Amide Functionalized Mesoporous MOF LOCOM-1 as a Stable Highly Active Basic Catalyst for Knoevenagel Condensation Reaction

Acyl-amide is extensively used as functional group and is a superior contender for the design of MOFs with the guest accessible functional organic sites. A novel acyl-amide-containing tetracarboxylate ligand, bis(3,5-dicarboxy-pheny1)terephthalamide, has been successfully synthesized. The H4L linker has some fascinating attributes as follows: (i) four carboxylate moieties as the coordination sites confirm affluent coordination approaches to figure a diversity of structure; (ii) two acyl-amide groups as the guest interaction sites can engender guest molecules integrated into the MOF networks through H-bonding interfaces and have a possibility to act as functional organic sites for the condensation reaction. A mesoporous MOF ([Cu2(L)(H2O)3]·4DMF·6H2O) has been prepared in order to produce the amide FOS within the MOF, which will work as guest accessible sites. The prepared MOF was characterized by CHN analysis, PXRD, FTIR spectroscopy, and SEM analysis. The MOF showed superior catalytic activity for Knoevenagel condensation. The catalytic system endures a broad variety of the functional groups and presents high to modest yields of aldehydes containing electron withdrawing groups (4-chloro, 4-fluoro, 4-nitro), offering a yield > 98 in less reaction time as compared to aldehydes with electron donationg groups (4-methyl). The amide decorated MOF (LOCOM-1-) as a heterogeneous catalyst can be simply recovered by centrifugation and recycled again without a flagrant loss of its catalytic efficiency.

[1]  W. Schuhmann,et al.  Graphene-Based Metal–Organic Framework Hybrids for Applications in Catalysis, Environmental, and Energy Technologies , 2022, Chemical reviews.

[2]  A. M. Qureshi,et al.  A facile synthesis of CeO2 from the GO@Ce-MOF precursor and its efficient performance in the oxygen evolution reaction , 2022, Frontiers in Chemistry.

[3]  Xiutang Zhang,et al.  Fluorine-Functionalized NbO-Type {Cu2}-Organic Framework: Enhanced Catalytic Performance on the Cycloaddition Reaction of CO2 with Epoxides and Deacetalization-Knoevenagel Condensation. , 2022, Inorganic chemistry.

[4]  Yong‐Liang Huang,et al.  Mixed-Linker Isoreticular Zn(II) Metal-Organic Frameworks as Brønsted Acid-Base Bifunctional Catalysts for Knoevenagel Condensation Reactions. , 2022, Inorganic chemistry.

[5]  S. Mandal,et al.  Shedding Light on the Lewis Acid Catalysis in Organic Transformations Using a Zn-MOF Microflower and Its ZnO Nanorod , 2022, Catalysis Letters.

[6]  Yaqing Liu,et al.  MOF-derived CoNi@C-silver nanowires/cellulose nanofiber composite papers with excellent thermal management capability for outstanding electromagnetic interference shielding , 2022, Composites Science and Technology.

[7]  T. Hagen,et al.  Explaining chemical clues of metal organic framework-nanozyme nano-/micro-motors in targeted treatment of cancers: benchmarks and challenges , 2022, Journal of Nanobiotechnology.

[8]  Yingtang Zhou,et al.  Bimetallic metal–organic frameworks and MOF-derived composites: Recent progress on electro- and photoelectrocatalytic applications , 2022, Coordination Chemistry Reviews.

[9]  Ping Liu,et al.  Supramolecular control of MOF pore properties for the tailored guest adsorption/separation applications , 2021 .

[10]  Q. Gu,et al.  Simultaneous quantitative recognition of all purines including N6-methyladenine via the host-guest interactions on a Mn-MOF , 2021 .

[11]  Huamin Zhang,et al.  A defect-free MOF composite membrane prepared via in-situ binder-controlled restrained second-growth method for energy storage device , 2021 .

[12]  J. Vittal,et al.  Two-Dimensional Metal-Organic Framework Materials: Synthesis, Structures, Properties and Applications. , 2021, Chemical reviews.

[13]  C. Hong,et al.  MOF-74-type frameworks: tunable pore environment and functionality through metal and ligand modification , 2021 .

[14]  M. Kurup,et al.  A 2D-layered Cd(II) MOF as an efficient heterogeneous catalyst for the Knoevenagel reaction , 2020 .

[15]  Hongqi Tian,et al.  Metal-Organic Framework (MOF)-Based Drug Delivery. , 2020, Current medicinal chemistry.

[16]  O. Farha,et al.  A historical overview of the activation and porosity of metal-organic frameworks. , 2020, Chemical Society reviews.

[17]  Qiang Xu,et al.  Metal-Organic Framework-Based Catalysts with Single Metal Sites. , 2020, Chemical reviews.

[18]  J. Caro,et al.  Balancing the Grain Boundary Structure and the Framework Flexibility through Bimetallic MOF Membranes for Gas Separation. , 2020, Journal of the American Chemical Society.

[19]  Stephen M. Martin,et al.  PCN-222 Metal-Organic Framework Nanoparticles with Tunable Pore Size for Nanocomposite Reverse Osmosis Membranes. , 2020, ACS applied materials & interfaces.

[20]  Agnes E. Thorarinsdottir,et al.  Metal-Organic Framework Magnets. , 2020, Chemical reviews.

[21]  O. Yaghi,et al.  Carbon capture and conversion using metal-organic frameworks and MOF-based materials. , 2019, Chemical Society reviews.

[22]  Sanliang Ling,et al.  Kinetic Control of Interpenetration in Fe-Biphenyl-4,4'-dicarboxylate Metal-Organic Frameworks by Coordination and Oxidation Modulation. , 2019, Journal of the American Chemical Society.

[23]  J. Ruiz,et al.  Fast ultrasound-assisted synthesis of highly crystalline MIL-88A particles and their application as ethylene adsorbents. , 2019, Ultrasonics sonochemistry.

[24]  Yadagiri Rachuri,et al.  Efficient heterogeneous catalysis by dual ligand Zn(II)/Cd(II) MOFs for the Knoevenagel condensation reaction: adaptable synthetic routes, characterization, crystal structures and luminescence studies , 2018 .

[25]  L. Dai,et al.  Pt-M bimetallic nanoparticles (M = Ni, Cu, Er) supported on metal organic framework-derived N-doped nanostructured carbon for hydrogen evolution and oxygen evolution reaction , 2018, Journal of Power Sources.

[26]  C. Petit Present and future of MOF research in the field of adsorption and molecular separation , 2018, Current Opinion in Chemical Engineering.

[27]  X. Lou,et al.  Metal-Organic-Framework-Based Materials as Platforms for Renewable Energy and Environmental Applications , 2017 .

[28]  Abdullah M. Asiri,et al.  Metal–organic frameworks for solar energy conversion by photoredox catalysis , 2017, Coordination Chemistry Reviews.

[29]  Jing Li,et al.  Metal-organic frameworks: functional luminescent and photonic materials for sensing applications. , 2017, Chemical Society reviews.

[30]  Jiwei Cui,et al.  Biomimetic Replication of Microscopic Metal–Organic Framework Patterns Using Printed Protein Patterns , 2015, Advanced materials.

[31]  Hussein A. Younus,et al.  Metal-organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations. , 2015, Chemical Society reviews.

[32]  Jie Han,et al.  A dual functional porous NbO-type metal–organic framework decorated with acylamide groups for selective sorption and catalysis , 2014 .

[33]  Wei‐Yin Sun,et al.  Zinc(II) coordination polymers with substituted benzenedicarboxylate and tripodal imidazole ligands: syntheses, structures and properties , 2014 .

[34]  Li Zhang,et al.  Applications of metal-organic frameworks in heterogeneous supramolecular catalysis. , 2014, Chemical Society reviews.

[35]  F. Moghaddam,et al.  Facile synthesis of highly substituted 2-pyrone derivatives via a tandem Knoevenagel condensation/lactonization reaction of β-formyl-esters and 1,3-cyclohexadiones , 2014 .

[36]  F. Kapteijn,et al.  Metal Organic Framework Catalysis: Quo vadis? , 2014 .

[37]  Kui Zhou,et al.  Metal-organic frameworks for upgrading biogas via CO2 adsorption to biogas green energy. , 2013, Chemical Society reviews.

[38]  S. Yin,et al.  One-pot synthesis of potassium-loaded MgAl oxide as solid superbase catalyst for Knoevenagel condensation , 2013 .

[39]  Yuhua Gao,et al.  Synthesis of a new urea derivative: a dual-functional organocatalyst for Knoevenagel condensation in water , 2013 .

[40]  G. Shimizu,et al.  Proton Conduction with Metal-Organic Frameworks , 2013, Science.

[41]  S. Kitagawa,et al.  A family of rare earth porous coordination polymers with different flexibility for CO2/C2H4 and CO2/C2H6 separation. , 2013, Inorganic chemistry.

[42]  J. Čejka,et al.  Deactivation Pathways of the Catalytic Activity of Metal–Organic Frameworks in Condensation Reactions , 2013 .

[43]  Xianyong Yu,et al.  Porous NbO-type metal–organic framework with inserted acylamide groups exhibiting highly selective CO2 capture , 2013 .

[44]  Alexander J. Blake,et al.  Modulating the packing of [Cu24(isophthalate)24] cuboctahedra in a triazole-containing metal–organic polyhedral framework , 2013 .

[45]  Teppei Yamada,et al.  Proton-conductive magnetic metal-organic frameworks, {NR3(CH2COOH)}[M(a)(II)M(b)(III)(ox)3]: effect of carboxyl residue upon proton conduction. , 2013, Journal of the American Chemical Society.

[46]  Anlian Zhu,et al.  Dual functions of N,N-dimethylethanolamnium-based ionic liquids for the Knoevenagel reactions at room temperature , 2013 .

[47]  Xingrui Wang,et al.  Understanding the Adsorption Mechanism of C2H2, CO2, and CH4 in Isostructural Metal–Organic Frameworks with Coordinatively Unsaturated Metal Sites , 2013 .

[48]  J. Čejka,et al.  Comparison of the catalytic activity of MOFs and zeolites in Knoevenagel condensation , 2013 .

[49]  Z. Su,et al.  Metal-organic frameworks as potential drug delivery systems , 2013, Expert opinion on drug delivery.

[50]  A. Mesecar,et al.  Synthesis of novel МТ3 receptor ligands via an unusual Knoevenagel condensation. , 2012, Bioorganic & medicinal chemistry letters.

[51]  M. Lah,et al.  A 3-dimensional coordination polymer with a rare lonsdaleite topology constructed from a tetrahedral ligand , 2012 .

[52]  Omar K Farha,et al.  Metal-organic framework materials with ultrahigh surface areas: is the sky the limit? , 2012, Journal of the American Chemical Society.

[53]  C. Su,et al.  Two ligand-functionalized Pb(II) metal-organic frameworks: structures and catalytic performances. , 2012, Dalton transactions.

[54]  Ran Zhao,et al.  A unique substituted Co(II)-formate coordination framework exhibits weak ferromagnetic single-chain-magnet like behavior. , 2012, Chemical communications.

[55]  J. F. Stoddart,et al.  Large-Pore Apertures in a Series of Metal-Organic Frameworks , 2012, Science.

[56]  P. K. Bharadwaj,et al.  Co(II) Coordination Polymers with Co-Ligand Dependent Dinuclear to Tetranuclear Core: Spin-Canting, Weak Ferromagnetic, and Antiferromagnetic Behavior , 2012 .

[57]  Shuhua Li,et al.  Highly selective CO2 capture of an agw-type metal-organic framework with inserted amides: experimental and theoretical studies. , 2012, Chemical communications.

[58]  Omar K Farha,et al.  Metal-organic framework materials as chemical sensors. , 2012, Chemical reviews.

[59]  Hong-Cai Zhou,et al.  Metal-organic frameworks for separations. , 2012, Chemical reviews.

[60]  Kimoon Kim,et al.  Homochiral metal-organic frameworks for asymmetric heterogeneous catalysis. , 2012, Chemical reviews.

[61]  Hongmei Ai,et al.  Sodium Benzoate as a Green, Efficient, and Recyclable Catalyst for Knoevenagel Condensation , 2012 .

[62]  Michael O'Keeffe,et al.  Isoreticular expansion of metal-organic frameworks with triangular and square building units and the lowest calculated density for porous crystals. , 2011, Inorganic chemistry.

[63]  E. Monzani,et al.  Structural variation from 1D chains to 3D networks: a systematic study of coordination number effect on the construction of coordination polymers using the terepthaloylbisglycinate ligand , 2011 .

[64]  Sung Min Shin,et al.  Asymmetric catalytic reactions by NbO-type chiral metal–organic frameworks , 2011 .

[65]  Jingui Duan,et al.  Enhanced CO2 binding affinity of a high-uptake rht-type metal-organic framework decorated with acylamide groups. , 2011, Journal of the American Chemical Society.

[66]  O. Shekhah,et al.  MOF thin films: existing and future applications. , 2011, Chemical Society reviews.

[67]  Seth M Cohen,et al.  Isoreticular synthesis and modification of frameworks with the UiO-66 topology. , 2010, Chemical communications.

[68]  Mark D. Allendorf,et al.  Luminescent Metal—Organic Frameworks , 2009 .

[69]  S. Natarajan,et al.  Time- and Temperature-Dependent Study in the Three-Component Zinc-Triazolate-Oxybis(benzoate) System: Stabilization of New Topologies , 2009 .

[70]  Omar K Farha,et al.  Metal-organic framework materials as catalysts. , 2009, Chemical Society reviews.

[71]  M. Allendorf,et al.  Luminescent metal-organic frameworks. , 2009, Chemical Society reviews.

[72]  Alexander J. Blake,et al.  High capacity hydrogen adsorption in Cu(II) tetracarboxylate framework materials: the role of pore size, ligand functionalization, and exposed metal sites. , 2009, Journal of the American Chemical Society.

[73]  Yuanjing Cui,et al.  A luminescent metal-organic framework with Lewis basic pyridyl sites for the sensing of metal ions. , 2009, Angewandte Chemie.

[74]  R. Kluger,et al.  Functional cross-linked hemoglobin bis-tetramers: geometry and cooperativity. , 2008, Biochemistry.

[75]  M. B. Gawande,et al.  Cross-aldol and Knoevenagel condensation reactions in aqueous micellar media , 2008 .

[76]  S. Kantevari,et al.  HClO4–SiO2 and PPA–SiO2 catalyzed efficient one-pot Knoevenagel condensation, Michael addition and cyclo-dehydration of dimedone and aldehydes in acetonitrile, aqueous and solvent free conditions: Scope and limitations , 2007 .

[77]  Matthias Boehm,et al.  An improved manufacturing process for the antimalaria drug coartem. Part II , 2007 .

[78]  S. Kitagawa,et al.  Three-dimensional porous coordination polymer functionalized with amide groups based on tridentate ligand: selective sorption and catalysis. , 2007, Journal of the American Chemical Society.

[79]  J. Tedrow,et al.  New conditions for the synthesis of thiophenes via the Knoevenagel/Gewald reaction sequence. Application to the synthesis of a multitargeted kinase inhibitor , 2006 .

[80]  T. Uemura,et al.  Nanochannel-promoted polymerization of substituted acetylenes in porous coordination polymers. , 2006, Angewandte Chemie.

[81]  S. Nguyen,et al.  A metal-organic framework material that functions as an enantioselective catalyst for olefin epoxidation. , 2006, Chemical communications.

[82]  In Su Lee,et al.  Rational Synthesis and Characterization of Robust Microporous Metal−Organic Frameworks with Base Functionality , 2006 .

[83]  C. Serre,et al.  Investigation of acid sites in a zeotypic giant pores chromium(III) carboxylate. , 2006, Journal of the American Chemical Society.

[84]  M. Hartmann,et al.  Knoevenagel condensation over β and Y zeolites in liquid phase under solvent free conditions , 2006 .

[85]  R. Custelcean,et al.  A metal-organic framework functionalized with free carboxylic acid sites and its selective binding of a Cl(H2O)4(-) cluster. , 2005, Journal of the American Chemical Society.

[86]  Chuan-De Wu,et al.  A homochiral porous metal-organic framework for highly enantioselective heterogeneous asymmetric catalysis. , 2005, Journal of the American Chemical Society.

[87]  E. Gutiérrez‐Puebla,et al.  Novel 2D and 3D Indium Metal-Organic Frameworks: Topology and Catalytic Properties† , 2005 .

[88]  J. Jenck,et al.  Products and processes for a sustainable chemical industry: a review of achievements and prospects , 2004 .

[89]  K. Nagaiah,et al.  An Efficient Knoevenagel Condensation Catalyzed by LaCl3×7H2O in Heterogeneous Medium. , 2004 .

[90]  In Su Lee,et al.  Self-assemblies of new rigid angular ligands and metal centers toward the rational construction and modification of novel coordination polymer networks. , 2003, Inorganic chemistry.

[91]  S. Toovey,et al.  Successful co-artemether (artemether-lumefantrine) clearance of falciparum malaria in a patient with severe cholera in Mozambique. , 2003, Travel medicine and infectious disease.

[92]  Jinho Oh,et al.  A homochiral metal–organic porous material for enantioselective separation and catalysis , 2000, Nature.

[93]  Pietro Tundo,et al.  Synthetic pathways and processes in green chemistry. Introductory overview , 2000 .

[94]  Katsuyuki Ogura,et al.  Preparation, Clathration Ability, and Catalysis of a Two-Dimensional Square Network Material Composed of Cadmium(II) and 4,4'-Bipyridine , 1994 .

[95]  P. S. Rao,et al.  Zinc Chloride as a New Catalyst for Knoevenagel Condensation. , 1992 .

[96]  A. Zilberstein,et al.  Tyrphostins inhibit epidermal growth factor (EGF)-receptor tyrosine kinase activity in living cells and EGF-stimulated cell proliferation. , 1989, The Journal of biological chemistry.

[97]  F. Freeman PROPERTIES AND REACTIONS OF YLIDENEMALONONITRILES , 1980 .

[98]  E. Knoevenagel Condensation von Malonsäure mit aromatischen Aldehyden durch Ammoniak und Amine , 1898 .

[99]  R. Winpenny,et al.  Cluster-Based Single-Molecule Magnets , 2014 .

[100]  Wenqin Zhang,et al.  Highly efficient Knoevenagel condensation reactions catalyzed by a proline-functionalized polyacrylonitrile fiber , 2013 .

[101]  Kikuo Okuyama,et al.  Progress in developing spray-drying methods for the production of controlled morphology particles: From the nanometer to submicrometer size ranges , 2011 .

[102]  F. Kapteijn,et al.  Amino-based metal-organic frameworks as stable, highly active basic catalysts , 2009 .

[103]  Pietro Tundo,et al.  Special Topic Issue on Green Chemistry , 2000 .

[104]  S. Batten,et al.  Structural isomers of M(dca)2 molecule-based magnets. Crystal structure of tetrahedrally coordinated sheet-like β-Zn(dca)2 and β-Co/Zn(dca)2, and the octahedrally coordinated rutile-like α-Co(dca)2, where dca– = dicyanamide, N(CN)2–, and magnetism of β-Co(dca)2 , 1999 .