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Relevant academic research and scientific papers

Solvent-assisted ligand exchange (SALE) for the enhancement of epoxide ring-opening reaction catalysis based on three amide-functionalized metal-organic frameworks

In recent years, functionalized pillar ligands have gained significant interests due to their important role in MOF structure and performance. The synthesis of MOF compounds with a particular functionalized ligand is not always successful, and sometimes, synthesis cannot be achieved easily or directly, even by employing several methods. However, this limitation can be overcome by applying a post-synthesis step that swaps the functional groups without changing the backbone of the pillar ligand. Solvent-assisted ligand exchange (SALE) is a post-synthesis method that has been used for confronting this challenge by replacing a functional group with an alternative. Through this investigation, we tried to improve the properties of MOF compounds and increase their catalytic efficiency by importing new functional groups into their structures. The N1,N3-di (pyridine-4-yl) malonamide linker (S) is a pillar ligand, which does not easily enter into the structure during the synthesis of MOF compounds. Therefore, to solve this issue, amide-functionalized, benzene-core ligand derivatives were designed as linkers to manufacture the new 3D structures [Co(oba)(bpta)]·(DMF)2 TMU-50 and [Co2(oba)2(bpfn)]·(DMF)2.5 TMU-51 and the novel 2D structure [Co(oba)(bpfb)]·(DMF)2 TMU-49. These structures were achieved by layering the compounds via hydrothermal reaction. Moreover, the ability of these structures to act as catalysts was evaluated using the methanolysis reaction of epoxides. To increase the MOF catalytic efficiency, we designed the N1,N3-di (pyridine-4-yl) malonamide linker (S) as a malonamide pillar ligand, which contains an acidic hydrogen that is suitable for catalyzing an epoxide ring-opening reaction and therefore enhancing the catalytic activity. As the synthesis of the MOF structure with this linker was not successful, we designed three new structures by incorporating different percentages of S linkers by exchanging the acylamide functional group with malonamide via the SALE pathway. The acylamide functional group was successfully replaced and produced daughter MOFs TMU-49S, TMU-50S and TMU-51S. PXRD and NMR spectroscopy confirmed that the S linker was incorporated into the acylamide-MOF structure. The obtained materials TMU-49S, TMU-50S and TMU-51S are isostructural with their parent frameworks. The S spacer significantly improved the catalytic properties of the MOF compounds in the ring-opening reaction of epoxides, with TMU-50S showing a 98% catalytic efficiency after incorporating the S linker. The catalysts could be recycled without any significant loss in the catalytic efficiency.

Target-Architecture Engineering of a Novel Two-dimensional Metal-Organic Framework for High Catalytic Performance

A novel 2D-MOF, [Zn(L1)(oba)], an effective heterogeneous H-bond donor catalyst, based on carbohydrazide moiety (L1), was synthesized. Remarkable enhanced catalytic activity was achieved for methanolysis of epoxides by applying two effective strategies: (i) increasing the acidic strength of the H-bond donors and (ii) providing more accessible active sites within the framework.

Zirconium triflate grafted on SBA-15 as a highly efficient solid acid catalyst for ring opening of epoxides by amines and alcohols

Metal (Al, Ti, Zr) triflate grafted mesoporous SBA-15 (AlTf/S, TiTf/S, ZrTf/S) samples were synthesized as inexpensive solid acid materials by a simple one-pot-two-step synthesis methodology. These materials were characterized by X-ray diffraction, N2-sorption, thermogravimetric analysis, Fourier transform infrared spectroscopy (FT-IR), in-situ pyridine FT-IR spectroscopy, and elemental analysis. ZrTf/S was found to be a highly efficient and reusable solid acid catalyst for ring opening of epoxides with amines and alcohols and produced β-amino alcohols and β-alkoxy alcohols respectively under ambient reaction conditions. The ZrTf/S catalyst showed the highest activity, which was attributed to its high acidity compared with that of the Ti and Al containing samples.

Enhancement of CO2 Adsorption and Catalytic Properties by Fe-Doping of [Ga2(OH)2(L)] (H4L = Biphenyl-3,3′,5,5′-tetracarboxylic Acid), MFM-300(Ga2)

Metal-organic frameworks (MOFs) are usually synthesized using a single type of metal ion, and MOFs containing mixtures of different metal ions are of great interest and represent a methodology to enhance and tune materials properties. We report the synthesis of [Ga2(OH)2(L)] (H4L = biphenyl-3,3′,5,5′-tetracarboxylic acid), designated as MFM-300(Ga2), (MFM = Manchester Framework Material replacing NOTT designation), by solvothermal reaction of Ga(NO3)3 and H4L in a mixture of DMF, THF, and water containing HCl for 3 days. MFM-300(Ga2) crystallizes in the tetragonal space group I4122, a = b = 15.0174(7) ? and c = 11.9111(11) ? and is isostructural with the Al(III) analogue MFM-300(Al2) with pores decorated with -OH groups bridging Ga(III) centers. The isostructural Fe-doped material [Ga1.87Fe0.13(OH)2(L)], MFM-300(Ga1.87Fe0.13), can be prepared under similar conditions to MFM-300(Ga2) via reaction of a homogeneous mixture of Fe(NO3)3 and Ga(NO3)3 with biphenyl-3,3′,5,5′-tetracarboxylic acid. An Fe(III)-based material [Fe3O1.5(OH)(HL)(L)0.5(H2O)3.5], MFM-310(Fe), was synthesized with Fe(NO3)3 and the same ligand via hydrothermal methods. [MFM-310(Fe)] crystallizes in the orthorhombic space group Pmn21 with a = 10.560(4) ?, b = 19.451(8) ?, and c = 11.773(5) ? and incorporates μ3-oxo-centered trinuclear iron cluster nodes connected by ligands to give a 3D nonporous framework that has a different structure to the MFM-300 series. Thus, Fe-doping can be used to monitor the effects of the heteroatom center within a parent Ga(III) framework without the requirement of synthesizing the isostructural Fe(III) analogue [Fe2(OH)2(L)], MFM-300(Fe2), which we have thus far been unable to prepare. Fe-doping of MFM-300(Ga2) affords positive effects on gas adsorption capacities, particularly for CO2 adsorption, whereby MFM-300(Ga1.87Fe0.13) shows a 49% enhancement of CO2 adsorption capacity in comparison to the homometallic parent material. We thus report herein the highest CO2 uptake (2.86 mmol g-1 at 273 K at 1 bar) for a Ga-based MOF. The single-crystal X-ray structures of MFM-300(Ga2)-solv, MFM-300(Ga2), MFM-300(Ga2)·2.35CO2, MFM-300(Ga1.87Fe0.13)-solv, MFM-300(Ga1.87Fe0.13), and MFM-300(Ga1.87Fe0.13)·2.0CO2 have been determined. Most notably, in situ single-crystal diffraction studies of gas-loaded materials have revealed that Fe-doping has a significant impact on the molecular details for CO2 binding in the pore, with the bridging M-OH hydroxyl groups being preferred binding sites for CO2 within these framework materials. In situ synchrotron IR spectroscopic measurements on CO2 binding with respect to the -OH groups in the pore are consistent with the above structural analyses. In addition, we found that, compared to MFM-300(Ga2), Fe-doped MFM-300(Ga1.87Fe0.13) shows improved catalytic properties for the ring-opening reaction of styrene oxide, but similar activity for the room-temperature acetylation of benzaldehyde by methanol. The role of Fe-doping in these systems is discussed as a mechanism for enhancing porosity and the structural integrity of the parent material.

Synthesis, structure and multifunctional catalytic properties of a Cu(i)-coordination polymer with outer-hanging CuBr2

A 1D Cu(i)-coordination polymer [(CuL1)(CuBr2), 1] carrying external copper bromide moieties was synthesized. The outer-hanging [CuBr2]- moiety is attached to the 1D Cu(i)-CP backbone via a Cu?Cu bonding interaction, which makes it look like a coordination polymer supported CuBr2 species. 1 exhibits excellent multifunctional catalytic activity for phenol acetylation, A3-coupling (aldehyde-alkyne-amine) and styrene oxide methanolysis reactions. Its heterogeneous catalytic nature was confirmed by solution leaching experiment and it can be reused without significant loss of its catalytic activity and selectivity for the above reactions.

Porous Zirconium-Phytic Acid Hybrid: A Highly Efficient Catalyst for Meerwein-Ponndorf-Verley Reductions

The utilization of compounds from natural sources to prepare functional materials is of great importance. Herein, we describe for the first time the preparation of organic-inorganic hybrid catalysts by using natural phytic acid as building block. Zirconium phosphonate (Zr-PhyA) was synthesized by reaction of phytic acid and ZrCl4 and was obtained as a mesoporous material with pore sizes centered around 8.5 nm. Zr-PhyA was used to catalyze the mild and selective Meerwein-Ponndorf-Verley (MPV) reduction of various carbonyl compounds, e.g., of levulinic acid and its esters into γ-valerolactone. Further studies indicated that both Zr and phosphate groups contribute significantly to the excellent performance of Zr-PhyA. All natural: Porous zirconium phosphonate (Zr-PhyA) was synthesized simply by reaction of natural phytic acid (PhyA) and ZrCl4 and applied as a very efficient catalyst for the Meerwein-Ponndorf-Verley reduction of various carbonyl compounds. Both the Zr element and phosphate groups contributed significantly to the excellent catalytic performance of Zr-PhyA.

Urea-containing metal-organic frameworks as heterogeneous organocatalysts

Two novel pillared metal-organic frameworks (MOFs) containing a urea-functional group are introduced. Herein, the urea functional group was incorporated into the MOF backbone by preparing a urea-ditopic ligand. These frameworks (TMU-18 and TMU-19) were fabricated using the synthesized urea-containing ligand, 4,4′-bipyridine (bipy) and 1,2-bis(4-pyridyl)ethane (bpe), and using zinc nitrate as the metal source. Subsequently, TMU-18 and TMU-19 were characterized by X-ray diffraction, IR spectroscopy, elemental analysis, scanning electron microscopy (SEM) and thermogravimetric analysis. Furthermore, their potential efficiency as organocatalysts was evaluated in the regioselective methanolysis of epoxides.

Organotin Phosphate Condensates as a Catalyst of Selective Ring-Opening of Oxiranes by Alcohols

The highly regioselective alcoholysis of oxiranes is catalyzed by organotin phosphate condensates, providing a variety of β-alkoxy alcohols in good yields.The selectivity of the nucleophilic attack is dependent on the structures of epoxides.The gem-dialkyloxiranes are cleaved on the tertiary carbon, while β,γ-epoxy alcohols and their derivatives gave C-3 attack products.The anti stereoisomers are solely produced in the latter case.Thus the catalysis is both acidic and coordinative.Of practical importance is the recycled use of the catalyst without any appreciable decrease in the activity and the selectivities.

HIGHLY REGIOSELECTIVE RING OPENING OF EPOXIDES WITH ALCOHOLS CATALYZED BY ORGANOTIN PHOSPHATE CONDENSATES

Organotin phosphate condensates proved to catalyze the ring opening reaction of epoxides with alcohols in a highly regioselective manner.