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1.
D. N. Dybtsev K. A. Kovalenko Yu. V. Mironov V. P. Fedin G. Férey N. A. Yakovleva E. A. Berdonosova S. N. Klyamkin E. V. Kogan 《Russian Chemical Bulletin》2009,58(8):1623-1626
The interaction of mesoporous chromium(iii) terephthalate [Cr3O(C8H4O4)3F(H2O)2] (MIL-101) with an aqueous solution of the anionic cluster [Re4S4F12]4− ({Re4}) afforded a novel hybrid material {Re4}@MIL-101. According to the elemental analysis data, one cavity of the nanoporous framework contains up to two-three tetranuclear
rhenium clusters. The hybrid sorbent obtained reversibly absorbs up to 3.7 wt.% hydrogen at 77 K and 30 atm. 相似文献
2.
Dr. Sanil E. Sivan Minhui Lee Su-Kyung Lee Dr. Ji Woong Yoon Dr. Kiwoong Kim Dr. Do-Young Hong Kyung-Ho Cho Dr. U-Hwang Lee Prof. Jong-San Chang Dr. Jaehoon Jung Prof. Young Kyu Hwang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):12889-12894
Oxo-bridged trimeric chromium acetate clusters [Cr3O(OOCCH3)6(H2O)3]NO3 have been encapsulated for the first time in the mesoporous cages of the chromium terephthalate MIL-101(Cr). The isolated clusters in MIL-101(Cr) have increased affinity towards propylene compared to propane, due to generation of a new kind of pocket-based propylene-binding site, as supported by DFT calculations. 相似文献
3.
《Journal of Molecular Catalysis #》1991,64(2):247-256
Novel catalytically active monooxomolybdenum(IV) species containing four thiolate ligands obtainable in solution by NaBH4 reduction of [MovO(SC6H5)4]−, [MovO(Z-cys-Val-OMe)4]−, (Z=benzyloxycarbonyl), or [MovO(S2C6H4)2]− perform the pyridine-N-oxide oxidation of benzoin in N,N-dimethylformamide at 30 °C. The order of catalytic activity is [MovO(Z-cys-Val-OMe)4]− > [MovO(S2C6H4)2]− > [MovO(SC6H5)4]− ([benzoin]/[oxidant]/[catalyst]= 20/20/1), while the oxidation by air under the same catalytic conditions gives a different order, [MovO(Z-cys-Val-OMe)4]−> [MovO(SC6H5)4]− >[MovO(S2C6H4)2]−. During the catalytic cycle in the amine-N-oxide oxidation, two intermediate species, [MoIVOL4]2− and [MoVIO2L4]2−, were detected by 1H NMR, while in the air oxidation an unidentified Mo(VT) species is involved. 相似文献
4.
Relativistic density functional calculations including scalar and spin-orbit effects via the ZORA approximation and including
solvent effects were carried out on the [Re6S8(CN)6]4−, [Re5MoS8(CN)6]5−, [Re4Mo2S8(CN)6]5−, [Re3Mo3S8(CN)6]5−, [Re2Mo4S8(CN)6]5−, [ReMo5S8(CN)6]5− and [Mo6S8(CN)6]6− clusters. By increasing the replacement of each Re atom with Mo atoms we find that for x > 2 the HOMO–LUMO gap decreases significantly. The calculated gap of the [Re3Mo3S8(CN)6]5−, [Re2Mo4S8(CN)6]5− and [ReMo5S8(CN)6]5− clusters is similar to the calculated and observed gap of the superconducting PbMo6S8 Chevrel phases. The current calculations also indicates that the electronic similarities of the lowest excited states of
the semiconducting 24e [Re5MoS8(CN)6]5− and 23e [Re4Mo2S8(CN)6]5− clusters with the strongly luminescent 24e [Re6S8(CN)6]4− cluster, suggest that these mixed metal clusters might be luminescent. 相似文献
5.
《Journal of Coordination Chemistry》2012,65(23):3970-3979
AbstractThree inorganic materials based on Strandberg polyoxoanion, Na10[Ag(P2Mo5O23)]2·8H2O (1), Na8[{Cu(H2O)4}(HP2Mo5O23)2]·8H2O (2), and Na8[{Co(H2O)4}(HP2Mo5O23)2]·6H2O (3), were hydrothermally synthesized and characterized by elemental analyses, IR, TG, and single crystal X-ray diffraction analyses. The compounds are based on the [P2Mo5O23]6? cluster and transition metal linkers. Compound 1 is a 1-D wave-like chain connected by Ag+ bridges. Compounds 2 and 3 are isostructural dimers bonded by {Cu(H2O)4} or {Co(H2O)4} linkers. The 1-D chain and dimeric clusters of 1-3 are further extended to 3-D supramolecular networks via hydrogen bonds and supramolecular interactions. Channels with different sizes are observed in 1-3, in which isolated Na+ and lattice water molecule fill the channels via intermolecular interactions. Weak interactions play important roles in stabilizing the three 3-D networks. Electrochemical and electrocatalytic properties of 1-3 have been investigated. 相似文献
6.
《Journal of Coordination Chemistry》2012,65(17):3028-3041
In this study, a series of compounds based on Dawson-type phosphomolybdates, H3(C6NO2H6)2[K(H2O)3(C6NO2H5)3][P2Mo18O62] ? 5.5H2O (1), (C6NO2H6)6[Ln(H2O)7(C6NO2H5)2]2[P2Mo18O62]2·13.5H2O (Ln = Ce (2), La (3)) have been synthesized and characterized by elemental analysis, IR and UV-Vis spectroscopy methods, TG analysis, and single-crystal X-ray diffraction. Compound 1 consists of [P2Mo18O62]6? building units joined by potassium-pyridine-3-carboxylic acid complexes, resulting in a wavelike polyoxometalate (POM) chain, which further interacts with each other via intermolecular interactions to form a 3-D supramolecular channel framework containing guest water molecules. Compounds 2 and 3 possess a 3-D supramolecular framework with 1-D tunnel constructed from [P2Mo18O62]6? and mononuclear lanthanide coordination complex fragments. To the best of our knowledge, 1 not only represents the first example of 1-D hybrid assembly based on Dawson-type phosphomolybdate, but also the first hybrid compound constructed from Dawson-type POMs and alkali–metal coordination complex fragments. 相似文献
7.
Organic‐Inorganic Hybrid Supramolecular Assemblies Based on Isomers [HxAs2Mo6O26](6–x)– Clusters
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The arsenomolybdates [H2As2Mo6O26(H2O)] · (H2biyb)2 · 2H2O ( 1 ) and [H3As2Mo6O26] · (H3pt)2 ( 2 ) [biyb = 1,4‐bis(imidazol‐1‐ylmethyl)benzene, pt = 4′‐(3′′‐pyridyl)‐2,3′:6′3′′‐terpyridine] were synthesized via hydrothermal method. The structures of the compounds were characterized by single‐crystal X‐ray diffraction analyses, elemental analyses, IR spectroscopy, and TG analysis. Compounds 1 and 2 exhibit two isomeric forms of [HxAs2Mo6O26](6–x)–. The structure of 1 is constructed from the B‐type [H2As2Mo6O26(H2O)]4– polyanions and free biyb ligands via weak interactions to form 3D supramolecular framework with a {3 · 4 · 53 · 6}{3 · 43 · 52}{3 · 5 · 6}2{3 · 52}2 topology structure. In compound 2 , the A‐type [H3As2Mo6O26]3– clusters are surrounded by pt ligands through hydrogen bond interactions forming 3D supramolecular framework with a {43 · 63}2{46 · 66 · 83} topology structure. The electrochemical behaviors, electrocatalytic and photocatalytic activities of 1 and 2 are detected. 相似文献
8.
9.
K. A. Brylev N. G. Naumov S. G. Kozlova M. R. Ryzhikov S. -J. Kim N. Kitamura 《Russian Journal of Coordination Chemistry》2012,38(3):183-191
New octahedral anionic heterometal rhenium-osmium cluster complexes [Re5OsSe8(OH)6]3− and [Re4Os2Se8(OH)6]2− were synthesized starting from [Re5OsSe8Cl6]3− and [Re4Os2Se8Cl6]2−, respectively. They were isolated as salts of the compositions Cs3[Re5OsSe8(OH)6] · 11H2O (I), K3[Re5OsSe8(OH)6] · 7H2O (II), and K2[Re4Os2Se8(OH)6] · 3H2O (III). The protonation of the terminal OH ligands of [Re5OsSe8(OH)6]3− in an aqueous solution resulted in crystallization of a neutral complex [Re5OsSe8(H2O)3(OH)3] · 12H2O (IV). The compounds have been characterized by single-crystal X-ray diffraction analysis. The luminescence properties of [Re5OsSe8(OH)6]3− and [Re4Os2Se8(OH)6]2− were studied. In addition, the electronic structures of the complexes were elucidated by DFT calculations. 相似文献
10.
Morteza Tahmasebi Masoud Mirzaei Hossein Eshtiagh-Hosseini Joel T. Mague Antonio Bauz Antonio Frontera 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(4):469-477
A new inorganic–organic hybrid based on an aspartate functionalized polyoxomolybdate, [pentaaquacobalt(II)]‐μ‐aspartate‐[γ‐octamolybdate]‐μ‐aspartate‐[pentaaquacobalt(II)] tetrahydrate, [Co2(C4H6NO4)2(γ‐Mo8O26)(H2O)10]·4H2O ( 1 ), has been synthesized under hydrothermal conditions from the reaction of an Evans–Showell‐type polyoxometalate, (NH4)6[Co2Mo10H4O38], and l ‐aspartic acid. The complex exhibits a supramolecular three‐dimensional framework structure in the crystal lattice. Compound 1 was structurally characterized by elemental analyses, IR and UV–Vis (diffuse reflectance) spectroscopy and single‐crystal X‐ray diffraction. In this compound, aspartic acid acts as a bridge between the two Co atoms and the Mo centres, with the –CH2COOH side chain directly linked to the Mo centre in γ‐[Mo8O26]4? and the α‐carboxylate side chain bound to the Co centre. Commonly, the binding of transition‐metal complexes to POMs involves coordination of the metal to a terminal O atom of the POM so that 1 , with a bridging ligand between Mo and Co atoms, belongs to a separate class of hybrid materials. While the starting materials are both chiral and one might expect them to form a chiral hybrid, the decomposition of the chiral Evans–Showell‐type POM and its conversion to the centrosymmetric γ‐octamolybdate POM, plus the presence of two aspartate ligands centrosymmetrically placed on either side of the POM, leads to the formation of an achiral hybrid. We have studied energetically by means of density functional theory (DFT) calculations and using the Bader's `atoms‐in‐molecules' analysis the electrostatically enhanced hydrogen bonds (EEHBs) observed in the solid state of 1 , which are crucial for the formation of one‐dimensional supramolecular assemblies. 相似文献
11.
Yu-Nan Zhang Bai-Bin Zhou Jing-Quan Sha Ji-Wen Cui 《Journal of solid state chemistry》2011,184(2):419-426
By using amines with different lengths, two layered cobalt-molybdenum phosphates with different interlayer distances, (C2N2H10) [HCo(H2O)2P2MoO10] (1), and (C3N2H12)4{Co3 [P4Mo6O26(OH)5]2}· 5H2O (2), have been hydrothermally synthesized and characterized. In compound 1, the H2en direct the [CoMoP2] clusters to form a layered framework. By changing the lengths of protonated organic amines (H2en to 1, 3-H2pn), compound 2 is obtained, in which the sandwich-shaped [Co (Mo6P4)2] clusters are linked by tetrahedrally coordinated cobalt into a layered framework. With the lengths of protonated organic amines increasing, the interlayer distances in compound 2 become larger. This work successfully demonstrates that tuning the lengths and conformation of the protonated organic amines can provide a facile route for the formation of organically templated inorganic open-framework materials. Additionally, susceptibility measurement shows that the two compounds both exhibit antiferromagnetic interactions. 相似文献
12.
《Solid State Sciences》2012,14(9):1289-1294
Two new three-dimensional (3D) organic–inorganic hybrid compounds [K2Ag8(pydc)2(Hpydc)2(H2O)4SiW12O40]·4H2O (1) and (NH4)4[KAg2(Hpydc) (H2O)4.5(H2W12O40)]·4H2O (2) [H2pydc = pyridine-2,3-dicarboxylate], were conventionally synthesized and characterized by IR, TG, elemental analysis, and single-crystal X-ray diffraction technique. In 1, six-nucleus [Ag6(Hpydc)2]4+ and two-nucleus [Ag2(pydc)2]2− are linked alternately through oxygen atoms of the carboxylic group leading to a grid-like 2D layer. These layers are supported by SiW12 clusters, giving a unique 3D framework. In 2, each W12 cluster connects five Ag ions and three K ions, and each Ag1 or Ag2 ion links three W12 clusters, forming a double chain. Furthermore, these double chains are linked together through K+ ions to form a 3D framework. The solid-state luminescence properties of compounds 1, 2 and pyridine-2,3-dicarboxylate have been studied at room temperature. 相似文献
13.
Microwave‐Assisted Preparation and Characterization of a Polyoxometalate‐Based Inorganic 2D Framework Anode for Enhancing Lithium‐Ion Battery Performance
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A pure inorganic 2D network molybdophosphate, [Mn3Mo12O24(OH)6(HPO3)8(H2O)6]4? ( 1 a ), synthesized through microwave irradiation with the existence of Mn2+ and organic cations and isolated as [(CH3)2NH2]3Na[Mn3Mo12O24(OH)6(HPO3)8(H2O)6] ? 12 H2O ( 1 ), is found to possess highly enhanced performance in lithium‐ion batteries’ anode materials. The molecule shows multielectron redox properties suitable for producing anode materials with a specific capacity of 602 mA h g?1 at 100 mA g?1 after 50 cycles in lithium‐ion batteries, although its specific capacity is the highest among all the reported pure inorganic 2D polyoxometalates to date, the cyclic stability is not that satisfactory. A hybrid nanocomposite of this 2D network and polypyrrole cations effectively reduces the capacity fading in initial cycles, and increases the stability and improves the electrochemical performance of lithium‐ion batteries as well. 相似文献
14.
Xiuli Wang Tianjiao Li Aixiang Tian Na Xu Rui Zhang 《Journal of Coordination Chemistry》2016,69(1):1-11
Two new isopolymolybdate-based metal–organic complexes, [Cu2(2-ptz)2(Mo4O14)0.5] (1) and [Cu3(OH)2(3-ptz)4(γ-H4Mo8O26)(H2O)4]·10H2O (2) (2-ptzH = 5-(2-pyridyl)-1H-tetrazole, 3-ptzH = 5-(3-pyridyl)-1H-tetrazole), constructed from isomeric ligands with different N-donor sites were synthesized under hydrothermal conditions. In 1, each [Mo4O14]4? cluster connected with six neighboring [Mo4O14]4? clusters through six binuclear [Cu2(2-ptz)2]2+ subunits to yield a 2-D layer. In 2, bidentate inorganic [Mo8O26]4? anions link the trinuclear [Cu3(OH)2(3-ptz)4] clusters to construct a 1-D chain. Adjacent chains connect through Mo–N bonds between the [Mo8O26]4? anions and pyridyl groups from the trinuclear clusters to form a 2-D layer. The effect of the N-donor sites of the rigid isomeric ligands on the structures of 1 and 2 was discussed. The electrochemical properties and photocatalytic activities of 1 and 2 have also been studied. 相似文献
15.
Ying Ma Yangguang Li Enbo Wang Ying Lu Xinxin Xu Xiuli Bai 《Transition Metal Chemistry》2006,31(2):262-267
A new compound, [Co(H2O)6][{Co2(H2O)6}{Co(H2PO4)2}{(PO4)6(HPO4)18(Mo16O32)Co16(H2O)18}] · 23H2O (1), has been prepared under mild hydrothermal conditions and structurally characterized by elemental analyses, i.r. spectrum,
XPS spectrum and single-crystal X-ray diffraction. Compound (1) consists of [(Mo16O32)Co16- (H2O)18(PO4)6(HPO4)18] wheel-shape clusters as the structural motif, which are covalently linked by [Co2(H2O)6] and [Co(H2PO4)2] fragments to form a two-dimensional layer framework. It is the first time that such wheels have been linked by both mononuclear
and dimeric CoII octahedra.
Electronic supplementary material Electronic supplementary material is available for this article at
and accessible for authorised users. 相似文献
16.
《Journal of Coordination Chemistry》2012,65(23):3754-3762
Two new organic–inorganic hybrid cobalt-molybdovanadates [Co(phen)3]H2[H2V2Mo6O26] · 7H2O (1) and [Co(2,2′-bipy)3][Na(H2O)7][VMo12O40] (2) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR, UV, XPS spectroscopy, thermogravimetric (TG) analyses, and X-ray single crystal diffraction. The molecular structure of 1 consists of a [V2Mo6(OH)2O24]4? polyoxoanion, a [Co(phen)3]2+, two H+ and seven lattice water molecules. The structure of [V2Mo6(OH)2O24]4? consists of six MoO6 octahedra and two VO4 tetrahedra; six MoO6 octahedra are linked by edge-sharing oxygens forming a {Mo6} ring, and two VO4 tetrahedra cap opposite sides of the {Mo6} ring. The molecular structural unit of 2 is constructed from a typical Keggin-type [VMo12O40]3? polyoxoanion and a [Co(2,2′-bipy)3]2+ cation and a Na+ countercation; Co2+ is coordinated by six nitrogens from three 2,2′-bipyridines forming a distorted octahedron. 相似文献
17.
Fedoseev A. M. Budantseva N. A. Andreev G. B. Yusov A. B. Shirokova I. B. 《Russian Journal of Coordination Chemistry》2002,28(4):279-284
The reactions of some rare-earth elements (La, Ce, Sm, Lu, Gd) and Am(III) with heteropolymolybdate anions are studied. The complexation rate constants of Am(III) in a solution with Al(OH)6Mo6O18
3- and Cr(OH)6MoO18
3-
6 (1 = 18 ± 6 and 25 ± 5, respectively) are determined by spectral methods. The Ln[Al(OH)6Mo6O18] · nH2O, Eu[Cr(OH)6Mo6O18] · nH2O, and Am[Al(OH)6Mo6O18] · nH2O isostructural compounds are synthesized. The crystal structure of the Sm[Al(OH)6Mo6O18] · 11H2O complex was determined by the X-ray diffraction analysis. The results of spectroscopic and thermogravimetric studies of the obtained compounds are presented. 相似文献
18.
Feng Geng Guo‐Hua Han Bi‐Zhou Lin 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(8):m355-m357
The crystal structure of the title compound, (C4H15N3)2[Mo5O15(HPO4)2]·4H2O, is made up of [Mo5O15(HPO4)2]4− clusters, iminodiethylenediammonium cations and solvent water molecules. The [Mo5O15(HPO4)2]4− cluster, with approximate C2 symmetry, can be considered as a ring formed by five distorted edge‐ and corner‐sharing MoO6 octahedra, capped on both poles by a hydrophosphate tetrahedron. There exist N—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds between the organic ammonium groups and the clusters, with interatomic N⋯O distances ranging from 2.675 (3) to 2.999 (3) Å, and C⋯O distances ranging from 3.139 (5) to 3.460 (5) Å. 相似文献
19.
Some Reactions with [Mo6Cl8]Cl4 The reaction of [Mo6Cl8]Cl4 with different chemical agents has been investigated: The methoxylation depends on the CH3O? concentration in CH3OH. The reaction with HF leads to a partial fluorinated [Mo6Cl8] product. With NH4F (NH4)2[Mo6Cl8]F6 in formed, the hydrolysis of which leads to [Mo6Cl8]F3(OH) · 2.5 H2O. This compound can be decomposed thermically into [Mo6Cl8]O2. [Mo6Br8]F62? on hydrolysis leads to [Mo6Br8]F3(OH) · 5 H2O. With CsF Cs2[Mo6Cl8]F6 is formed, which by hydrolysis is transformed into [Mo6Cl8]F3(OH) · 2.5 H2O and possibly to [Mo6Cl8]F4 · xH2O(?). In reaction of [Mo6Cl8]Cl4 with H2SO4 one gets [Mo6Cl8](SO4)2. Salts e. g. [(C6H5)4As]2[Mo6Cl8](OC6F5)6 and adducts e. g. [Mo6Cl8](OC6F5)4 · 2 HMPA are prepared. The compounds have been characterized by X-ray powder-diagramms and by IR-spectra. 相似文献
20.
Y. V. Mironov S. S. Yarovoi A. V. Ermolaev K. A. Brylev 《Russian Journal of Coordination Chemistry》2012,38(4):264-272
The compounds [Ni(H2O)2(En)2][{Ni(En)2}Re6S8(OH)6] · 7H2O (I), [{Cu(En)2}Re6S8(H2O)2(OH)4] · 4H2O (II), and [Ni(H2O)2(En)2]0.5[Re6Se8(H2O)3(OH)3] · 10H2O (III) were synthesized by layering aqueous solutions of Ni(En)2Cl2 or Cu(En)2Cl2 (En is ethylenediamine) onto aqueous solutions of the potassium salts of the corresponding octahedral chalcohydroxo rhenium
cluster complexes [Re6Q8(OH)6]4− (Q = S, Se). The structure of the obtained compounds was determined by X-ray diffraction analysis. 相似文献