Enhanced sorption in an indium-acetylenedicarboxylate metal–organic framework with unexpected chains of <i>cis</i>-μ-OH-connected {InO<sub>6</sub>} octahedra

Woschko, Dennis; Yilmaz, Süheyla; Jansen, Christian; Spieß, Alex; Oestreich, Robert; Ntep, Tobie Junior J. Matemb Ma; Janiak, Christoph

doi:10.1039/d2dt03719j

Cited by 3 publications

(19 citation statements)

References 76 publications

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“…The average P–N–P bond angle is 120.3° and the N–P–N bond angle is 117.3°. These values closely resemble those reported for previously studied P 3 N 3 derivatives. – ,– The bond lengths of In–O carboxylates in the inorganic SBUs {InO 7 } are in the range from 2.117 to 2.373 Å, which is analogous to other In–O carboxylate bond distances reported in the literature, and the distorted C aromatic –O substituted –P central angle are in the range of 117.2 to 131.9°. The In–O(water) and In–O(DMF) bond distances are 2.163(3) and 2.173(3) Å, respectively.…”

Section: Resultssupporting

confidence: 87%

Construction of Indium(III)–Organic Framework Based on a Flexible Cyclotriphosphazene-Derived Hexacarboxylate as a Reusable Green Catalyst for the Synthesis of Bioactive Aza-Heterocycles

Jeevananthan,

Senadi,

Muthu

et al. 2024

Inorg. Chem.

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The constant demand for eco-friendly methods of synthesizing complex organic compounds inspired researchers to design and develop modern, highly efficient heterogeneous catalytic systems. Herein, In-HCPCP metal−organic framework (SRMIST−1), a heterogeneous Lewis acid catalyst containing less toxic indium and eco-friendly robust cyclotriphosphazene and exhibiting notable chemical and thermal stability, durable catalytic activity, and exceptional reusability was produced through the reaction between indium(III) nitrate hydrate and hexakis(4-carboxylatophenoxy)-cyclotriphosphazene. In the SRMIST−1 structure, secondary building units {InO 7 } are assembled by a connection of η 2 -and η 1 -carboxylic oxo atoms from different HCPCP ligands, forming a three-dimensional network. The occurrence of regularly distributed In(III) sites in SRMIST−1 confers superior reactivity on the catalyst toward the synthesis of 2,3-dihydroquinazolin-4(1H)-ones and 3,4-dihydro-2H-1,2,4-benzothiadiazine-1,1-dioxides by the cyclization reaction of 2-aminobenzamides and 2-aminobenzenesulphonamides with aldehydes under optimized reaction conditions, respectively. The notable features of this method include broad functional group compatibility, low catalyst loading (1−5 mol %), mild reaction conditions, easy workup procedures, good to excellent reaction yields, ethanol as a green solvent, reusability of the catalyst (five cycles), and economic attractiveness, which is mainly due to sustainability of SRMIST−1 as a reusable green catalyst. Our findings demonstrate that the highly reactive and reusable green catalyst finds widespread applications in medicinal chemistry.

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Section: Resultssupporting

confidence: 87%

Construction of Indium(III)–Organic Framework Based on a Flexible Cyclotriphosphazene-Derived Hexacarboxylate as a Reusable Green Catalyst for the Synthesis of Bioactive Aza-Heterocycles

Jeevananthan,

Senadi,

Muthu

et al. 2024

Inorg. Chem.

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“…The absence of significant hysteresis in ortho-1 indicates that there are no kinetic restrictions for the guest molecule desorption. 12,56,114 The vapor uptake for ortho-1 is in the lower relative pressure regions significantly higher than for 2, which we trace to the presence of the small channels in ortho-1. The small channels in ortho-1 with a cross-section of 4 Å × 8 Å can provide good interactions with both ends of the adsorbed molecule to opposite surfaces of the adsorbent.…”

Section: Gas Sorptionmentioning

confidence: 57%

“…This could be interpreted as an advantage of a −C�C− triple bond over a phenylene spacer in the linker for CO 2 adsorption. 16,39,53,56 However, comparison of adsorption data from different sources must be done with care and can be misleading, for example, in view of different activation protocols and the thereby achieved porosity.…”

Section: Gas Sorptionmentioning

confidence: 99%

“…The removal of nhexane is relevant because of its metabolization to 2,5hexanedione, which is a nerve-damaging and toxic compound. 10,56,112 Furthermore, benzene and cyclohexane have similar physical properties such as boiling point and vapor pressure. Consequently, the petrochemical industry has to rely on cost-intensive devices and energy-intensive distillation processes to obtain phase-pure products and is looking for better alternatives, such as using MOFs for physisorptive separation.…”

Section: Gas Sorptionmentioning

confidence: 99%

“…Consequently, the petrochemical industry has to rely on cost-intensive devices and energy-intensive distillation processes to obtain phase-pure products and is looking for better alternatives, such as using MOFs for physisorptive separation. 56,111,113 MOFs with triple bonds, as in ortho-1 and 2, are interesting candidates for separation since double or triple bonds could interact with benzene through π⋯π interactions. 56,93 Similar to the gas sorption measurements, ortho-1 was activated for 3 h at 120 °C in vacuum (10 −7 mbar) and 2 for 7 h at 130 °C in vacuum (10 −7 mbar).…”

Section: Gas Sorptionmentioning

confidence: 99%

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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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A comprehensive review on the enantiomeric separation of chiral drugs using metal-organic frameworks

Abbas,

Ahmad,

Cheng

et al. 2024

Chemosphere

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Enhanced sorption in an indium-acetylenedicarboxylate metal–organic framework with unexpected chains of cis-μ-OH-connected {InO₆} octahedra

Abstract: Single crystals of the new metal-organic framework (MOF) In-adc (HHUD-4) were obtained through the reaction of the linear acetylenedicarboxylic acid (H2adc) with In(NO3)3·x H2O as a racemic conglomerate in the...

Cited by 3 publications

References 76 publications

Construction of Indium(III)–Organic Framework Based on a Flexible Cyclotriphosphazene-Derived Hexacarboxylate as a Reusable Green Catalyst for the Synthesis of Bioactive Aza-Heterocycles

Construction of Indium(III)–Organic Framework Based on a Flexible Cyclotriphosphazene-Derived Hexacarboxylate as a Reusable Green Catalyst for the Synthesis of Bioactive Aza-Heterocycles

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

A comprehensive review on the enantiomeric separation of chiral drugs using metal-organic frameworks

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Enhanced sorption in an indium-acetylenedicarboxylate metal–organic framework with unexpected chains of cis-μ-OH-connected {InO6} octahedra

Abstract: Single crystals of the new metal-organic framework (MOF) In-adc (HHUD-4) were obtained through the reaction of the linear acetylenedicarboxylic acid (H2adc) with In(NO3)3·x H2O as a racemic conglomerate in the...

Cited by 3 publications

References 76 publications

Construction of Indium(III)–Organic Framework Based on a Flexible Cyclotriphosphazene-Derived Hexacarboxylate as a Reusable Green Catalyst for the Synthesis of Bioactive Aza-Heterocycles

Construction of Indium(III)–Organic Framework Based on a Flexible Cyclotriphosphazene-Derived Hexacarboxylate as a Reusable Green Catalyst for the Synthesis of Bioactive Aza-Heterocycles

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

A comprehensive review on the enantiomeric separation of chiral drugs using metal-organic frameworks

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Product

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Enhanced sorption in an indium-acetylenedicarboxylate metal–organic framework with unexpected chains of cis-μ-OH-connected {InO₆} octahedra