diverse Applications

et al. 2020

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Tens of thousands of metal–organic frameworks (MOFs) have been developed in the past two decades, and only ≈100 of them have been demonstrated as porous and hydrophobic. These hydrophobic MOFs feature not only a rich structural variety, highly crystalline frameworks, and uniform micropores, but also a low affinity toward water and superior hydrolytic stability, which make them promising adsorbents for diverse applications, including humid CO2 capture, alcohol/water separation, pollutant removal from air or water, substrate‐selective catalysis, energy storage, anticorrosion, and self‐cleaning. Herein, the recent research advancements in hydrophobic MOFs are presented. The existing techniques for qualitatively or quantitatively assessing the hydrophobicity of MOFs are first introduced. The reported experimental methods for the preparation of hydrophobic MOFs are then categorized. The concept that hydrophobic MOFs normally synthesized from predesigned organic ligands can also be prepared by the postsynthetic modification of the internal pore surface and/or external crystal surface of hydrophilic or less hydrophobic MOFs is highlighted. Finally, an overview of the recent studies on hydrophobic MOFs for various applications is provided and suggests the high versatility of this unique class of materials for practical use as either adsorbents or nanomaterials.

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Isoreticular expansion of polyMOFs achieves high surface area materials

Abstract: Polymer–MOF hybrid materials (polyMOFs) are shown to adhere to the principle of isoreticular expansion, generating polyMOFs with large surface areas and enhanced stability.

Cited by 59 publications

References 36 publications

polyMOF Formation from Kinked Polymer Ligands via ortho‐Substitution

polyMOF Formation from Kinked Polymer Ligands via ortho‐Substitution

Supramolecular Metallopolymers: From Linear Materials to Infinite Networks

Hydrophobic Metal–Organic Frameworks: Assessment, Construction, and Diverse Applications

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