Three 3D Metal-Organic Frameworks Constructed from Keggin Polyanions and Multi-nuclear AgI Clusters: Assembly, Structures and Properties

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.

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.


2015 ◽  
Vol 71 (7) ◽  
pp. 618-622 ◽  
Author(s):  
Shao-Ming Ying ◽  
Jing-Jing Ru ◽  
Wu-Kui Luo

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.


CrystEngComm ◽  
2021 ◽  
Author(s):  
Li Tian ◽  
Zhi Long Ma ◽  
Mengchen Wang ◽  
Jian Yun Shi

Solvothermal reaction of a novel multidentate ligand 2,5-bis-(1,2,4-triazol-1-yl)-terephthalic acid (H2TTPA), with MnCl2 afforded three structurally different coordination polymers with the similar formula [Mn(TTPA)•H2O]n (Mn-(1-3)). Single-crystal X-ray diffraction analyses show that...


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.


2017 ◽  
Vol 72 (2) ◽  
pp. 107-113 ◽  
Author(s):  
Sheng-Chun Chen ◽  
Feng Tian ◽  
Ming-Yang He ◽  
Qun Chen

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.


CrystEngComm ◽  
2021 ◽  
Author(s):  
Guoshuai Zhang ◽  
Chen Fu ◽  
Heyi Zhang ◽  
Hong Zhang

A new cadmium metal-organic framework [Cd(IsoNDI)(ClO4)·H2O]n (ZH-102, IsoNDI = N,N′-di(4-pyridylacylamino)-1,4,5,8-naphthalene diimide) has been synthesized under solvothermal conditions and characterized systematically by elemental analyses, IR spectroscopy, powder X-ray diffraction, and thermogravimetric...


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.


2013 ◽  
Vol 68 (11) ◽  
pp. 1214-1218 ◽  
Author(s):  
Heng Liu ◽  
Ying Guo ◽  
Rui Ran ◽  
Huiyuan Ma ◽  
Haijun Pang ◽  
...  

A heterometallic metal-organic complex (MOC), K[Co(1,10-phen)2(H2O)]2[BW12O40]·2H2O (phen=1,10-phenanthroline) (1), has been synthesized hydrothermally and characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction. The complex exhibits cobaltbisupported tungstoborate units and potassium cations. The luminescence of the title complex has been investigated.


2015 ◽  
Vol 68 (8) ◽  
pp. 1299 ◽  
Author(s):  
Haiyan Liu ◽  
Xufeng Meng ◽  
Lihui Zhang ◽  
Anqiang Jia

Under urothermal conditions, the self-assembly of ZnII ions, 1,2,3-triazole, and two isomeric dicarboxylate ligands (1,4-H2ndc and 2,6-H2ndc) afforded two new metal–organic frameworks, namely [Zn(1,4-ndc)0.5(taz)]n·n(e-urea) (1) and [Zn(2,6-ndc)0.5(taz)]n·n(H2O)·n(e-urea) (2) (1,4-H2ndc = 1,4-naphthalenedicarboxylic acid; 2,6-H2ndc = 2,6-naphthalenedicarboxylic acid; Htaz = 1,2,4-triazole; e-urea = ethyleneurea), which were further determined by single-crystal X-ray diffraction analyses, elemental analyses, powder X-ray diffraction analyses, and IR spectra. Compound 1 features a 3D pillar-layered framework with 6-connected pcu topology (pcu = α-Po), and compound 2 also features a 3D pillar-layered framework with 6-connected pcu topology. In addition, the thermal stabilities and solid-state photoluminescent properties of compounds 1 and 2 were also studied.


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.


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