Various pH-Dependent Copper(II) Coordination Architectures Constructed from N,N′-Di(3-pyridyl)succinamide and Two Different Dicarboxylates

2015 ◽  
Vol 68 (7) ◽  
pp. 1076 ◽  
Author(s):  
Xiu-Li Wang ◽  
Fang-Fang Sui ◽  
Hong-Yan Lin ◽  
Guo-Cheng Liu

Using a bis-pyridyl-bis-amide N,N′-di(3-pyridyl)succinamide (L) and two dicarboxylates as mixed ligands, four 2D copper(ii) metal–organic networks, formulated as [Cu(1,4-chdc)(L)]·3H2O (1), [Cu(1,4-chdc)(L)]·H2O (2), [Cu(2,5-tdc)(L)]·H2O (3), and [Cu(2,5-tdc)(L)]·2H2O (4) (L = N,N′-di(3-pyridyl)succinimide; 1,4-H2chdc = 1,4-cyclohexanedicarboxylic acid; 2,5-H2tdc = thiophen-2,5-dicarboxylic acid) have been hydrothermally synthesized under different pH conditions, and characterized by IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. Compound 1, formed at pH 5.4, contains two rare types of left-, right-handed [Cu-L]n helix chains, which are further connected by [Cu-1,4-chdc]n zigzag chains, affording a 2D wave-like polymeric network. Compound 2 was obtained at pH 5.9, and shows a 2D square-grid layer constructed from zigzag [Cu-L]n chains and linear [Cu-1,4-chdc]n chains. Compounds 3 and 4 possess a similar 2D grid layer to that of 2 with 44-sql topology, formed at pH 4.8 and 5.4 respectively, and are constructed from zigzag [Cu-L]n chains and linear [Cu-2,5-tdc]n chains. The effects of pH and secondary dicarboxylates on the diversity of structures are discussed. In addition, the thermal stabilities, photoluminescence properties, and photocatalytic activity of compounds 1–4 were also studied.

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.


Author(s):  
Hong-Tao Zhang ◽  
Xiao-Long Wang

The design and synthesis of metal–organic frameworks (MOFs) have attracted much interest due to the aesthetics of their crystalline architectures and their potential applications as new functional materials. A new twofold interpenetrated three-dimensional (3D) MOF, namely, poly[[triaqua(μ4-(2R,2′R)-2,2′-{[1,4-phenylenebis(carbonyl)]bis(azanediyl)}dipropionato-κ7 O 1:O 1,O 1′:O 4:O 4,O 4′,O 4′′)(μ3-(2R,2′R)-2,2′-{[1,4-phenylenebis(carbonyl)]bis(azanediyl)}dipropionato-κ3 O 1:O 4:O 4)dicadmium(II)] dihydrate], {[Cd2(C14H14N2O6)2(H2O)3]·2H2O} n , (I), has been synthesized by the reaction of Cd(CH3COO)2·2H2O with the synthesized ligand (2R,2′R)-2,2′-{[1,4-phenylenebis(carbonyl)]bis(azanediyl)}dipropionic acid (H2 L). Single-crystal X-ray diffraction analysis reveals that the carboxylate groups from two crystallographically independent L 2− dianions link the cadmium cations into a one-dimensional helical secondary building unit (SBU). The resulting SBUs are extended into a 3D metal–organic framework via the terephthalamide moiety of the ligand as a spacer. In the crystal, two independent MOFs interpenetrate each other, thus producing a twofold interpenetrated 3D architecture, which shows an unprecedented 2-nodal (7,9)-connected net with the point (Schläfli) symbol (37·46·58)(38·411·516·6). MOF (I) was further characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction and thermogravimetric analysis. The photoluminescence properties and UV–Vis absorption spectrum of (I) have also been investigated. The MOF exhibits enhanced fluorescence emission with a high photoluminescence quantum yield of 31.55% and a longer lifetime compared with free H2 L.


2011 ◽  
Vol 66 (2) ◽  
pp. 125-132 ◽  
Author(s):  
Guo-Cheng Liu ◽  
Jin-Xia Zhang ◽  
Xiu-Li Wang ◽  
Hong-Yan Lin ◽  
Ai-Xiang Tian ◽  
...  

Three new Cd(II) metal-organic coordination polymers, [Cd(bbi)(DNBA)2] (1), [Cd(bbbi)- (DNBA)2] (2), and [Cd(dmbbbi)(DNBA)Cl]·0.38H2O (3) [HDNBA = 3,5-dinitrobenzoic acid, bbi = 1,1-(1,4-butanediyl)bis(imidazole), bbbi = 1,1-(1,4-butanediyl)bis(benzimidazole), and dmbbbi = 1,1-(1,4-butanediyl)bis(5,6-dimethylbenzimidazole)], have been obtained from hydrothermal reactions of cadmium(II) chloride with the mixed ligands HDNBA and the three structurally related flexible bis(imidazole) derivatives. Single-crystal X-ray diffraction analyses have revealed that the dinuclear cadmium clusters acting as nodes interlinked by two μ2-carboxylic groups, are connected to four other clusters through bridging bbi (for 1) and bbbi (for 2) units to generate two extended two-dimensional (2-D) networks. Compound 3 features a 1-D zigzag chain structure. A systematic structural comparison of the title compounds indicates that the conformations and the steric hindrance of flexible bis(imidazole) derivatives each play an important role in the formation of the Cd(II) coordination polymers. The thermal stability of 1 and 2, and the luminescence behavior of 3 were also investigated.


2017 ◽  
Vol 70 (3) ◽  
pp. 314 ◽  
Author(s):  
Chuan-Bin Fan ◽  
Xiang-Min Meng ◽  
Yu-Hua Fan ◽  
Zi-Ao Zong ◽  
Xiao-Yin Zhang ◽  
...  

Two novel coordination polymers, namely {[Zn(sbdc)(bmib)]·0.4H2O}n (1) and {[Zn(sbdc)(bibd)]·DMF}n (2) (H2sbdc = 4,4′-stilbenedicarboxylic, bmib = 1,4-bis(2-methylimidazol-1-yl)butane, bibd = 1,1′-(1,4-butanediyl)bis(imidazole), DMF = N,N-dimethylformamide), have been acquired under solvothermal conditions, and have been characterised by elemental analysis, infrared spectra, thermogravimetric analysis, and single-crystal X-ray diffraction (XRD). Single-crystal XRD analysis reveals that 1 shows eight-fold interpenetrating 3D frameworks with a four-connected (66) sqc6 topology and 2 displays four-connected three-fold interpenetrating 3D frameworks. The flexible N-donor ligands play an important role in the construction of the final topological structures for 1 and 2. Furthermore, 1 and 2 exhibit good photodegradation capability and photoluminescence properties.


2017 ◽  
Vol 72 (8) ◽  
pp. 579-584 ◽  
Author(s):  
Feng Da Bao ◽  
Ya Jie Ruan ◽  
Ge Ge Du ◽  
Shu Kai Zou ◽  
Jie Zhang ◽  
...  

AbstractTwo metal-organic coordination polymers constructed from tris(p-carboxylphenyl)phosphine oxide (TPOH3), namely, [Zn(TPOH)(2,2′-bipy)(H2O)·H2O·DMF]n (1) and [Zn2(TPOH)2(1,4-bix)2·5H2O]n (2) (2,2′-bipy=2,2′-bipydine, 1,4-bix=1,4-bis(imidazol-1-ylmethyl)benzene), were synthesized and identified by IR, elemental analysis and single-crystal X-ray diffraction analysis. Both of the 2,2′-bipy and 1,4-bix ligands tailor the complexes 1 and 2 into chain structures. The thermal behavior and solid state photoluminescence properties correlated with the corresponding structural features were 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.


2019 ◽  
Vol 75 (6) ◽  
pp. 643-649 ◽  
Author(s):  
Xiao-Fei Li ◽  
Di Cheng ◽  
Xiang-Ru Meng ◽  
Huai-Xia Yang

Compared with the monomorphic type of ligand, combining mixed ligands in one coordination polymer offers greater tunability of the structural framework. Employment of N-heterocyclic ligands and aromatic polycarboxylates is an effective approach for the construction of metal–organic frameworks (MOFs). Two new coordination polymers incorporating both 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole (imb) and benzenedicarboxylic acid isomers, namely, catena-poly[[[di-μ-chlorido-bis[(2-carboxybenzoato-κ2 O 1,O 1′)cadmium(II)]]-bis{μ-2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole-κ2 N:N′}] dihydrate], {[Cd(C8H5O4)Cl(C11H10N4)]·H2O} n , (I), and poly[[aqua(μ2-benzene-1,3-dicarboxylato-κ3 O 1,O 1′:O 3){μ2-2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole-κ2 N:N′}cadmium(II)] dihydrate], {[Cd(C8H4O4)(C11H10N4)(H2O)]·2H2O} n , (II), have been prepared and structurally characterized by single-crystal X-ray diffraction. In polymer (I), imb ligands bridge CdII ions, forming a one-dimensional chain, and 2-carboxybenzoate anions coordinate to the CdII ions in a terminal fashion. Polymer (II) exhibits a two-dimensional network structure in which imb ligands and the benzene-1,3-dicarboxylate anions join CdII ions co-operatively. This indicates that changing of the aromatic dicarboxylic acids can result in polymers with different compositions and architectures. Moreover, their IR spectra, PXRD (powder X-ray diffraction) patterns, thermogravimetric analyses and fluorescence properties were also investigated.


2019 ◽  
Vol 10 (2) ◽  
pp. 180-188
Author(s):  
Leonã Da Silva Flores ◽  
Roselia Ives Rosa ◽  
Jefferson Da Silva Martins ◽  
Roberto Rosas Pinho ◽  
Renata Diniz ◽  
...  

In order to build a metal-organic framework with mixed ligands (acid-acid), a 3D coordination network based on manganese metal center was obtained [Mn3(BTC)2(DMSO)4]n; where BTC = Benzene-1,3,5-tricarboxylic acid and DMSO = Dimethylsulfoxide. The crystal structure was determined by single crystal X-ray diffraction, showing the assembly of a tridimensional 3,6-connected non-entangled polymeric network, with RTL topology. The secondary building unit (SBU) acts as a node of the 3-periodic expansion and involves carboxylate- and oxo-bridged metals. The DMSO employed in the synthesis is chemically involved in the coordination as a µ2-O bridge between distinct manganese metal centers. The structural characterization of the material was supported by spectroscopic (infrared absorption and Raman scattering), thermal (TG, DTG, and DTA) and elemental analysis.


2010 ◽  
Vol 6 (1) ◽  
pp. 891-896
Author(s):  
Manel Halouani ◽  
M. Dammak ◽  
N. Audebrand ◽  
L. Ktari

One nickel 1,4-cyclohexanedicarboxylate coordination polymers, Ni2 [(O10C6H4)(COO)2].2H2O  (I), was hydrothermally synthesized from an aqueous solution of Ni (NO3)2.6H2O, (1,4-CDC) (1,4-CDC = 1,4-cyclohexanedicarboxylic acid) and tetramethylammonium nitrate. Compound (I) crystallizes in the monoclinic system with the C2/m space group. The unit cell parameters are a = 20.1160 (16) Å, b = 9.9387 (10) Å, c = 6.3672 (6) Å, β = 97.007 (3) (°), V= 1263.5 (2) (Å3) and Dx= 1.751g/cm3. The refinement converged into R= 0.036 and RW = 0.092. The structure, determined by single crystal X-ray diffraction, consists of two nickel atoms Ni (1) and Ni (2). Lots of ways of which is surrounded by six oxygen atoms, a carboxyl group and two water molecules.


2020 ◽  
Author(s):  
Pia Vervoorts ◽  
Stefan Burger ◽  
Karina Hemmer ◽  
Gregor Kieslich

The zeolitic imidazolate frameworks ZIF-8 and ZIF-67 harbour a series of fascinating stimuli responsive properties. Looking at their responsitivity to hydrostatic pressure as stimulus, open questions exist regarding the isotropic compression with non-penetrating pressure transmitting media. By applying a state-of-the-art high-pressure powder X-ray diffraction setup, we revisit the high-pressure behaviour of ZIF-8 and ZIF-67 up to <i>p</i> = 0.4 GPa in small pressure increments. We observe a drastic, reversible change of high-pressure powder X-ray diffraction data at <i>p</i> = 0.3 GPa, discovering large volume structural flexibility in ZIF-8 and ZIF-67. Our results imply a shallow underlying energy landscape in ZIF-8 and ZIF-67, an observation that might point at rich polymorphism of ZIF-8 and ZIF-67, similar to ZIF-4(Zn).<br>


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