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 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.

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.

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

Synthesis, designing strategies and photocatalytic charge dynamics of Metal-Organic Frameworks (MOFs): A catalyzed Photo-degradation approach towards Organic Dyes

2021 ◽  
Author(s):  
Ayushi Singh ◽  
Ashish Kumar Singh ◽  
Jian-Qiang Liu ◽  
Abhinav Kumar
Keyword(s):  
Small Molecule ◽  
Coordination Polymers ◽  
Organic Dyes ◽  
Metal Organic Frameworks ◽  
Gas Storage ◽  
New Variety ◽  
Photo Degradation ◽  
Charge Dynamics ◽  
Potential Applications ◽  
Metal Organic

Metal-organic frameworks (MOFs) or coordination polymers (CPs) are regarded as new variety of materials that find potential applications in plethora of areas such as gas/small molecule absorption/separation, gas storage, membranes...

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.

scholarly journals Four Novel d10 Metal-Organic Frameworks Incorporating Amino-Functionalized Carboxylate Ligands: Synthesis, Structures, and Fluorescence Properties

2021 ◽  
Vol 9 ◽  
Author(s):  
Wang Xie ◽  
Jie Wu ◽  
Xiaochun Hang ◽  
Honghai Zhang ◽  
Kang shen ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Three Dimensional ◽  
Fluorescence Properties ◽  
Gravimetric Analysis ◽  
X Ray Diffraction ◽  
X Ray ◽  
Quenching Effect ◽  
D10 Metal ◽  
Metal Organic ◽  
Point Symbol

By employment of amino-functionalized dicarboxylate ligands to react with d10 metal ions, four novel metal-organic frameworks (MOFs) were obtained with the formula of {[Cd(BCPAB)(μ2-H2O)]}n (1), {[Cd(BDAB)]∙2H2O∙DMF}n (2), {[Zn(BDAB)(BPD)0.5(H2O)]∙2H2O}n (3) and {[Zn(BDAB)(DBPB)0.5(H2O)]∙2H2O}n (4) (H2BCPAB = 2,5-bis(p-carbonylphenyl)-1-aminobenzene; H2BDAB = 1,2-diamino-3,6-bis(4-carboxyphenyl)benzene); BPD = (4,4′-bipyridine); DBPB = (E,E-2,5-dimethoxy-1,4-bis-[2-pyridin-vinyl]-benzene; DMF = N,N-dimethylformamide). Complex 1 is a three-dimensional (3D) framework bearing seh-3,5-Pbca nets with point symbol of {4.62}{4.67.82}. Complex 2 exhibits a 4,4-connected new topology that has never been reported before with point symbol of {42.84}. Complex 3 and 4 are quite similar in structure and both have 3D supramolecular frameworks formed by 6-fold and 8-fold interpenetrated 2D coordination layers. The structures of these complexes were characterized by single crystal X-ray diffraction (SC-XRD), thermal gravimetric analysis (TGA) and powder X-ray diffraction (PXRD) measurements. In addition, the fluorescence properties and the sensing capability of 2–4 were investigated as well and the results indicated that complex 2 could function as sensor for Cu2+ and complex 3 could detect Cu2+ and Ag+via quenching effect.

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

2020 ◽  
Author(s):  
Stephen Shearan ◽  
Jannick Jacobsen ◽  
Ferdinando Costantino ◽  
Roberto D’Amato ◽  
Dmitri Novikov ◽  
...  
Keyword(s):  
Crystal Growth ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Nucleation And Growth ◽  
X Ray Diffraction ◽  
X Ray ◽  
Rate Determining Step ◽  
Wide Range ◽  
Metal Organic

We report on the results of a thorough <i>in situ</i> synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated Ce(IV)-based metal-organic frameworks (MOFs), analogues of the already well investigated Zr(IV)-based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as building blocks, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds <i>in situ</i> in a wide range of conditions, varying parameters such as temperature, amount of the protonation modulator nitric acid (HNO<sub>3</sub>) and amount of the coordination modulator acetic acid (AcOH). When only HNO<sub>3</sub> is present in the reaction environment, F4_MIL-140A(Ce) is obtained as a pure phase. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C, whereas the modulator influences nucleation and crystal growth to a similar extent. Upon addition of AcOH to the system, alongside HNO<sub>3</sub>, mixed-phased products, consisting of F4_MIL-140A(Ce) and F4_UiO-66(Ce), are obtained. In these conditions, F4_UiO-66(Ce) is always formed faster and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate determining step. An increase in the amount of HNO<sub>3</sub> slows down both nucleation and growth rates for F4_MIL-140A(Ce), whereas nucleation is mainly affected for F4_UiO-66(Ce). In addition, a higher amount HNO<sub>3</sub> favours the formation of F4_MIL-140A(Ce). Similarly, increasing the amount of AcOH leads to slowing down of the nucleation and growth rate, but favours the formation of F4_UiO-66(Ce). The pure F4_UiO-66(Ce) phase could also be obtained when using larger amounts of AcOH in the presence of minimal HNO<sub>3</sub>. Based on these <i>in situ</i> results, a new optimised route to achieving a pure, high quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.

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