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1.
Abstract Two new Keggin-polyoxometalate hybrids, {[Cu2(4,4′-bpy)2][PW10VIW2VO40]}[Cu2(obpy)2]4 · 2 H2O (1) and {[Cu4(2,2′-bpy)4(4,4′-bpy)3][SiW12O40]} · 2H2O (2) (4,4′-/2,2′-bpy = 4,4′-/2,2′-bipyridyl, Hobpy = 6-hydroxy-2,2′-bipyridyl), were hydrothermally synthesized and structurally
characterized. Gillard type hydration of 2,2′-bipy is observed during the synthesis of 1, resulting in a new obpy ligand in situ. X-ray structural analyses show that 1 consists of 1D hybrid chain {[Cu2(4,4′-bpy)2][PW10VIW2VO40]}∞ and [Cu2(obpy)2] dimer, whereas 2 possesses 1D hybrid structure based on Keggin-type [SiW12O40]4− anions and tetra-nuclear copper complexes [Cu4(2,2′-bpy)4(4,4′-bpy)3]4+. Both compounds present interesting supramolecular architectures based on π–π stacking and hydrogen bonds.
Graphical Abstract Compounds {[Cu2(4,4′-bpy)2][PW12O40]}[Cu2(obpy)2]4 · 2H2O (1) and [Cu4(2,2′-bpy)4(4,4′-bpy)3][SiW12O40] · 2H2O (2) were hydrothermally synthesized. 1 features that the [Cu2(obpy)2] dimers based on in situ generated obpy ligands are stumped between the layers where 1D hybrid chain {[Cu2(4,4′-bpy)2][PW12O40]}∞ locates, while 2 exhibits 1D chain-like structure based on anions [SiW12O40]4− and tetra-copper complexes [Cu4(2,2′-bpy)4(4,4′-bpy)3]4+.
相似文献
2.
Franz A. Mautner Febee R. Louka August A. Gallo Jörg H. Albering Mohamed R. Saber Nagua B. Burham Salah S. Massoud 《Transition Metal Chemistry》2010,35(5):613-619
Two thiocyanato-Cu(II) complexes including mononuclear dithiocyanato Cu(Me3dpt)(NCS)2 (1) and the polymeric 1D [Cu(d,l-Ala)(μN,S–NCS)(H2O)]
n
(2) were synthesized and structurally characterized (Me3dpt = bis(N-methyl-3-propyl)methylamine, Ala = alaninate anion). The IR spectrum of complex 1 confirmed the N-bonding coordination mode of the thiocyanate groups, and its visible spectrum revealed the square pyramidal
geometry around the central Cu2+ ion. Single X-ray crystallography of 1 showed that the Cu(II) center displays square pyramidal geometry with severe distortion toward trigonal bipyramidal environment. Complex 2 forms a 1-D polymeric chain with the NCS− acting as a μN,S-ligand. A distorted SP geometry around the Cu2+ centers was achieved by the O and N atoms of alaninato anion, the aqua ligand and by the N and S atoms of the bridging thiocyanate
groups. Hydrogen bonds of the type N–H···O, N–H···S and O–H···O are formed in this complex leading to the extension of the
1D chain to a supramolecular network. 相似文献
3.
The reaction of [M(L)]Cl2 · 2H2O (M = Ni2+ and Cu2+, L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane) with 1,1-cyclobutanedicarboxylic acid (H2-cbdc) generates 1D and 2D hydrogen-bonded infinite chains [Ni(L)(H-cbdc−)2] (1) and [Cu(L)(H-cbdc−)2] (2). (H-cbdc− = cyclobutane-1-carboxylic acid-1-carboxylate). These complexes have been characterized by X-ray crystallography, spectroscopy,
and cyclic voltammetry. The crystal structure of 1 shows a distorted octahedral coordination geometry around the nickel(II) ion, with four secondary amines and two oxygen atoms
of the H-cbdc− ligand at the trans position. In 2, the coordination environment around the central copper(II) ion shows a Jahn–Teller distorted octahedron with four Cu–N bonds
and two long Cu–O distances. The cyclic voltammogram of the complexes undergoes two one-electron waves corresponding to MII/MIII and MII/MI processes. The electronic spectra and electrochemical behavior of the complexes are significantly affected by the nature
of the axial H-cbdc− ligand. 相似文献
4.
Emanuel Makrlík J. Budka P. Vaňura P. Selucky 《Monatshefte für Chemie / Chemical Monthly》2009,287(3):157-160
Abstract
From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium \textM2 + ( \textaq ) + 1 ·\textSr2 + ( \textnb ) \rightleftarrows 1 ·\textM2 + ( \textnb ) + \textSr2 + ( \textaq ) {\text{M}}^{2 + } \left( {\text{aq}} \right) + {\mathbf{1}} \cdot {\text{Sr}}^{2 + } \left( {\text{nb}} \right) \rightleftarrows {\mathbf{1}} \cdot {\text{M}}^{2 + } \left( {\text{nb}} \right) + {\text{Sr}}^{2 + } \left( {\text{aq}} \right) taking place in the two-phase water–nitrobenzene system (M2+ = Ca2+, Ba2+, Cu2+, Zn2+, Cd2+, Pb2+, UO2 2+, Mn2+, Co2+, Ni2+; 1 = tetraphenyl p-tert-butylcalix[4]arene tetraketone; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Further, the stability constants of the 1 · M2+ complexes in water-saturated nitrobenzene were calculated; they were found to increase in the cation order Ba2+, Mn2+ < Co2+ < Cu2+, Ni2+ < Zn2+, Cd2+, UO2 2+ < Ca2+ < Pb2+. 相似文献5.
通过使用一个半刚性的多齿羧酸配体3,3',3"-(((2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene))tris(oxy))tribenzoic acid (H3L),在溶剂热条件下合成了4个配位聚合物{[Cd3(L)2(H2O)2]·5DMF·6H2O}n (1),{[Co3(L)2(H2O)2]·2DMF·6H2O}n (2),{[Mn3(L)2(H2O)2]·3DMF·6H2O}n (3),{[Zn3(L)2(H2O)2]·5DMA·5H2O}n (4),并通过X射线单晶衍射,热重分析对配合物结构进行了表征。4个化合物都是同构的,由沙漏型的M3簇和L3-配体作为次级结构单元,从而给出了一个金属-有机纳米笼的三维结构,从拓扑学的观点看,4个配合物的结构可以看作是三节点的(3,3,6)-连接的网络。荧光光谱测试表明配合物1和4在激发波长为272 nm下,在385 nm处显示了强的宽发射峰。荧光传感测试结果表明,配合物1是一种潜在的硝基苯类化合物的传感材料。 相似文献
6.
Xing Chen Wen-Tao Yin Qian Huang Hong-Rong Zuo Jia-Rong Zhou Lin-Liang Yu Chun-Lin Ni Xue-Lei Hu 《Transition Metal Chemistry》2010,35(2):143-149
Two new salts, [BzTPP]2[Cu(mnt)2] (1) and [4NO2BzTPP]2[Cu(mnt)2] (2) (BzTPP+ = benzyltriphenylphosphonium and mnt2− = maleonitriledithiolate) have been prepared and characterized by elemental analyses, UV, IR, molar conductivity and single-crystal
X-ray diffraction. The single-crystal structure analysis shows that 1 crystallizes in the monoclinic space group P21/n, while 2 crystallizes in the triclinic space group P−1. The effects of weak intramolecular interactions such as C–H···O, C–H···S, C–H···N, C–H···Cu hydrogen bonds and p···π, π···π stacking interactions in the solids generate a 3D network structure. It is noted that the change in the molecular
topology of the counteraction when the 4-substituted group in the benzyl ring is changed from H to NO2 results in differences in the crystal system, space group, weak interactions and the stacking mode of the cations and anions
of 1 and 2. The magnetic susceptibilities of these salts measured in the temperature range 2.0 to 300 K show weak ferromagnetic coupling
features with θ = 2.05 × 10−2 K for 1 and 5.13 × 10−3 K for 2. 相似文献
7.
Xiuli Wang Yufei Wang Guocheng Liu Hailiang Hu Aixiang Tian 《Journal of Cluster Science》2011,22(2):211-223
Two new inorganic–organic hybrid compounds constructed from different polyoxometalates (POMs) and copper multinuclear clusters,
[Cu(bmte)(H2Mo8O26)0.5]·3H2O (1) and [Cu3(bmte)3(HSiMo12O40)]·H2O (2) (bmte = 1,2-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)ethane), have been synthesized under hydrothermal conditions with
a flexible double tetrazole-based thioether and characterized by IR, TG and single-crystal X-ray diffraction analyses. In
compound 1, two bmte ligands chelate two CuI ions with three N atoms to form a binuclear nano-scale subunit [Cu2(bmte)2]2+, then the binuclear CuI subunits are connected by [Mo8O26]4− anions to build a one dimensional (1D) chain. In compound 2, a trinuclear nano-scale subunit [Cu3(bmte)3]3+ constructed from three CuI ions and three bmte ligands has been obtained, and the adjacent trinuclear subunits are linked by [SiMo12O40]4− anions to form a “zipper” 1D chain. The adjacent chains of the title compounds are ultimately extended into 2D layers by
hydrogen bonds between bmte and POMs. The structural difference of the two compounds indicates that the POMs play an important
structure-directed role on the final networks. In addition, the electrochemical behavior of 2-modified carbon paste electrode (2-CPE) and its electrocatalytic reduction of nitrite have been discussed. 相似文献
8.
Synthesis, structure characterization, and magnetic properties of three novel cyano-bridged complexes {[MnII(bpy)(DMF)2]2[MoIV(CN)8]·1.5H2O}
n
(1), [CuII(L)]2[MoIV(CN)8]·6.75H2O (2), and [MnII(bpy)2]4[MoIV(CN)8]2·4MeOH·4H2O (3) (where DMF = N,N′-dimethylformamide; bpy = 2,2-bipyridine and L = 1,3,6,8,11,14-hexaazatricyclo[12.2.1.18,11]octadecane) have been studied. The X-ray single-crystal structure reveals that 1 is a cyanide-bridged 1D infinite chain with the alternating of MnII(bpy)(DMF)2 and MoIV(CN)8 moieties. The neighboring chains interact with each other by hydrogen bonding to form a sheet-like network, and the layers
further extend to a 3D network due to the face-to-face π···π stack interactions. For 2, the MoIV center adopts a distorted square antiprism coordination environment, while the CuII center adopts a distorted square pyramidal geometry. The weak Mo–CN···Cu interactions between neighboring molecules lead
to a 2D network structure of 2. For 3, basic structural unit is centrosymmetric and contains four MnII centers bridged by two octacyanomolybdate(IV). Here, their magnetic properties have also been studied.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
9.
Two new neodymium complexes, [Nd2(abglyH)6(2,2′-bipy)2(H2O)2] · 4H2O 1 and {[Nd(abglyH)3(H2O)2] · (4,4′-bipy) · 7H2O}n
2 (abglyH2 = N-P-acetamidobenzenesulfonyl-glycine acid, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), have been synthesized and
their structures have been measured by X-ray crystallography. In 1, nine-coordinated Nd(III) ions are bridged by two syn–syn bidentate and two tridentate bridging carboxylate groups from four different abglyH− anions to form dinuclear motifs, which are further connected into a 3-D supramolecular framework via hydrogen bonds between
the binuclear motifs and the uncoordinated water molecules. In 2, eight-coordinated Nd(III) ions are linked by six carboxylate groups adopting a syn–syn bidentate bridging fashion to form a 1-D inorganic–organic alternating linear chain. These polymeric chains generate microchannels
extending along the a direction, and these cavities are occupied by discrete tetradecameric water clusters, which interact with their surroundings
and finally furnish the 3-D supramolecular network via hydrogen bonds. At the same time, π–π stacking interactions between
benzene rings from abglyH− anions also play an important role in stabilizing the network. 相似文献
10.
Abstract Two novel organic–inorganic composite phosphotungstates, [H9{Ce(α-PW11O39)2}Cu(en)2] · 6H2O (1) and H7[Cu(en)2{Er(α-PW11O39)2}Cu(en)2] · 12H2O (2) (en = ethylenediamine) have been synthesized by the hydrothermal reaction of the trivacant Keggin polyoxoanion [α-A-PW9O34]9− with CeIII or ErIII ions in the presence of Cu2+ ions and en, and structurally characterized by IR spectra, elemental analysis and thermogravimetric analysis. X-ray crystallographic
analyses indicate that they are all built by sandwich-type [Ln(α-PW11O39)2]11− (Ln = CeIII, ErIII) polyoxoanions and [Cu(en)2]2+ cations generating infinite one-dimensional arrangements. To our knowledge, this 1-D chain structures constituted by mono-Ln
sandwiched POM units and transition-metal complex cations are very rare.
Graphical Abstract Two novel organic–inorganic composite phosphotungstates, [H9{Ce(α-PW11O39)2}Cu(en)2] · 6H2O (1) and H7[Cu(en)2{Er(α-PW11O39)2}Cu(en)2] · 12H2O (2) (en = ethylenediamine) have been synthesized by the hydrothermal reaction of the trivacant Keggin polyoxoanion [α-A-PW9O34]9− with CeIII or ErIII ions in the presence of Cu2+ ions and en, and structurally characterized by IR spectra, elemental analysis and thermogravimetric analysis. X-ray crystallographic
analyses indicate that they are all built by sandwich-type [Ln(α-PW11O39)2]11− (Ln = CeIII, ErIII) polyoxoanions and [Cu(en)2]2+ cations generating infinite one-dimensional arrangements. To our knowledge, this 1-D chain structures constituted by mono-Ln
sandwiched POM units and transition-metal complex cations are very rare.
相似文献
11.
E. Makrlík P. Toman P. Vaňura P. Selucký R. Rathore 《Journal of Radioanalytical and Nuclear Chemistry》2010,286(1):55-59
From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Cs+(aq) + A−(aq) + 1(nb) ⇆ 1·Cs+(nb) + A− (nb) taking part in the two-phase water–nitrobenzene system (A− = picrate, 1 = hexaarylbenzene-based receptor; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K
ex (1·Cs+, A−) = 2.8 ± 0.1. Further, the stability constant of the hexaarylbenzene-based receptor·Cs+ complex (abbrev. 1·Cs+) in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log β
nb (1·Cs+) = 4.7 ± 0.1. By using quantum mechanical DFT calculations, the most probable structure of the 1·Cs+ complex species was solved. In this complex having C
3 symmetry, the cation Cs+ synergistically interacts with the polar ethereal oxygen fence and with the central hydrophobic benzene bottom via cation–π
interaction. Finally, the calculated binding energy of the resulting complex 1·Cs+ is −220.0 kJ/mol, confirming relatively high stability of the considered cationic complex species. 相似文献
12.
Ming-Li Liu Jian-Min Dou Da-Cheng Li Da-Qi Wang Jian-Zhong Cui 《Transition Metal Chemistry》2012,37(1):117-124
The thiosemicarbazide and hydrazide Cu(II) complexes, [Cu3L21(py)4Cl2] (1), [Cu(HL2)py] (2) and [Cu(HL3)py] (3), (H2L1 = 1-picolinoylthiosemicarbazide, H3L2 = N′-(2-hydroxybenzylidene)-3-hydroxy-2-naphthohydrazide, H3L3 = 2-hydroxy-N′-((2-hydroxy-naphthalen-1-yl)methylene)benzohydrazide) have been prepared and characterized through physicochemical and spectroscopic
methods as well as X-ray crystallography. Complex 1 has a centrosymmetric structure with –N–N– bridged Cu3 skeleton. Neighboring molecules are linked into a 3D supermolecular framework by π–π stacking interactions, N–H···Cl and
C–H···Cl hydrogen bonds. Complexes 2 and 3 have similar planar structures but different dimers formed by concomitant Cu···N and Cu···O interactions, respectively. Solvent
accessible voids with a volume of 391 ?3 are included in the structure of complex 2, indicating that this complex is a potential host candidate. Thermogravimetric analysis shows that the three complexes are
stable up to 100 °C. 相似文献
13.
Wei Li Yun-Li Liu Jian Liu Huai-teng Zhang Shu-Zhong Zhan De-Rong Cao 《Transition Metal Chemistry》2011,36(3):255-260
The triazenide, 1-[(2-carboxyethyl)benzene]-3-[2-pyridine]triazene (HL), has been synthesized. In the presence of Et3N, the reaction of HL with Cu(OAc)2·H2O or CuCl2·2H2O gives the tetranuclear copper(II) complexes {Cu4(L)2(μ2-OH)2(OAc)4} 1 and {Cu4L4(μ4-O)Cl2} 2, respectively. The X-ray crystal structures of both complexes have been obtained. Magnetic studies indicate significant antiferromagnetic
coupling between the copper(II) centers for both complexes, with coupling constants (J) of −493.4 cm−1 for 1 and −165 cm−1 for 2. 相似文献
14.
15.
A new ligand, 3-methyl-4-(p-bromophenyl)-5-(2-pyridyl)-1,2,4-triazole (L) and its complexes, trans-[CuL2(ClO4)2] (1) and cis-[CoL2(H2O)2](ClO4)2·H2O·CH3OH (2), have been synthesized and characterized by UV, IR, electrospray ionization mass spectrum, elemental analyses, and single-crystal
X-ray diffraction methods. In the structure, two L ligands are stabilized by intermolecular π···π interactions between the triazole rings. In the complexes, each L ligand adopts a chelating bidentate mode through N atom of pyridyl group and one N atom of the triazole. Both complexes have
a similar distorted octahedral [MN4O2] core (M = Cu2+ and Co2+) with two ClO4
− ions in the trans position in 1 but two H2O molecules in the cis arrangement in 2. 相似文献
16.
Derivative of 8-hydroxyquinoline i.e. Clioquinol is well known for its antibiotic properties, drug design and coordinating
ability towards metal ion such as Copper(II). The structure of mixed ligand complexes has been investigated using spectral,
elemental and thermal analysis. In vitro anti microbial activity against four bacterial species were performed i.e. Escherichia coli, Pseudomonas aeruginosa, Serratia marcescens, Bacillus substilis and found that synthesized complexes (15–37 mm) were found to be significant potent compared to standard drugs (clioquinol
i.e. 10–26 mm), parental ligands and metal salts employed for complexation. The kinetic parameters such as order of reaction
(n = 0.96–1.49), and the energy of activation (E
a = 3.065–142.9 kJ mol−1), have been calculated using Freeman–Carroll method. The range found for the pre-exponential factor (A), the activation entropy (S* = −91.03 to−102.6 JK−1 mol−1), the activation enthalpy (H* = 0.380–135.15 kJ mol−1), and the free energy (G* = 33.52–222.4 kJ mol−1) of activation reveals that the complexes are more stable. Order of stability of complexes were found to be [Cu(A4)(CQ)OH] · 4H2O > [Cu(A3)(CQ)OH] · 5H2O > [Cu(A1)(CQ)OH] · H2O > [Cu(A2)(CQ)OH] · 3H2O 相似文献
17.
Two-dimensional complexes of [Cd(cpoa)(o-pbim)]
n
(1) and {[Cd3(cpoa)3(o-pbim)2] · 2H2O}
n
(2) (cpoa2− = 4-carboxyphenoxy acetate, o-pbim = 2-(2-pyridyl)benzimidazole) are synthesized under hydrothermal condition. Single crystal
X-ray diffraction analysis shows that complex 1 contains a mono-nuclear unit, whereas complex 2 contains a trinuclear unit. The structural difference of 1 and 2 can be attributed to the various coordination modes of asymmetrically semi-flexible cpoa2− ligand. The luminescent properties of these two compounds are also investigated. 相似文献
18.
Xiao-Lan Wang Ying Lu Jing-Xin Meng En-Bo Wang Hai Fu 《Transition Metal Chemistry》2011,36(2):201-206
Three new organic–inorganic hybrid complexes based on the Wells–Dawson polyoxoanion, namely (H2bpp)[Ni2(bpp)2(H2O)4(P2W18O62)]·H2O 1, [Cu6(Hbpy)6(bpy)3(P2W18O62)2]·2H2O 2 and (Him)5[Cu(im)2(P2W18O62)]·4H2O 3 [bpp = 1,3-bis (4-pyridyl) propane, bpy = 4,4′-bipyridine, im = imidazole] have been synthesized and characterized. Complex
1 exhibits a three-dimensional (6, 3)-connected framework with anatase topology constructed from [α-P2W18O62]6− clusters and [Ni(bpp)]2+ fragments. Each [α-P2W18O62]6− anion links to six nickel atoms through six terminal oxygen atoms from four polar and two equatorial WO6 octahedra, which shows a novel coordination mode of a Wells–Dawson cluster with a transition-metal atom. Complex 2 displays an interesting one-dimensional double-chain structure built from [α-P2W18O62]6− clusters and [Cu2(bpy)(Hbpy)2]2+ fragments. To our knowledge, complex 2 represents the first double-chain organic–inorganic hybrid complex based on a Wells–Dawson-type cluster. Complex 3 possesses a one-dimensional zigzag chain structure constructed from [α-P2W18O62]6− anions and [Cu(im)2]+ units through weak Cu···O interactions. 相似文献
19.
Chi Won Kim Jungmin Ahn Sung Min Kim Tae Hwan Noh Ok-Sang Jung 《Transition Metal Chemistry》2011,36(5):545-551
Type studies on competitive polyatomic anion versus acetonitrile coordination in the self-assembly of a series of [Ag2(X)
m
(bip)(NCCH3)
n
](X)2−m
(X− = NO3
−, CF3SO3
−, ClO4
−, BF4
−, and PF6
−; m = 0, 2; n = 0, 2, 4; bip = 1,4-bis(2-isonicotinoyloxyethyl)piperazine) were carried out. Each bip spacer acts as an N4 tetradentate ligand and is linked to four silver(I) centers through two pyridine and two piperazine moieties, producing a
double strand consisting of two 20-membered ring units. The coordinating environment around the silver(I) center is subtly
determined by the competition of the polyatomic anions with acetonitrile, that is, by the Ag···NCCH3 versus Ag···X interactions. The coordinating ability of acetonitrile is inversely proportional to the order of the coordination
ability of the Hoffmeister series of polyatomic anions, NO3
− ≫ CF3SO3
− > ClO4
− > BF4
− ≫ PF6
−. 相似文献
20.
Yan-Fen Peng Lin-Lu Qian Jian-Gang Ding Tian-Rui Zheng Ya-Qian Zhang 《Journal of Coordination Chemistry》2018,71(9):1392-1402
Two copper(II) coordination polymers, {[Cu2(btre)(hsuc)Cl(H2O)]·1.5H2O}n (1) and {[Cu2(btre)(hsuc)Br(H2O)]·1.5H2O}n (2) (btre = 1,2-bis(1,2,4-triazol-4-yl)ethane, H3hsuc = 2-hydroxysuccinic acid), were synthesized by the hydrothermal method via in situ hydroxylation reaction with fumarate (fum), btre and CuCl2/CuBr2, and characterized by elemental analyses, IR, TG and X-ray diffraction. 1 and 2 are isostructural and show a 4-connected 2-D network based on [Cu2O] dimers. 1 and 2 show good photocatalytic activity for the degradation of organic dyes methylene blue and methyl orange under UV light irradiation. 相似文献