A Highly Chemically Robust 3D Interpenetrated MOF Heterogeneous Catalyst for the Synthesis of Hantzsch 1,4‐Dihydropyridines and Drug Molecules

Small, Journal Year: 2024, Volume and Issue: 20(25)

Published: Jan. 8, 2024

Abstract Metal–organic frameworks (MOFs) have attracted immense attention as efficient heterogeneous catalysts over other solid catalysts, however, their chemical environment instability often limits catalytic potential. Herein, utilizing a flexible unexplored tetra‐acid ligand and employing the mixed approach, 3D interpenetrated robust framework is strategically developed, IITKGP‐51 (IITKGP stands for Indian Institute of Technology Kharagpur), which retained its crystallinity wide range pH solution (4–12). Having ample open metal sites (OMSs), explored catalyst in one‐pot Hantzsch condensation reaction, with low loading broad substrates. The synthesis drug molecules remains one most significant emergent areas organic medicinal chemistry. Considering such practical utility, biologically important Nemadipine B Nifedipine (calcium channel protein inhibitor) are synthesized first time by using this fully characterized via SC‐XRD spectroscopic methods. This report inaugurates usage MOF material molecules.

Language: Английский

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Nanoporous {Pb₃}-Organic Framework for Catalytic Cycloaddition of CO₂ with Epoxides and Knoevenagel Condensation

ACS Applied Nano Materials, Journal Year: 2023, Volume and Issue: 6(24), P. 23196 - 23206

Published: Dec. 5, 2023

Because of increasingly serious environmental problems and resource shortages, chemically fixing surplus CO2 into value-added products has gradually become a challenging hot research topic, in which the preparation zeolite-like metal–organic frameworks (MOFs) with rich Lewis acid–base sites nanopores is cornerstone. Herein, butterfly-shaped [Pb3(COO)6(H2O)2(Npyridine)2] cluster, polynitro tritopic carboxylic acid 2,4,6-tri(4-carboxy-2-nitrophenyl)-1,3,5-trinitrobenzene (H3TCNT), 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (TPT) engender highly robust microporous framework [Pb3(TCNT)2(TPT)(H2O)2]n (NUC-91) rectangular nanochannels (15.28 × 12.16 Å2) along b axis. extremely functional such as acidic Pb2+ ions basic free nitrogen atoms on inner surface void volumes, activated NUC-91a heterogeneous catalyst can effectively catalyze cycloaddition various epoxides under mild conditions. For substrates 2-methyloxirane, 2-fluorooxirane, 2-ethyloxirane, 2-(trifluoromethyl)oxirane, oxiran-2-ylmethanol, 2-vinyloxirane, 2-phenyloxirane, transformation to related cyclic carbonates could reach 99% turnover number (TON) frequency (TOF) 825 206 h–1, respectively. Moreover, Knoevenagel condensation reactions aldehydes malononitrile be efficiently effected by NUC-91a. Therefore, this work provided simple strategy for prefunctionalizing widely used ligands, employed design catalytic facilitate capture conversion CO2.

Language: Английский

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Advances on silver-based MOFs and/or CPs and their composites: Synthesis strategies and applications

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 514, P. 215924 - 215924

Published: May 11, 2024

Language: Английский

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Mechanistical Insights into the Ultrasensitive Detection of Radioactive and Chemotoxic UO₂²⁺ Ions by a Porous Anionic Co-Metal–Organic Framework

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(22), P. 10403 - 10413

Published: May 18, 2024

Development of a simple, cost-efficient, and portable UO22+ sensory probe with high selectivity sensitivity is highly desirable in the context monitoring radioactive contaminants. Herein, we report luminescent Co-based metal–organic framework (MOF), {[Me2NH2]0.5[Co(DATRz)0.5(NH2BDC)]·xG}n (1), equipped abundant amino functionalities for selective detection uranyl cations. The ionic structure consists two types channels decorated plentiful Lewis basic moieties, which trigger stronger acid–base interaction diffused cationic units thus can selectively quench fluorescence intensity presence other interfering ions. Furthermore, limit sensing was achieved to be as low 0.13 μM (30.94 ppb) rapid responsiveness multiple recyclabilities, demonstrating its excellent efficacy. Density functional theory (DFT) calculations further unraveled preferred binding sites ions tubular channel MOF structure. Orbital hybridization between NH2BDC/DATRz together significantly large electron-accepting ability identified responsible luminescence quenching. More importantly, prepared 1@PVDF {poly(vinylidene difluoride)} mixed-matrix membrane (MMM) displayed good activity comparable 1, great significance their practical employment MOF-based luminosensors real-world application.

Language: Английский

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Recent progress on organic metal compound/MOF hybrids: From controllable synthesis to potential catalytic applications

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 515, P. 215972 - 215972

Published: May 27, 2024

Language: Английский

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Two-Dimensional Cu(II)-MOF with Lewis Acid–Base Bifunctional Sites for Chemical Fixation of CO₂ and Bioactive 1,4-DHP Synthesis via Hantzsch Condensation

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(23), P. 10832 - 10842

Published: May 29, 2024

Five- and six-membered heterocycles containing nitrogen or oxygen have been considered as privileged scaffolds in organic chemistry the chemical industry because of their usage high-value commodities. Herein, we report a two-dimensional (2D) Cu(II)-based MOF catalyst, IITKGP-40, via strategic employment ample Lewis acid–base bifunctional sites (open metal nodes free pyrazine moieties) along pore wall. IITKGP-40 could convert toxic CO2 to cyclic carbonates an atom-economical manner under solvent-free conditions aromatic aldehyde bioactive 1,4-DHPs Hantzsch condensation. Exceptional catalytic performance (99%) turnover number mild reaction for fixation using sterically hindered styrene oxide, good-to-excellent yields wide range aldehydes toward 1,4-dihydropyridines (1,4-DHPs) make promising multipurpose heterogeneous catalyst. Moreover, demonstrate practical utility two biologically important drug molecules, diludine nitrendipine analogue, also synthesized. is recyclable at least three consecutive runs without significant loss activity, making it real-time applications.

Language: Английский

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A Chemically Robust 2D Ni‐MOF as an Efficient Heterogeneous Catalyst for One‐Pot Synthesis of Therapeutic and Bioactive 2‐Amino‐3‐Cyano‐4H‐Pyran Derivatives

ChemSusChem, Journal Year: 2024, Volume and Issue: unknown

Published: July 10, 2024

Abstract Despite possessing numerous catalytic advantages of MOFs, developing 2D frameworks having excellent chemical stability along with new properties remains a grand challenge. Herein, by employing mixed ligand synthetic approach, we have constructed Ni‐MOF, IITKGP‐52 , which exhibits framework robustness in open air, water, as well over wide range aqueous pH solutions (2–12). Benefitting from its and abundant Lewis acidic metal sites (OMSs), is explored catalyzing the heterogeneous three‐component condensation reaction for tandem synthesis bioactive 2‐amino‐3‐cyano‐4H‐pyran derivatives low loading, greater compatibility substrates, recyclability superior efficiency than previously employed homo systems. inaugurates employment MOF‐based catalysts one‐pot therapeutic derivatives.

Language: Английский

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Isoreticular Metal–Organic Frameworks Confined Mononuclear Ru-Hydrides Enable Highly Efficient Shape-Selective Hydrogenolysis of Polyolefins

JACS Au, Journal Year: 2023, Volume and Issue: 3(12), P. 3473 - 3484

Published: Dec. 9, 2023

Upcycling nonbiodegradable plastics such as polyolefins is paramount due to their ever-increasing demand and landfills after usage. Catalytic hydrogenolysis highly appealing convert into targeted value-added products under mild reaction conditions compared with other methods, high-temperature incineration pyrolysis. We have developed three isoreticular zirconium UiO-metal–organic frameworks (UiO-MOFs) node-supported ruthenium dihydrides (UiO-RuH2), which are efficient heterogeneous catalysts for of polyethylene at 200 °C, affording liquid hydrocarbons a narrow distribution excellent selectivity via shape-selective catalysis. UiO-66-RuH2 catalyzed single-use low-density (LDPE) produced C12 centered bell-shaped C8–C16 alkanes in >80% yield 90% the phase. By tuning pore sizes UiO-RuH2 MOF catalysts, could be systematically altered, different fuel-grade from LDPE high yields. Our spectroscopic theoretical studies control experiments reveal that enable upcycling plastic wastes owing unique combination coordinatively unsaturated single-site Ru-active sites, uniform tunable pores, well-defined porous structure, superior stability. The kinetics calculations also identify C–C bond scission involving β-alkyl transfer turnover-limiting step.

Language: Английский

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Separation of Propylene and Propane Using Metal–Organic Frameworks

Comments on Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 44(3), P. 203 - 233

Published: Sept. 27, 2023

ABSTRACTPropylene (C3H6) is a crucial olefin raw material used in the production of polypropylene, which world's second-most produced synthetic plastic. Separating propylene from propane (C3H8) an important and significant challenge for industry due to similar molecular sizes physical properties these gases. At present, usual method this separation energy-intensive cryogenic distillation, has low efficiency high energy consumption. Therefore, energy-efficient alternative way urgent demand. Metal-organic frameworks (MOFs) are promising candidates propylene/propane separation, thanks well-defined, designable, modifiable, flexible structures. This review provides summary recent development MOFs that able discriminate between propane. The key factors determine performance MOFs, primarily perspectives pore size, presence open metal sites (OMS) membranes summarized. Besides, challenges must be addressed further separations utilizing also discussed.KEYWORDS: frameworksseparationadsorptionpore sizeopen Disclosure statementNo potential conflict interest was reported by author(s).Additional informationFundingThis work supported "The Belt Road" Innovative Talent Exchange Foreign Experts Project (DL2022006007L), Scientific Research Educational Department Liaoning Province (LJ2019011), National Natural Science Foundation China (22301191, 21671139), postdoctoral (2023M731798). A.S.P. acknowledges Ministry Higher Education Russian Federation (121031700321-3).

Language: Английский

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Highly Scalable and Robust Ribbon-like Coordination Polymer as Green Catalyst for Hantzsch Condensation in Synthesis of DHPs and Bioactive Drug Molecule

Materials Today Catalysis, Journal Year: 2024, Volume and Issue: 5, P. 100051 - 100051

Published: May 12, 2024

Ribbon-like coordination polymers (CP) represents a highly unexplored innovative class of metal-coordination network. Herein, we have developed scalable and chemically robust (pH=3-10 stable) ribbon-like CP [{Cu(Pim)(L)(H2O).H2O}]n (1) following complete environment-friendly green synthesis route. Considering the presence surface flanked labile coordinated water molecules their appealing correlation with one-dimensional structural characteristics, such sort was explored for first time as excellent heterogeneous catalyst largely three-component Hantzsch condensation different classes dihydropyridine (DHP). Moreover, 1 is employed to synthesize bio-responsive drug 'Ethidine' (possessing high anti-oxidant anticarcinogenic properties) characterized Single Crystal X-ray Diffraction (SCXRD) analysis. Several DHP-based products are also analysed through in-depth SCXRD This report inaugurates usage Cu(II) based CPs environmentally benign manner bioactive DHPs Drugs.

Language: Английский

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