Syntheses and crystal structures of two new silver–organic frameworks based on N-pyrazinesulfonyl-glycine: weak Ag···O/N interaction affecting the coordination geometry

AbstractTwo new metal–organic frameworks, namely, [Ag2(L)]n (1) and {[Ag2.5(L)(bpy)2]·(NO3)0.5·(H2O)4.5}n (2), where H2L=N-pyrazinesulfonyl-glycine and bpy=4,4′-bipyridine, have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analysis. X-ray diffraction crystallographic analyses indicate that 1 displays a silver carboxylate-sulfonamide layer structure containing an uncommon heptanuclear [Ag7] cluster wherein four silver(I) atoms form an Ag4 plane with in a three-connected (6, 3) net. The molecular structure of 2 has three crystallographically independent two-coordinate Ag centers with an intersecting Ag-bpy chain structure in a six-connected (3, 6) or a four-connected (4, 4) topology. The L2− ligand serves as a μ7-(η2-O,N), (η2-O′,N′), O,O″,O″′,N,N″ ligand in 1 and as a μ3-(η2-O,N), N,O′ ligand in 2. In the crystal, a 3D supramolecular architecture is formed by coordinative bonding in 1, but through O–H···O bonding as well as π···π stacking in 2. The two compounds show a combination of coordinative bonds, ligand-supported Ag···Ag interactions and weak Ag···O/N coordinative interactions in the solid state.

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Synthesis, crystal structures, and thermal and spectroscopic properties of two Cd(II) metal-organic frameworks with a versatile ligand

Zeitschrift für Naturforschung B ◽

10.1515/znb-2016-0077 ◽

2016 ◽

Vol 71 (8) ◽

pp. 909-917 ◽

Cited By ~ 3

Author(s):

Jia-Ming Li ◽

Kun-Huan He ◽

Zhong-Feng Shi ◽

Hui-Yuan Gao ◽

Yi-Min Jiang

Keyword(s):

Room Temperature ◽

Metal Organic Frameworks ◽

Spectroscopic Properties ◽

Supramolecular Architecture ◽

X Ray Diffraction ◽

X Ray ◽

Bridging Ligand ◽

Hydrogen Bond Interactions ◽

Distorted Octahedral ◽

Metal Organic

AbstractTwo new metal-organic frameworks, namely, [Cd(L)(H2O)]n (1) and {[Cd0.5(L)(4,4′-bipy)0.5][Cd0.5(H2O)(4,4′-bipy)0.5]·H2O}n (2), where H2L = N-pyrazinesulfonyl-glycine and 4,4′-bipy = 4,4′-bipyridine, have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental, thermogravimetric, and photoluminescent analysis. X-ray diffraction crystallographic analyses indicate that 1 displays a distorted octahedral metal coordination in a 3-connected (4, 82) topology, while the molecular structure of 2 has a 4-connected (4, 4) topology with two perfectly octahedrally coordinated Cd centers. The L2– ligand serves as a N,N,O-tridentate, μ2-pyrazine-bridging, and μ2-carboxylate-bridging ligand in 1, and as a N,O-bidentate and μ2-carboxylate-bridging ligand in 2. In the crystal, a 3D supramolecular architecture is formed by O–H···O hydrogen bond interactions in 1, but through O–H···O as well as π···π stacking in 2. The two compounds show intense fluorescence in the solid state at room temperature.

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Hydrothermal synthesis, crystal structure and photoluminescence of two homochiral zinc(II) coordination polymers

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229615012115 ◽

2015 ◽

Vol 71 (7) ◽

pp. 618-622 ◽

Cited By ~ 3

Author(s):

Shao-Ming Ying ◽

Jing-Jing Ru ◽

Wu-Kui Luo

Keyword(s):

Crystal Structure ◽

Coordination Polymers ◽

Layer Structure ◽

Metal Organic Frameworks ◽

Two Dimensional ◽

X Ray Diffraction ◽

Strong Emission ◽

X Ray ◽

Elemental Analyses ◽

Metal Organic

Metal–organic frameworks (MOFs) have potentially useful applications and an intriguing variety of architectures and topologies. Two homochiral coordination polymers have been synthesized by the hydrothermal method, namely poly[(μ-N-benzyl-L-phenylalaninato-κ4O,O′:O,N)(μ-formato-κ2O:O′)zinc(II)], [Zn(C16H16NO2)(HCOO)]n, (1), and poly[(μ-N-benzyl-L-leucinato-κ4O,O′:O,N)(μ-formato-κ2O:O′)zinc(II)], [Zn(C13H18NO2)(HCOO)]n, (2), and studied by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy and fluorescence spectroscopy. Compounds (1) and (2) each have a two-dimensional layer structure, with the benzyl or isobutyl groups of the ligands directed towards the interlayer interface. Photoluminescence investigations show that both (1) and (2) display a strong emission in the blue region.

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Between MOFs and molecules: organolead(IV) compounds with chain structures

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229618004850 ◽

2018 ◽

Vol 74 (5) ◽

pp. 523-528

Author(s):

Abdel-Fattah Shihada ◽

Frank Weller ◽

Werner Massa

Keyword(s):

Linear Chain ◽

Metal Organic Frameworks ◽

Chain Structure ◽

One Dimension ◽

X Ray Diffraction ◽

X Ray ◽

Polydentate Ligands ◽

Metal Organic ◽

A Chain ◽

Organolead Compounds

Organolead compounds are of interest mainly as catalysts and organolead halides have proved to be very efficient materials for solar cells. Two organolead(IV) dimethylarsinates, namely catena-poly[[triphenyllead(IV)]-μ-chlorido-[triphenyllead(IV)]-μ-dimethylarsinato-κ2 O:O′], [Pb2(C6H5)6(C2H6AsO2)Cl] n or [(Ph3Pb)2Cl(O2AsMe2)], (1), and poly[chlorido(μ3-dimethylarsinato-κ3 O:O,O′:O′)diphenyllead(IV)], [Pb(C6H5)2(C2H6AsO2)Cl] n or [(Ph2ClPb)(O2AsMe2)], (2), together with the triphenyllead(IV) diphenylphosphinate catena-poly[[triphenyllead(IV)]-μ-diphenylphosphinato-κ2 O:O′], [Pb(C6H5)3(C12H10O2P)] n or [(Ph3Pb)(O2PPh2)], (3), have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy and mass spectrometry. In (1), a chain structure was found with alternating chloride and Pb—O—As—O—Pb arsinate bridges between five-coordinate PbIV atoms. In (2), bidentate and chelate-like bonded dimethylarsinate ligands form double chains with heptacoordinated PbIV atoms. In (3), a pentacoordinated PbIV atom is connected by Pb—O—P—O—Pb phosphinate bridges to form a linear chain. Obviously, the steric demand of the phenyl ligands at PbIV reduces the possibility of interconnections via polydentate ligands to one dimension only. Thus, no metal–organic frameworks (MOF) are formed but instead various chain structures are observed.

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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

Zeitschrift für Naturforschung B ◽

10.1515/znb-2020-0041 ◽

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.

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

Chemistry - A European Journal ◽

10.1002/chem.202005085 ◽

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

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

Dalton Transactions ◽

10.1039/d1dt03188k ◽

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...

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Compressibility Studies of Zirconium Based Metal-Organic Frameworks

Acta Crystallographica Section A Foundations and Advances ◽

10.1107/s2053273314098428 ◽

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

Frontiers in Chemistry ◽

10.3389/fchem.2021.708314 ◽

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.

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

10.26434/chemrxiv.13252544 ◽

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 in situ 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 in situ in a wide range of conditions, varying parameters such as temperature, amount of the protonation modulator nitric acid (HNO3) and amount of the coordination modulator acetic acid (AcOH). When only HNO3 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 HNO3, 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 HNO3 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 HNO3 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 HNO3. Based on these in situ 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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