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 ◽  
...  

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.

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.


2020 ◽  
Vol 76 (2) ◽  
pp. 148-158
Author(s):  
Fang-Hua Zhao ◽  
Zhong-Lin Li ◽  
Shu-Fang Zhang ◽  
Jian-Hui Han ◽  
Mei Zhang ◽  
...  

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.


2020 ◽  
Vol 76 (5) ◽  
pp. 398-404
Author(s):  
Zhong-Xuan Xu ◽  
Chun-Yan Ou ◽  
Chun-Xue Zhang

Two three-dimensional cobalt-based metal–organic frameworks with 5-(hydroxymethyl)isophthalic acid (H2HIPA), namely poly[[μ2-1,4-bis(2-methyl-1H-imidazol-1-yl)benzene-κ2 N 3:N 3′][μ2-5-(hydroxymethyl)isophthalato-κ2 O 1:O 3]cobalt(II)], [Co(C9H6O5)(C14H14N4)] n (1), and poly[tris[μ2-1,4-bis(1H-imidazol-1-yl)benzene-κ2 N 3:N 3′]bis[μ3-5-(hydroxymethyl)isophthalato-κ2 O 1:O 3:O 5]dicobalt(II)], [Co2(C9H6O5)2(C12H10N4)3] n (2), were synthesized under similar hydrothermal conditions. Single-crystal X-ray diffraction analyses revealed that 5-(hydroxymethyl)isophthalate (HIPA2−) and 1,4-bis(2-methyl-1H-imidazol-1-yl)benzene (1,4-BMIB) are simple linkers connecting cobalt centres to build a fourfold interpenetration dia framework in complex 1. However, complex 2 is a pillared-layer framework with a (3,6)-connected network constructed by 1,4-bis(1H-imidazol-1-yl)benzene (1,4-DIB) linkers, 3-connected HIPA2− ligands and 6-connected CoII centres. The above significant structural differences can be ascribed to the introduction of the different auxiliary N-donor ligands. Moreover, UV–Vis spectroscopy and Mott–Schottky measurements confirmed that complexes 1 and 2 are typical n-type semiconductors.


2020 ◽  
Vol 76 (4) ◽  
pp. 314-321
Author(s):  
Bing-Feng Li ◽  
Xi-Ting Xu ◽  
Tong-Min Dong ◽  
Wan-Ying Zhou ◽  
Yang Gu ◽  
...  

The judicious selection of suitable ligands is vitally important in the construction of novel metal–organic frameworks (MOFs) with fascinating structures and interesting properties. Recently, imidazole-containing multidentate ligands have received much attention. Two new CdII coordination frameworks, namely, poly[tris{μ-1,4-bis[(1H-imidazol-1-yl)methyl]benzene-κ2 N 3:N 3′}tetrakis(nitrato-κ2 O,O′)dicadmium], [Cd2(NO3)4(C14H14N4)3] n , (I), and poly[[bis{μ3-1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene-κ3 N 3:N 3′:N 3′′}cadmium] hexafluorosilicate], {[Cd(C18H18N6)2](SiF6)} n , (II), have been synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. In polymer (I), the 1,4-bis[(1H-imidazol-1-yl)methyl]benzene ligand bridges Cd2+ ions with a distorted seven-coordinated pentagonal bipyramidal geometry, forming a one-dimensional ladder chain, and the nitrate anions coordinate to the Cd2+ ions in a terminal bidentate fashion. In the crystal, adjacent chains are further connected by C—H...O hydrogen bonds to generate a two-dimensional (2D) supramolecular structure. Polymer (II) exhibits a 2D layered structure in which 1,3,5-tris[(1H-imidazol-1-yl)methyl] benzene ligands join Cd2+ centres having a six-coordinated octahedral structure. The layers are connected by hexafluorosilicate anions via C—H...F hydrogen-bond interactions, giving rise to a three-dimensional supramolecular network structure in the solid state. In addition, powder X-ray diffraction (PXRD) patterns were recorded, thermogravimetric analyses (TGA) carried out and fluorescence properties investigated.


2017 ◽  
Vol 73 (2) ◽  
pp. 78-83
Author(s):  
Xiong-Wen Tan ◽  
Heng-Feng Li ◽  
Chang-Hong Li

Many factors, such as temperature, solvent, the central metal atom and the type of coligands, may affect the nature of metal–organic frameworks (MOFs) and the framework formation in the self-assembly process, which results in the complexity of these compounds and the uncertainty of their structures. Two new isomeric ZnIImetal–organic frameworks (MOFs) based on mixed ligands, namely, poly[[μ-1,5-bis(2-methyl-1H-imidazol-1-yl)pentane-κ2N3:N3′](μ-5-methylisophthalato-κ2O1:O3)zinc(II)], [Zn(C9H6O4)(C13H20N4)]n, (I), and poly[[μ-1,5-bis(2-methyl-1H-imidazol-1-yl)pentane-κ2N3:N3′](μ3-5-methylisophthalato-κ3O1:O1′:O3)(μ3-5-methylisophthalato-κ4O1:O1′:O3,O3′)dizinc(II)], [Zn2(C9H6O4)2(C13H20N4)]n, (II), have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and thermogravimetric analysis. Complex (I) displays a two-dimensional layer net, while complex (II) exhibits a twofold interpenetrating three-dimensional framework. Both complexes show high stability and good fluorescence in the solid state at room temperature.


Author(s):  
Yanwen Sun ◽  
Zhen Chen ◽  
Xiaozhong Wang ◽  
Lei Wang ◽  
Xue Yang ◽  
...  

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.


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 ◽  
...  

2014 ◽  
Vol 919-921 ◽  
pp. 2013-2016 ◽  
Author(s):  
Ya Bing Liu ◽  
Hong Jie Wang ◽  
Hong Kai Zhao

A POM - based organice - inorganic hybrid compound with the chemical formula of[Cu (phen)2]3[W6O19] (phen = 1,10-phenanthroline) (1) has been hydrothermally synthesized andstructurally characterized by the elemental analysis, and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space groupC2/c witha=18.319(4) Å,b= 17.311(4) Å,c= 22.248(4) Å,β= 112.40(3) o,V= 6523(2) Å3,Z= 4, R1= 0.0448, andwR2=0.1218. Compound 1 consists of the [W6O19]3-building blocks and [Cu (phen)2]+metal organic cationic moieties, which are packed together via the extensive hydrogen-bonding interactions to form a three-dimensional supramolecular framework. The adsorption of methylene blue (MB) under UV irradiation with 1 as the heterogeneous adsorbent has been investigated, showing a good adsorptive property of 1 for MB degradation.


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...


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