Three Novel Polymeric CoII/CuII Complexes Assembled from 5-Nitro-1,2,3-benzenetricarboxylate and 4,4'-Bipyridine: Syntheses, Crystal Structures, and Magnetic Properties

2011 ◽  
Vol 64 (10) ◽  
pp. 1346 ◽  
Author(s):  
Xiaofei Zhu ◽  
Ning Wang ◽  
Yuhui Luo ◽  
Yu Pang ◽  
Dan Tian ◽  
...  
Keyword(s):  
Magnetic Properties ◽  
Magnetic Susceptibility ◽  
Thermogravimetric Analysis ◽  
Metal Organic Frameworks ◽  
X Ray Diffraction ◽  
X Ray ◽  
Secondary Building Units ◽  
Coordination Behaviour ◽  
Metal Organic ◽  
3D Framework

To investigate the coordination behaviour of tricarboxylate ligands that always induced the formation of intriguing metal organic frameworks, three CoII/CuII complexes constructed with bi-/tri-nuclear secondary building units (SBUs), namely CoII3(O2N-btc)2(4,4′-bpy)3(H2O)2 (1), [CuII3(O2N-btc)2(4,4′-bpy)2(H2O)2]·2H2O(2) and [CuII5(O2N-btc)2(O2N-btcH)2(4,4′-bpy)2(μ2 -OH2)2(H2O)8]·4H2O(3) (O2N-btcH3 = 5-nitro-1,2,3-benzenetricarboxylate, 4,4′-bpy = 4,4-bipyridyl), were hydrothermally synthesized using O2N-btcH3 and 4,4′-bpy as ligands. Complexes 1 and 2 exhibit the 3D framework constructed from a binuclear [M2(COO)2] (M = CuII and CoII) unit and a mononuclear MII unit, displaying (4·6·8)2(64·82) (42·68·83·102) and (4·6·8)2(62·84) (42·62·810·12) topology, respectively. Complex 3 displays an interesting 2D ladder-layered network constructed from a trinuclear [Cu3(μ2-OH2)2] unit and a mononuclear CuII unit as the linking nodes, showing (42.6)2(46.66.83) nets. These compounds are well characterized by elemental analysis, FTIR, thermogravimetric analysis and powder X–ray diffraction. The direct current magnetic susceptibility measurements were carried out to study their magnetic properties.

scholarly journals 2D Porphyrinic Metal-Organic Frameworks Featuring Rod-Shaped Secondary Building Units

Molecules ◽  
2021 ◽  
Vol 26 (10) ◽  
pp. 2955
Author(s):  
Rory Elliott ◽  
Aoife A. Ryan ◽  
Aviral Aggarwal ◽  
Nianyong Zhu ◽  
Friedrich W. Steuber ◽  
...  
Keyword(s):  
Photophysical Properties ◽  
Metal Organic Frameworks ◽  
Gas Storage ◽  
X Ray Diffraction ◽  
X Ray ◽  
Molecular Separation ◽  
Potential Applications ◽  
Secondary Building Units ◽  
Metal Organic ◽  
Solvent Molecules

Metal-organic frameworks (MOFs) encompass a rapidly expanding class of materials with diverse potential applications including gas storage, molecular separation, sensing and catalysis. So-called ‘rod MOFs’, which comprise infinitely extended 1D secondary building units (SBUs), represent an underexplored subclass of MOF. Further, porphyrins are considered privileged ligands for MOF synthesis due to their tunable redox and photophysical properties. In this study, the CuII complex of 5,15-bis(4-carboxyphenyl)-10,20-diphenylporphyrin (H2L-CuII, where H2 refers to the ligand’s carboxyl H atoms) is used to prepare two new 2D porphyrinic rod MOFs PROD-1 and PROD-2. Single-crystal X-ray analysis reveals that these frameworks feature 1D MnII- or CoII-based rod-like SBUs that are coordinated by labile solvent molecules and photoactive porphyrin moieties. Both materials were characterised using infrared (IR) spectroscopy, powder X-ray diffraction (PXRD) spectroscopy and thermogravimetric analysis (TGA). The structural attributes of PROD-1 and PROD-2 render them promising materials for future photocatalytic investigations.

Two new NiII and ZnII metal–organic frameworks of glutarate and 1,4-bis[(2-methyl-1H-imidazol-1-yl)methyl]benzene ligands: syntheses, structures and luminescence sensing properties

2020 ◽  
Vol 76 (2) ◽  
pp. 148-158
Author(s):  
Fang-Hua Zhao ◽  
Zhong-Lin Li ◽  
Shu-Fang Zhang ◽  
Jian-Hui Han ◽  
Mei Zhang ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Three Dimensional ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
One Dimensional ◽  
X Ray ◽  
Vis Spectroscopy ◽  
Metal Organic ◽  
3D Framework ◽  
Methyl Benzene

Two new metal–organic frameworks (MOFs), namely, three-dimensional poly[diaquabis{μ2-1,4-bis[(2-methyl-1H-imidazol-1-yl)methyl]benzene}bis(μ2-glutarato)dinickel(II)] monohydrate], {[Ni2(C5H6O4)2(C16H18N4)2(H2O)2]·H2O} n or {[Ni2(Glu)2(1,4-mbix)2(H2O)2]·H2O} n , (I), and two-dimensional poly[[{μ2-1,4-bis[(2-methyl-1H-imidazol-1-yl)methyl]benzene}(μ2-glutarato)zinc(II)] tetrahydrate], {[Zn(C5H6O4)(C16H18N4)]·4H2O} n or {[Zn(Glu)(1,4-mbix)]·4H2O} n (II), have been synthesized hydrothermally using glutarate (Glu2−) mixed with 1,4-bis[(2-methyl-1H-imidazol-1-yl)methyl]benzene (1,4-mbix), and characterized by single-crystal X-ray diffraction, IR and UV–Vis spectroscopy, powder X-ray diffraction, and thermogravimetric and photoluminescence analyses. NiII MOF (I) shows a 4-connected 3D framework with point symbol 66, but is not a typical dia network. ZnII MOF (II) displays a two-dimensional 44-sql network with one-dimensional water chains penetrating the grids along the c direction. The solid-state photoluminescence analysis of (II) was performed at room temperature and the MOF exhibits highly selective sensing toward Fe3+ and Cr2O7 2− ions in aqueous solution.

Two topologically different 3D CuII metal–organic frameworks assembled from the same ligands: control of reaction conditions

2019 ◽  
Vol 75 (6) ◽  
pp. 1060-1068 ◽  
Author(s):  
Shunlin Zhang ◽  
Sheng Gao ◽  
Xin Wang ◽  
Xin He ◽  
Jing Zhao ◽  
...  
Keyword(s):  
Thermogravimetric Analysis ◽  
Metal Organic Frameworks ◽  
High Water ◽  
High Dimensional ◽  
X Ray Diffraction ◽  
Reaction Conditions ◽  
X Ray ◽  
X Ray Crystallography ◽  
Bifunctional Ligands ◽  
Metal Organic

Bifunctional ligands containing both carboxylic and sulfonate groups can adopt versatile coordination modes to produce novel metal–organic frameworks (MOFs) with high-dimensional networks and interesting topologies. Using 2,2′-disulfonylbiphenyl-4,4′-dicarboxylic acid (H4 L) as a linker and 4,4′-bipyridine (4,4′-bpy) as a co-ligand, two novel 3D CuII MOFs, {[Cu2(L)(4,4′-bpy)2.5(H2O)]·1.7H2O} n , (1), and {[Cu2(L)(4,4′-bpy)2]·DMA·3H2O} n , (2), have been synthesized and structurally characterized by X-ray crystallography (DMA is N,N-dimethylacetamide). MOF (1) shows an unprecedented trinodal 4,4,5-connected topology network with the Schläfli symbol (4.62.73)(43.65.7.8)(6.73.8.10), while MOF (2) indicates a binodal 4,6-connected fsc network with the Schläfli symbol (44.610.8)(44.62). MOFs (1) and (2) were further characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction and thermogravimetric analysis. MOF (1) shows a high water and chemical stability. The proton conductivity of (1) and CO2 adsorption of (2) were also investigated.

Two isostructural fluorinated metal-organic frameworks with rare rod-packing architecture: syntheses, structures and luminescent properties

2017 ◽  
Vol 72 (2) ◽  
pp. 107-113 ◽  
Author(s):  
Sheng-Chun Chen ◽  
Feng Tian ◽  
Ming-Yang He ◽  
Qun Chen
Keyword(s):  
Fluorescence Spectra ◽  
Metal Organic Frameworks ◽  
Luminescent Properties ◽  
X Ray Diffraction ◽  
Hydrothermal Conditions ◽  
X Ray ◽  
Secondary Building Units ◽  
Metal Organic ◽  
Solid State Fluorescence ◽  
Methyl Benzene

AbstractTwo isostructural fluorinated metal-organic frameworks, formulated as [M2(Fbix)(1,4-NDC)2]n (M=Cd for 1 and Mn for 2), were synthesized by employing 1,4-naphthalenedicarboxylic acid (1,4-H2NDC) and the flexible fluorinated ligand 2,3,5,6-tetrafluoro-1,4-bis(imidazole-1-yl-methyl)benzene (Fbix) under hydrothermal conditions. Their structures were determined by single-crystal X-ray diffraction and further characterized by infrared spectroscopy, powder X-ray diffraction, and thermogravimetric analyses. Structure analyses have revealed that compounds 1 and 2 show an unusual hex net based on infinite rod-shaped secondary building units. The solid-state fluorescence spectra of 1 and 2 were measured and indicate a ligand-based emission for both complexes.

Novel Ba2+ and Pb2+ metal–organic frameworks based on a semi-rigid tetracarboxylic acid: syntheses, structures, topologies and luminescence properties

2021 ◽  
Vol 77 (6) ◽  
Author(s):  
Yanwen Sun ◽  
Zhen Chen ◽  
Xiaozhong Wang ◽  
Lei Wang ◽  
Xue Yang ◽  
...  
Keyword(s):  
Self Assembly ◽  
Metal Organic Frameworks ◽  
Three Dimensional ◽  
Luminescence Properties ◽  
Tetracarboxylic Acid ◽  
X Ray Diffraction ◽  
X Ray ◽  
Secondary Building Units ◽  
Metal Organic ◽  
The Rich

Multidentate carboxylate ligands have been widely used in the construction of metal–organic frameworks (MOFs) owing to the rich variety of their coordination modes, which can lead to crystalline products with interesting structures and properties. Two new main-group MOFs, namely, poly[[di-μ-aqua-diaqua(dimethylformamide)[μ7-5,5′-methylenebis(2,4,6-trimethylbenzene-1,3-dicarboxylato)]dibarium(II)] trihydrate], {[Ba2(C23H20O8)(C3H7NO)(H2O)4]·3H2O} n or {[Ba2(BTMIPA)(DMF)(H2O)4]·3H2O} n (1), and poly[[diaqua[μ6-5,5′-methylenebis(2,4,6-trimethylbenzene-1,3-dicarboxylato)]dilead(II)] 2.5-hydrate], {[Pb2(C23H20O8)(H2O)2]·2.5H2O} n or {[Pb2(BTMIPA)(H2O)2]·2.5H2O} n (2), were prepared by the self-assembly of metal salts with the semi-rigid tetracarboxylic acid ligand 5,5′-methylenebis(2,4,6-trimethylisophthalic acid) (H4BTMIPA). Both structures were characterized by elemental analysis (EA), single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectroscopy and thermogravimetric analysis (TGA). Complex 1 reveals a three-dimensional (3D) flu network formed via bridging tetranuclear secondary building units (SBUs) and complex 2 displays a 3D framework with an sqp topology based on one-dimensional metal chains. The BTMIPA4− ligands adopt a rare coordination mode in 2, although the ligands in both 1 and 2 are X-shaped. The luminescence properties of both complexes were investigated in the solid state.

Synthesis, crystal structure, luminescence, and photocatalytic properties of a 2D Cu(II) metal-organic frameworks based on 3,5-di(1H-benzimidazol-1-yl)pyridine and 4,4′-oxybis(benzoate) ligands

2020 ◽  
Vol 75 (8) ◽  
pp. 727-732
Author(s):  
Chen Zhang ◽  
Jian-Qing Tao
Keyword(s):  
Crystal Structure ◽  
Thermal Analysis ◽  
Uv Light ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
X Ray Diffraction ◽  
X Ray ◽  
Uv Light Irradiation ◽  
Photocatalytic Activities ◽  
Metal Organic

AbstractA new Cu(II) metal-organic framework, [Cu(L)(OBA)·H2O]n (1) [H2OBA = 4,4′-oxybis(benzoic acid), L = 3,5-di(1H-benzimidazol-1-yl)pyridine] was hydrothermally synthesized and characterized through IR spectroscopy, elemental and thermal analysis and single-crystal X-ray diffraction. Complex 1 is a four-connected uni-nodal 2D net with a (44·62) topology which shows an emission centered at λ ∼393 nm upon excitation at λ = 245 nm. Moreover, complex 1 possesses high photocatalytic activities for the decomposition of Rhodamine B (RhB) under UV light irradiation.

scholarly journals In situ X‐ray Diffraction Investigation of the Crystallisation of Perfluorinated Ce(IV)‐based Metal‐Organic Frameworks with UiO‐66 and MIL‐140 architectures

2021 ◽  
Author(s):  
Stephen J. I. Shearan ◽  
Jannick Jacobsen ◽  
Ferdinando Costantino ◽  
Roberto D’Amato ◽  
Dmitri Novikov ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
X Ray Diffraction ◽  
X Ray ◽  
Metal Organic

A MOF based on a lead(II) 2-oxido-6-methylpyridine-4-carboxylate network

2020 ◽  
Vol 75 (4) ◽  
pp. 365-369
Author(s):  
Long Tang ◽  
Yu Pei Fu ◽  
Na Cui ◽  
Ji Jiang Wang ◽  
Xiang Yang Hou ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Carboxylic Acid ◽  
Thermogravimetric Analysis ◽  
Metal Organic Framework ◽  
X Ray Diffraction ◽  
X Ray ◽  
Connected Node ◽  
Metal Organic ◽  
Solid State Fluorescence

AbstractA new metal-organic framework, [Pb(hmpcaH)2]n (1), has been hydrothermally synthesized from Pb(OAc)2 · 3H2O and 2-hydroxy-6-methylpyridine-4-carboxylic acid (hmpcaH2; 2), and characterized by IR spectroscopy, elemental and thermogravimetric analysis, and single-crystal X-ray diffraction. In complex 1, each hmpcaH− ligand represents a three-connected node to combine with the hexacoordinated Pb(II) ions, generating a 3D binodal (3,6)-connected ant network. The crystal structure of 2 was determined. The solid-state fluorescence properties of 1 and 2 were investigated.

A series of microporous and robust Ln-MOFs showing luminescent properties and catalytic performances towards Knoevenagel reactions

2021 ◽  
Author(s):  
Qing-Xia Yao ◽  
Miaomiao Tian ◽  
Jun Zheng ◽  
Jintang Xue ◽  
Xuze Pan ◽  
...  
Keyword(s):  
Single Crystal ◽  
Metal Organic Frameworks ◽  
Luminescent Properties ◽  
X Ray Diffraction ◽  
X Ray ◽  
Metal Organic ◽  
Catalytic Performances

A series of microporous Ln(III)-based metal-organic frameworks (1-Ln) have been hydrothermally synthesized by using 4,4',4''-nitrilotribenzoic acid (H3NTB). Single crystal X-ray diffraction analyses show 1-Ln are isostructural and have 3D porous...

scholarly journals Compressibility Studies of Zirconium Based Metal-Organic Frameworks

2014 ◽  
Vol 70 (a1) ◽  
pp. C157-C157
Author(s):  
Claire Hobday ◽  
Stephen Moggach ◽  
Carole Morrison ◽  
Tina Duren ◽  
Ross Forgan
Keyword(s):  
High Pressure ◽  
Mechanical Stability ◽  
Metal Organic Frameworks ◽  
External Pressure ◽  
X Ray Diffraction ◽  
X Ray ◽  
X Ray Crystallography ◽  
Pressure Medium ◽  
Metal Organic ◽  
University Of Oslo

Metal-organic frameworks (MOFs) are a well-studied class of porous materials with the potential to be used in many applications such as gas storage and catalysis.[1] UiO-67 (UiO = University of Oslo), a MOF built from zirconium oxide units connected with 4,4-biphenyldicarboxylate (BDC) linkers, forms a face centred cubic structure. Zirconium has a high affinity towards oxygen ligands making these bridges very strong, resulting in UiO-based MOFs having high chemical and thermal stability compared to other MOF structures. Moreover, UiO-67 has become popular in engineering studies due to its high mechanical stability.[2] Using high pressure x-ray crystallography we can exert MOFs to GPa pressures, experimentally exploring the mechanical stability of MOFs to external pressure. By immersing the crystal in a hydrostatic medium, pressure is applied evenly to the crystal. On surrounding a porous MOF with a hydrostatic medium composed of small molecules (e.g. methanol), the medium can penetrate the MOF, resulting in medium-dependant compression. On compressing MOF-5 (Zn4O(BDC)3) using diethylformamide as a penetrating medium, the framework was shown to have an increased resistance to compression, becoming amorphous several orders of magnitude higher in pressure than observed on grinding the sample.[3] Here we present a high-pressure x-ray diffraction study on the UiO-based MOF UiO-67, and several new synthesised derivatives built from same metal node but with altered organic linkers, allowing us to study in a systematic way, the mechanical stability of the MOF, and its pressure dependence on both the linker, and pressure medium.

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