Pillar-layered MOFs: functionality, interpenetration, flexibility and applications

Zarekarizi, Farnoosh; Joharian, Monika; Morsali, Ali

doi:10.1039/c8ta03306d

Cited by 157 publications

(103 citation statements)

References 602 publications

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“…The second structural motif prototypical for go ‐type SPCs are pillared‐layer structures in which π–π‐type interactions stabilize the cp state . These SPCs predominantly consist of carboxylate‐based ligands coordinated to paddle‐wheel‐type metal nodes that are connected by axially coordinated neutral ligands, forming a 3D framework . This building concept provides local modes predesigned for lattice distortion via hinging along the 1D pore channels .…”

Section: Structural Softness Transitions and Dynamicsmentioning

confidence: 99%

Chemistry of Soft Porous Crystals: Structural Dynamics and Gas Adsorption Properties

2020

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In this Minireview, we discuss the fundamental chemistry of soft porous crystals (SPCs) by characterizing their common structural features and the resulting structural softness and transitions. In particular, we focus on the recently emerging properties based on metastable transitions and those arising from local dynamics. By comparing the resulting adsorption properties to those of commonly applied rigid adsorbents, we highlight the potential of SPCs to revolutionize adsorption‐based technologies, considering our current understanding of the thermodynamic and kinetic aspects. We provide brief outlines for the experimental and computational characterization of such phenomena and offer an outlook toward next‐generation SPCs likely to be discovered in the next decade.

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Section: Structural Softness Transitions and Dynamicsmentioning

confidence: 99%

Chemistry of Soft Porous Crystals: Structural Dynamics and Gas Adsorption Properties

2020

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“…The importance of metal-node hinges and their energetics for framework switchability has been widely investigated for compounds such as M(bdp) (M ¼ Co, Fe, bdp ¼ 1,4-benzenedipyrazolate), 11,23,24 M(m-OH)(bdc) (MIL-53, M ¼ Cr, Al, Fe, bdc ¼ 1,4-benzenedicarboxylate) 25-27 and pillared layer MOFs with the general formula M 2 L 2 P, (L ¼ ditopic carboxylate, P ¼ neutral pillar). 17,28,29 In pillared layer MOFs, binuclear paddle wheel nodes M 2 (COO) 4 are connected by ditopic carboxylates to form 2D grids, which are pillared by neutral diamine donor ligands to form a 3D framework with pcu topology. Several pillared layer MOFs show some degree of framework exibility and they can be synthesised using a variety of transition metals, such as Co, Ni, Cu, and Zn, rendering them an ideal model system to achieve a deeper understanding of framework switchability.…”

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confidence: 99%

Crystal size versus paddle wheel deformability: selective gated adsorption transitions of the switchable metal–organic frameworks DUT-8(Co) and DUT-8(Ni)

et al. 2019

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Crystal size versus paddle wheel deformability: selective gated adsorption transitions of the switchable metal-organic frameworks and † Switchable pillared layer metal-organic frameworks M 2 (2,6-ndc) 2 (dabco) (DUT-8(M), M ¼ Ni, Co, 2,6-ndc ¼ 2,6naphthalenedicarboxylate, dabco ¼ 1,4-diazabicyclo-[2.2.2]octane, DUT -Dresden University of Technology) were synthesised in two different crystallite size regimes to produce particles up to 300 mm and smaller particles around 0.1 mm, respectively. The textural properties and adsorption-induced switchability of the materials, obtained from both syntheses, were studied by physisorption of N 2 at 77 K, CO 2 at 195 K and nbutane at 273 K, revealing pronounced differences in adsorption behavior for Ni and Co analogues. While the smaller nano-sized particles (50-200 nm) are rigid and show no gating transitions confirming the importance of crystallite size, the large particles show pronounced switchability with characteristic differences for the two metals resulting in distinct recognition effects for various gases and vapours. Adsorption of various vapours demonstrates consistently a higher energetic barrier for the "gate opening" of DUT-8(Co) in contrast to , as the "gate opening" pressure for Co based material is shifted to a higher value for adsorption of dichloromethane at 298 K. Evaluation of crystallographic data, obtained from single crystal and powder X-ray diffraction analysis, showed distinct geometric differences in the paddle wheel units of the respective MOFs.These differences are further disclosed by solid-state UV-vis, FT-IR and Raman spectroscopy. Magnetic properties of DUT-8(Co) and DUT-8(Ni) were investigated, indicating a high-spin state for both materials at room temperature. Density functional theory (DFT) simulations confirmed distinct energetic differences for Ni and Co analogues with a higher energetic penalty for the structural "gate opening" transformation for DUT-8(Co) compared to DUT-8(Ni) explaining the different flexibility behaviour of these isomorphous MOFs.underlying structural phase transitions are triggered by adsorption or desorption of guest molecules and generally characterised by an activation energy barrier, which causes hysteresis in physisorption experiments. Due to their switchable nature, so porous crystals are oen discussed as materials with huge application potential in gas storage, 11 separation processes, 12,13 sensor technology 14,15 and catalysis. 16 Despite rapidly growing research in the eld of exible MOFs, 1,17-21 the role of critical factors inuencing and controlling framework switchability are barely understood. 22 As MOFs are modular networks, the exibility of the linker but also the hinges of the metal node are key features that affect switchability. The importance of metal-node hinges and their energetics for framework switchability has been widely investigated for compounds such as M(bdp) (M ¼ Co, Fe, bdp ¼ 1,4-benzenedipyrazolate), 11,23,24 M(m-OH)(bdc) (MIL-53, M ¼ Cr, Al, Fe, bdc ¼ 1,4-benzenedicarboxylate)...

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“…The new MOF, KSU-100, has the BPDC-(NH 2 ) 2 linkers connected by Zn paddle-wheel clusters, defining the xy-plane in a sql net. This 2D net is then pillared together by the DPG ligand to form a pcu framework with large pore dimensions of 11Å × 11Å × 9Å, and a low calculated density of 0.392 g/cm 3 . Powder X-ray diffraction (PXRD) of bulk samples of single-crystals of the material confirmed the purity of the structure (Figure 3a, and Figure S1 in Supporting Information for the indexed pattern).…”

Section: Resultsmentioning

confidence: 99%

“…While there are a variety of ways to assemble well-defined, multifunctional metal-organic framework (MOF) materials [1], the construction of mixed-linker, pillared paddle-wheel MOFs is the most efficacious ( Figure 1) [2]. Their assembly provides a reliable strategy for introducing two different organic linkers into an MOF, allowing for the chemical pore environment to be tuned with high fidelity [3]. Despite the advantages that they offer, following their first introduction, pillared paddle-wheel frameworks have received much less attention than their potential would warrant.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen-Bonding Linkers Yield a Large-Pore, Non-Catenated, Metal-Organic Framework with pcu Topology

2020

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Pillared paddle-wheel-based metal-organic framework (MOF) materials are an attractive target as they offer a reliable method for constructing well-defined, multifunctional materials. A drawback of these materials, which has limited their application, is their tendency to form catenated frameworks with little accessible volume. To eliminate this disadvantage, it is necessary to investigate strategies for constructing non-catenated pillared paddle-wheel MOFs. Hydrogen-bonding substituents on linkers have been postulated to prevent catenation in certain frameworks and, in this work, we present a new MOF to further bolster this theory. Using 2,2′-diamino-[1,1′-biphenyl]-4,4′-dicarboxylic acid, BPDC-(NH2)2, linkers and dipyridyl glycol, DPG, pillars, we assembled a MOF with pcu topology. The new material is non-catenated, exhibiting large accessible pores and low density. To the best of our knowledge, this material constitutes the pcu framework with the largest pore volume and lowest density. We attribute the lack of catenation to the presence of H-bonding substituents on both linkers.

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Pillar-layered MOFs: functionality, interpenetration, flexibility and applications

Abstract: Pillar-layered metal–organic frameworks (MOFs) are among the most interesting research areas in crystalline materials.

Cited by 157 publications

References 602 publications

Chemistry of Soft Porous Crystals: Structural Dynamics and Gas Adsorption Properties

Chemistry of Soft Porous Crystals: Structural Dynamics and Gas Adsorption Properties

Crystal size versus paddle wheel deformability: selective gated adsorption transitions of the switchable metal–organic frameworks DUT-8(Co) and DUT-8(Ni)

Hydrogen-Bonding Linkers Yield a Large-Pore, Non-Catenated, Metal-Organic Framework with pcu Topology

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