A diamantane-4,9-dicarboxylate based UiO-66 analogue: challenging larger hydrocarbon cage platforms

Gvilava, Vasily; Vieten, Maximilian; Oestreich, Robert; Woschko, Dennis; Steinert, Moritz; Boldog, Ishtvan; Bulánek, Roman; Fokina, Natalie A.; Schreiner, Peter R.; Janiak, Christoph

doi:10.1039/d2ce01170k

Cited by 4 publications

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“…In this work, we investigate two MOFs with the linker 1,2-bis(1 H -pyrazol-4-yl)ethyne (H 2 bpe) (Figure d), which adds to the topical subject of MOFs with acetylene-units in the linker backbone. ,,,− The −CC– triple bond spacer in the acetylene-dicarboxylate linker was said to result in the HHUD MOFs in high hydrophilicity, high CO 2 adsorption capacity, and enthalpy compared to aliphatic or aromatic spacer moieties. ,,, Based on the structural similarity of carboxylates and pyrazolates regarding the bridging action of adjacent metal atoms in metal-cluster SBUs, − we investigate here the shortest acetylene-bis-pyrazolate linker 4,4′-(ethyne-1,2-diyl)bis(pyrazolate) (bpe 2– ) (Figure d) in a Zn- and in a Ni-MOF. We introduce the single-crystal structure of [Zn(bpe)]·1.8DMF (ortho- 1 ·1.8DMF, HHUD-5), − which crystallizes in an orthorhombic space group. For this MOF [Zn(bpe)]·1.2DMF, Moroni et al recently published a Rietveld-refined structure in a tetragonal space group (tetra- 1 ·1.2DMF), which had been the only publication of a bpe-MOF, so far .…”

Section: Introductionmentioning

confidence: 99%

Metal–Organic Azolate Frameworks with an Acetylene-bis-pyrazolate Linker: Assessing the Role of the Triple-Bond Spacer in Gas and Vapor Sorption

Jordan,

Müller,

Oestreich

et al. 2024

Crystal Growth & Design

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The reaction of the diprotonated linker precursor in the form of the salt [H 4 bpe 2+ ](TFA − ) 2 (H 2 bpe = 1,2-bis(1Hpyrazol-4-yl)ethyne; HTFA = trifluoroacetic acid) with Zn(NO 3 ) 2 • 4H 2 O in DMF at 75 °C for 9 days led to single crystals of the metal−organic framework (MOF) [Zn(bpe)]•1.8DMF (ortho-1• 1.8DMF) (HHUD-5). The compounds crystallize in the orthorhombic space group Fddd with rhombic channels, and is a polymorph of the previously reported structure of [Zn(bpe)]• 1.2DMF (tetra-1•1.2DMF) that crystallizes in the tetragonal space group P4 2 /mmc and features square channels as established from powder X-ray diffraction (PXRD) data. Microporous ortho-1 and tetra-1 demonstrate similar porosities with surface areas (pore volumes) of 2135 m 2 /g (0.77 cm 3 /g at p/p 0 = 0.95) and 1904 m 2 /g (0.73 cm 3 /g at p/p 0 = 0.95) when an optimized activation is employed (1380 m 2 /g was reported previously for tetra-1). Reaction of the boc-protected linker precursor Boc 2 bpe with Ni(OAc) 2 • 4H 2 O in DMF/water under reflux yielded the MOF [Ni 8 (OH) 4 (H 2 O) 2 (bpe) 6 ]•nSolv (2•nSolv, HHUD-6), which crystallized in the cubic space group Fm m 3 established from PXRD. Compound 2 is the newest member of the isoreticular series of [Ni 8 (OH) 4 (H 2 O) 2 L 6 ] (L = bis-pyrazolate or carboxylate-pyrazolate) and exhibits a surface area of 1415 m 2 /g and a pore volume of 0.78 cm 3 /g at p/p 0 = 0.80. The CO 2 uptake at 273 K and 1 bar was 3.99 mmol/g for ortho-1 and 5.84 mmol/g for 2; the CH 4 uptake was 1.11 mmol/g for ortho-1 and 1.64 mmol/g for 2, all in line with the higher heat of adsorption of the gases in 2, where open metal sites are possible after activation. Above 2 bar for CO 2 , and above 6 bar for CH 4 , the uptake in ortho-1 surpasses that in 2 due to the higher surface area of ortho-1. Both MOFs show high H 2 uptakes of 11.6 mmol/g for ortho-1 and 8.7 mmol/g for 2 at 77 K and 1 bar. Comparison to the CO 2 , CH 4 , and H 2 uptake in the analogous MOFs with the slightly longer 4,4′-(1,4phenylene)bis(pyrazolate) linker (having phenylene instead of acetylene spacer) suggests an advantage of the −C�C− triple bond.Vapor adsorption experiments with volatile organic compounds at 293 K for ortho-1 yielded uptakes of 8.2 mmol/g for benzene, 6.6 mmol/g for cyclohexane, and 5.7 mmol/g for n-hexane with type I isotherms. Compound 2 gave uptakes of 10.4 mmol/g for benzene, 10.7 mmol/g for cyclohexane, and 8.8 mmol/g for n-hexane with type II isotherms. Both MOFs are water stable as indicated by water vapor sorption and stability tests which also show a hydrophobicity of the bpe 2− linker.

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Section: Introductionmentioning

confidence: 99%

Metal–Organic Azolate Frameworks with an Acetylene-bis-pyrazolate Linker: Assessing the Role of the Triple-Bond Spacer in Gas and Vapor Sorption

Jordan,

Müller,

Oestreich

et al. 2024

Crystal Growth & Design

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“…Therefore, having a new sub‐set of linkers with a “3D‐core” introduced to the synthetic toolbox is imperative to enrich the MOF database through providing MOFs with pore walls made from non‐traditional linkers. These 3D‐linkers are already emerging in the MOF literature in the form of 3D‐linker MOFs (3DL‐MOFs), which often show exceptional properties in comparison to their aromatic analogues [11–16] . To introduce these valuable 3D‐linkers into our synthetic toolbox, a clearer understanding of exactly what characteristics define a 3D‐linker is important.…”

Section: Introductionmentioning

confidence: 99%

“…These 3Dlinkers are already emerging in the MOF literature in the form of 3D-linker MOFs (3DL-MOFs), which often show exceptional properties in comparison to their aromatic analogues. [11][12][13][14][15][16] To introduce these valuable 3D-linkers into our synthetic toolbox, a clearer understanding of exactly what characteristics define a 3D-linker is important. These characteristics are based on how the linker affects the local pore environment with sub-angstrom control and precision.…”

Section: Introductionmentioning

confidence: 99%

Expanding Linker Dimensionality in Metal‐organic Frameworks for sub‐Ångstrom Pore Control for Separation Applications

et al. 2023

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Metal-organic frameworks (MOFs) are a class of porous materials with high surface areas, which are acquiring rapid attention on an exponential basis. A significant characteristic of MOFs is their ability to act as adsorbents to selectively separate component mixtures of similar size, thereby addressing the technological need for an alternative approach to conventional distillation methods. Recently, MOFs comprising a 3-Dimensional (3D) linker have shown outstanding capabilities for difficult separations compared to the parent 2-Dimensional (2D) analogue. 3D-linkers with a polycyclic core are underrepresented in the MOF database due to the widespread preferred use of 2D-linkers and the misconceived high-cost of 3D linkers. We summarize the recent research of 3D-linker MOFs and highlight their beneficial employment for selective gas and hydrocarbon adsorption and separation. Furthermore, we outline forecasts in this area to create a platform for widespread adoption of 3D-linkers in MOF synthesis.

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“…UiO‐66 analogs with relatively small cage‐based bridging ligands were reported with bicyclo[1.1.1]pentane‐1,3‐dicarboxylate [36] and bicyclo[2.2.2]octane‐1,4‐dicarboxylate (NU‐403) [37] . Recently, we have reported the bulky 4,9‐adamantanedicarboxylate‐based analogue (HHUD‐3), [38] which shows porosity only due to the presence of defects.…”

Section: Introductionmentioning

confidence: 99%

[Zr₆(μ₃‐O)₄(μ₃‐OH)₄](1‐adamantanecarboxylate)₁₂]: a model for extrinsic “defect‐engineerable” porosity

Gvilava

Vieten

Heinen

et al. 2023

Zeitschrift anorg allge chemie

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The molecular zirconium‐oxo cluster with 1‐adamantanecarboxylate of ideal formula [Zr6O4(OH)4(AdCA)12] (AdCA=1‐adamantanecarboxylate) has a near spherical shape with a hydrophobic “shell” of bulky rigid adamantyl groups. The use of formic acid as a modulator and a large excess of the HAdCA were found to be crucial for its reproducible synthesis and the formation of ~100‐150 μm well‐formed rhombohedral single crystals. Crystallization in the presence of formic acid leads, however, to ligand‐substitution defects (1‐2 out of 12) which were quantified by thermogravimetry and NMR. A defect‐engineering with a higher defect ratio in such oxo clusters is a promising approach aiming at extrinsic porosity.

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A diamantane-4,9-dicarboxylate based UiO-66 analogue: challenging larger hydrocarbon cage platforms

Abstract: The first use of the bulky barrel-shaped ligand is demonstrated in HHUD-3, with accessible porosity only feasible for a defect structure. With 35%+ missing linker defects and SBET=890 m2g–1 (N2),...

Cited by 4 publications

References 50 publications

Metal–Organic Azolate Frameworks with an Acetylene-bis-pyrazolate Linker: Assessing the Role of the Triple-Bond Spacer in Gas and Vapor Sorption

Metal–Organic Azolate Frameworks with an Acetylene-bis-pyrazolate Linker: Assessing the Role of the Triple-Bond Spacer in Gas and Vapor Sorption

Expanding Linker Dimensionality in Metal‐organic Frameworks for sub‐Ångstrom Pore Control for Separation Applications

[Zr₆(μ₃‐O)₄(μ₃‐OH)₄](1‐adamantanecarboxylate)₁₂]: a model for extrinsic “defect‐engineerable” porosity

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A diamantane-4,9-dicarboxylate based UiO-66 analogue: challenging larger hydrocarbon cage platforms

Abstract: The first use of the bulky barrel-shaped ligand is demonstrated in HHUD-3, with accessible porosity only feasible for a defect structure. With 35%+ missing linker defects and SBET=890 m2g–1 (N2),...

Cited by 4 publications

References 50 publications

Metal–Organic Azolate Frameworks with an Acetylene-bis-pyrazolate Linker: Assessing the Role of the Triple-Bond Spacer in Gas and Vapor Sorption

Metal–Organic Azolate Frameworks with an Acetylene-bis-pyrazolate Linker: Assessing the Role of the Triple-Bond Spacer in Gas and Vapor Sorption

Expanding Linker Dimensionality in Metal‐organic Frameworks for sub‐Ångstrom Pore Control for Separation Applications

[Zr6(μ3‐O)4(μ3‐OH)4](1‐adamantanecarboxylate)12]: a model for extrinsic “defect‐engineerable” porosity

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[Zr₆(μ₃‐O)₄(μ₃‐OH)₄](1‐adamantanecarboxylate)₁₂]: a model for extrinsic “defect‐engineerable” porosity