Eight-fold Interpenetrating Diamond-like Metal-Organic Frameworks Constructed with an N- and O-Donor Ligand for Cadmium(II) and Manganese(II)

2012 ◽  
Vol 67 (12) ◽  
pp. 1248-1254 ◽  
Author(s):  
Xiao-Chun Cheng ◽  
Xiao-Hong Zhu ◽  
Hai-Wei Kuai

Hydrothermal reactions of (E)-4-(2-(1H-imidazol-4-yl)vinyl)benzoic acid (HL) with Cd(II) and Mn(II) salts yield the complexes [Cd(L)2] (1) and [Mn(L)2] (2), which have been characterized by single-crystal and powder X-ray diffraction, IR spectroscopy, and elemental and thermogravimetric analyses. Complexes 1 and 2 are isomorphous and isostructural, displaying an uninodal 4-connected 8-fold interpenetrating 3D dia framework architecture with (66) topology. These frameworks exhibit high thermal stability up to 400 °C. The luminescence and non-linear optical (NLO) properties were investigated.

2021 ◽  
Vol 47 (9) ◽  
pp. 593-600
Author(s):  
A. A. Lysova ◽  
V. A. Dubskikh ◽  
K. D. Abasheeva ◽  
A. A. Vasileva ◽  
D. G. Samsonenko ◽  
...  

Abstract Three new metal−organic frameworks based on scandium(III) cations and 2,5-thiophenedicarboxylic acid (H2Tdc) are synthesized: [Sc(Tdc)(OH)]·1.2DMF (I), [Sc(Tdc)(OH)]·2/3DMF (II), and (Me2NH2)[Sc3(Tdc)4(OH)2]·DMF (III) (DMF is N,N-dimethylformamide). The structures of the compounds are determined by single-crystal X-ray structure analysis (CIF file CCDC nos. 2067819 (I), 2067820 (II), and 2067821 (III)). The chemical and phase purity of compound I is proved by elemental analysis, thermogravimetry, X-ray diffraction analysis, and IR spectroscopy.


2018 ◽  
Vol 73 (5) ◽  
pp. 311-317
Author(s):  
Zhao Xu ◽  
Fengqin An ◽  
Xiaohui Ma ◽  
Huiliang Zhou ◽  
Weiming Song ◽  
...  

AbstractBased on 2-(4-carboxyphenyl)imidazo[4,5-f]-1,10-phenanthroline (HNCP) and 2,5-thiophenedicarboxylate (TDC2−) ligands, three new lanthanide-containing (Sm, Nd, and Pr) compounds, [Sm(NCP)(TDC)]n (1), [Nd(NCP)(TDC)]n·2n(H2O)0.5 (2), and [Pr(NCP)(TDC)]n·n(H2O)0.5 (3), have been synthesized using the hydrothermal method and structurally characterized using single-crystal X-ray diffraction. Structural analyses have revealed that compounds 1–3 are 3D isostructural metal-organic frameworks in which the [Ln2(COO)4] dimers can be regarded as 6-connecting nodes, and the TDC2− and NCP− ligands are simplified as connectors to achieve the double interspersed 3D networks with the point symbol {412·63}. Thermogravimetric analysis has illustrated that the rigid architecture contributes to superior thermal stability with a thermal decomposition temperature of more than 400°C for the resulting metal-organic frameworks.


2013 ◽  
Vol 68 (7) ◽  
pp. 778-788 ◽  
Author(s):  
Xiu-Li Wang ◽  
Na Li ◽  
Ai-Xiang Tian ◽  
Jun Ying ◽  
Guo-Cheng Liu ◽  
...  

Three Keggin-based metal-organic frameworks (MOFs) containing multi-nuclear silver subunits, [Ag7(ptz)5(H2O)2][H2SiMo12O40] (1), [Ag8(ptz)5(H2O)2][AsW12O40] (2) and [Ag7(ptz)5(H2O)][HAsMo12O40] (3) (ptzH=5-(4-pyridyl)-tetrazole), have been synthesized under hydrothermal conditions by changing the inorganic polyanions. The new compounds have been characterized by elemental analyses, TG analyses, IR spectroscopy, and single-crystal X-ray diffraction. In compound 1, the multi-nuclear Ag5(ptz)5 subunits are interconnected to form chains, which are further linked by AgI cations to construct a 3D MOF with large channels. Pairs of SiMo12O404- polyanions reside in the channels as penta-dentate inorganic ligands. In 2, six AgI cations link five ptz- anions to construct a hexa-nuclear subunit [Ag6(ptz)5]+, which is interconnected to form chains. These chains are further linked by AgI cations to construct a 3D MOF, where AsW12O403- polyanions reside as hexa-dentate ligands. Compound 3exhibits a 3D MOF based on Ag5(ptz)5 subunits, in which the hexa-dentate AsMo12O403- polyanions are incorporated. The rigid tetrazole-based ligand ptz- plays an important role in the formation of the multi-nuclear subunits of the title compounds. The electrochemical properties of compound 1and the photocatalytic properties of compounds 1and 3have been investigated.


2020 ◽  
Vol 75 (8) ◽  
pp. 727-732
Author(s):  
Chen Zhang ◽  
Jian-Qing Tao

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.


Author(s):  
Stephen J. I. Shearan ◽  
Jannick Jacobsen ◽  
Ferdinando Costantino ◽  
Roberto D’Amato ◽  
Dmitri Novikov ◽  
...  

2021 ◽  
Author(s):  
Qing-Xia Yao ◽  
Miaomiao Tian ◽  
Jun Zheng ◽  
Jintang Xue ◽  
Xuze Pan ◽  
...  

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...


2014 ◽  
Vol 70 (a1) ◽  
pp. C157-C157
Author(s):  
Claire Hobday ◽  
Stephen Moggach ◽  
Carole Morrison ◽  
Tina Duren ◽  
Ross Forgan

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.


2021 ◽  
Vol 9 ◽  
Author(s):  
Wang Xie ◽  
Jie Wu ◽  
Xiaochun Hang ◽  
Honghai Zhang ◽  
Kang shen ◽  
...  

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.


2020 ◽  
Author(s):  
Stephen Shearan ◽  
Jannick Jacobsen ◽  
Ferdinando Costantino ◽  
Roberto D’Amato ◽  
Dmitri Novikov ◽  
...  

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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