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1.
A new coordination polymer, [Ni(pydc)(H2O)2]?·?H2O (1) (H2pydc?=?pyridine-3,4-dicarboxylic acid), have been synthesized by treating Ni(II) nitrate with 3,4-pyridinedicarboxylic acid under hydrothermal conditions. The single-crystal X-ray structure reveals that 1 is a 2D bi-layered coordination polymer. Single-crystals are triclinic, space group P 1 , with a?=?7.065(3), b?=?7.812(4), c?=?9.031(4)?Å, α?=?75.568(8), β?=?68.970(8), γ?=?75.927(8)°, V?=?444.0(3)?Å3, Z?=?2. Variable temperature magnetic susceptibility measurements demonstrate a ferromagnetic interaction in 1.  相似文献   

2.
The transition metal compounds Pd(OAc)2, RhCl3·4H2O and RuCl3 · nH2O were adsorbed onto the nanoporous silica polyamine composite (SPC) particles (150–250 µm), WP‐1 [poly(ethyleneimine) on amorphous silica], BP‐1 [poly(allylamine) on amorphous silica], WP‐2 (WP‐1 modified with chloroacetic acid) and BP‐2 (BP‐1 modified with chloroacetic acid). Inductively coupled plasma‐atomic emission spectrometry analysis of the dried samples after digestion indicated metal loadings of 0.4–1.2 mmol g?1 except for RhCl3·4H2O on BP‐2 which showed a metal loading of only 0.1 mmol g?1. The metal loaded composites were then screened as hydrogenation catalysts for the reduction of 1‐octene, 1‐decene, 1‐hexene and 1, 3‐cyclohexadiene at a hydrogen pressure of 5 atm in the temperature range of 50–90 °C. All 12 combinations of SPC and transition metal compound proved active for the reduction of the terminal olefins, but isomerization to internal alkenes was competitive in all cases. Under these conditions, selective hydrogenation of 1,3‐cyclohexadiene to cyclohexene was observed with some of the catalysts. Turnover frequencies were estimated for the hydrogenation reactions based on the metal loading and were in some cases comparable to more conventional heterogeneous hydrogenation catalysts. Examination of the catalysts before and after reaction with X‐ray photoelectron spectroscopy and transmission electron microscopy revealed that, in the cases of Pd(OAc)2 on WP‐2, BP‐1 and BP‐2, conversion of the surface‐ligand bound metal ions to metal nano‐particles occurs. This was not the case for Pd(OAc)2 on WP‐1 or for RuCl3 · nH2O and RhCl3· 4H2O on all four composites. The overall results are discussed in terms of differences in metal ion coordination modes for the composite transition‐metal combinations. Suggested ligand interactions are supported by solid state CPMAS 13C NMR analyses and by analogy with previous structural investigations of metal binding modes on these composite materials. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

3.
We have succeeded in constructing a metal–organic framework (MOF), [Cu(bpdc)(H2O)2]n (H2bpdc=2,2′‐bipyridyl‐3,3′‐dicarboxylic acid, 1 ), and two poly‐POM–MOFs (POM=polyoxometalate), {H[Cu(Hbpdc)(H2O)2]2[PM12O40] ? n H2O}n (M=Mo for 2 , W for 3 ), by the controllable self‐assembly of H2bpdc, Keggin‐anions, and Cu2+ ions based on electrostatic and coordination interactions. Notably, these three compounds all crystallized in the monoclinic space group P21/n, and the Hbpdc? and bpdc2? ions have the same coordination mode. Interestingly, in compounds 2 and 3 , Hbpdc? and the Keggin‐anion are covalently linked to the transition metal copper at the same time as polydentate organic ligand and as polydentate inorganic ligand, respectively. Complexes 2 and 3 represent new and rare examples of introducing the metal N‐heterocyclic multi‐carboxylic acid frameworks into POMs, thereby, opening a pathway for the design and the synthesis of multifunctional hybrid materials based on two building units. The Keggin‐anions being immobilized as part of the metal N‐heterocyclic multi‐carboxylic acid frameworks not only enhance the thermal stability of compounds 2 and 3 , but also introduce functionality inside their structures, thereby, realizing four approaches in the 1D hydrophilic channel used to engender proton conductivity in MOFs for the first time. Complexes 2 and 3 exhibit good proton conductivity (10?4 to ca. 10?3 S cm?1) at 100 °C in the relative humidity range 35 to about 98 %.  相似文献   

4.
Three new coordination polymers, [Cu(butca)0.5(bipy)(H2O)] n · 2nH2O (1), [Zn(H2butca) (phen)(H2O)] n · nH2O (2), and [Cd(H2chhca)0.5(phen)(H2O)] n · 2nH2O (3) (H4butca =1,2,3,4-butanetetracarboxylic acid, H6chhca = 1,2,3,4,5,6-cyclohexanehexacarboxylic acid), were prepared and characterized by EA, IR, TG, and X-ray crystallography. Complex 1 is a 1-D double-chain coordination polymer in which tetradentate butca4? coordinates to four Cu(II) ions through four monodentate carboxylates. Complex 2 is a 1-D chain with tridentate H2butca2? coordinating to two Zn(II) ions through monodentate and chelating carboxylates. Complex 3 is a 1-D double-chain coordination polymer. H2chhca4? is octadentate coordinating to four Cd(II) ions through four chelating carboxylates. Hydrogen bonds and π–π stacking interactions play important roles in the formation of supramolecular architectures. The thermal stabilities of 13 show dehydrated coordination polymers are thermally stable in the range 260–400°C.  相似文献   

5.
Two ternary copper(II) complexes [Cu(L1)(py)] (1) and [Cu(L2)(Himdz]?·?CH3OH (2) with substituted aroylhydrazones, 5-bromo-salicylaldehyde-3,5-dimethoxy-benzoylhydrazone (H2L1) and 5-bromo-salicylaldehyde-p-methyl-benzoylhydrazone (H2L2), pyridine (py) and imidazole (Himdz), have been synthesized. Their crystal structures and spectroscopic properties have been studied. In each complex, the metal is in a square-planar N2O2 coordination formed by the phenolate-O, the imine-N and the deprotonated amide-O atoms of L2?, and the sp2?N atom of the neutral heterocycle. In the solid state, 1 exists as a centrosymmetric dimer due to very weak apical coordination of the metal bound phenolate-O. Complex 2 has no such apical coordination and exists as a monomer. Self-assembly via C–H?···?O, N–H?···?O and O–H?···?N interaction leads to a one-dimensional chain arrangement; other non-covalent interactions such as C–H?···?π and π?···?π are not involved.  相似文献   

6.
{[CdCl(2,2′-bipy)2(H2O)]+·[Cd(3-O?-2,7-NDS)(2,2′-bipy)2]?·3H2O} (1) and {[Cd(phen)3]2+·2[Cd(3-O?-2,7-NDS)(phen)2]?·8.5H2O} (2) (3-OH-2,7-NDS?=?3-hydroxy-2,7-naphthalenedisulfonate, phen?=?1,10-phenanthroline, and 2,2′-bipy?=?2,2′-bipydine) were prepared and characterized by X-ray single-crystal diffraction. Compound 1 contains a discrete coordination cation [CdCl(2,2′-bipy)2(H2O)]+ and a coordination anion [Cd(3-O?-2,7-NDS)(2,2′-bipy)2]?; 2 contains a discrete coordination cation [Cd(phen)3]2+ and two coordination anions [Cd(3-O?-2,7-NDS)(phen)2]?. There are numerous weak interactions among the coordination cation, coordination anion, and free water molecules, such as O–H?···?O hydrogen bonds, π?···?π stacking, and Cl??···?π interactions in 1 and π?···?π stacking and C–H?···?π interactions in 2. The cations and anions as building blocks are connected to construct different 3-D supramolecular architectures via weak intermolecular interactions. Particularly, the capsule structure of 1 was observed.  相似文献   

7.
Two new isostructural complexes, [Ca(H2O)2(μ2-Detba-O,O′)2]n (1) and [Sr(H2O)2(μ2-Detba-O,O′)2]n (2) (HDetba = 1,3-diethyl-2-thiobarbituric acid), were synthesized and characterized by single-crystal and powder X-ray diffraction analysis, TG-DSC, FT-IR, and emission spectroscopy. The single-crystal X-ray diffraction data revealed that 1 and 2 are polymeric where M2+ (M = Ca, Sr) is a six-coordinate octahedral binding four Detba? ions and two water molecules. The octahedra are linked through bridging Detba? ions forming a 2-D layer. Two intermolecular hydrogen bonds O–H…S in the crystal form a 3-D net. The comparison of M(Detba)2 and M(Htba)2 (H2tba = 2-thiobarbituric acid) structures showed that the coordination number of metals in M(Detba)2 does not exceed six and there are no ππ interactions, unlike compounds with Htba?; Detba? ions are only bridges in HDetba coordination compounds. Thermal decomposition of 1 and 2 includes dehydration, which mainly ends at 200 °C, and organic ligand oxidation at 300–350 °C with a release of CO2, SO2, H2O, NH3, and isocyanate. Upon excitation at 220 nm, 1 and 2 exhibit an intense emission maximum at 557 nm.  相似文献   

8.
Four coordination polymers, [Ag(L1)](m-Hbdc) (1), [Ag(L1)]2(p-bdc)?·?8H2O (2), [Ag(Hbtc)(L1)][Ag(L1)]?·?2H2O (3) and [Ag2(L2)2](OH-bdc)2?·?4H2O (4), where L1?=?1,1′-(1,4-butanediyl)bis(imidazole), L2?=?1,2-bis(imidazol-1-ylmethyl)benzene, m-H2bdc?=?1,3-benzenedicarboxylic acid, p-H2bdc?=?1,4-benzenedicarboxylic acid, H3btc?=?1,3,5-benzenetricarboxylic acid, and OH–H2bdc?=?5-hydroxisophthalic acid, were synthesized under hydrothermal conditions. Compound 1 contains a–Ag-L1–Ag-L1–chain and a hydrogen-bonding interaction induced–(m-Hbdc)-(m-Hbdc)–chain. Compound 2 consists of two independent–Ag-L1–Ag-L1–chains. P-bdc anions are not coordinated. Hydrogen bonds form a 3D supramolecular structure. A novel (H2O)16 cluster is formed by lattice water molecules in 2. Compound 3 contains a–Ag-L1–Ag-L1–and a–Ag(Hbtc)-L1–Ag(Hbtc)-L1–chain. The packing diagram shows a 2D criss-cross supramolecular structure, with?π?···?π?and C–H ···?π?interactions stabilizing the framework. Compound 4 contains a [Ag2(L2)2]2+ dimer with hydrogen-bonding,?π?··· π, and Ag ··· O interactions forming a 3D supramolecular framework. The luminescent properties for these compounds in the solid state are discussed.  相似文献   

9.
A novel coordination polymer {[Cd(BDAC)]2 · H2O}n ( 1 ) [HBDAC = (1′H‐[2, 2′]biimidazoly‐1‐yl)‐acetic acid] was synthesized under hydrothermal conditions and characterized by elemental analysis and single‐crystal X‐ray diffraction. Complex 1 crystallizes in the acentric orthorhombic space group Ccc2. The Cd1 atoms and BDAC2– ligands construct [Cd1(BDAC)] rhomboid grid (4, 4)‐topology layer motifs, whereas the Cd2 atoms and BDAC2– ligands form [Cd2(BDAC)] 1D coordination polymer ribbons. Furthermore, adjacent lay motifs are linked into 3D net structures by 1D coordination polymer ribbons with 4‐connected 3D trinodal {4282102}{4462}{43628}2 topology. The measurement of electric hysteresis loops indicated that complex 1 displays a ferroelectric characteristic.  相似文献   

10.
The mechanism of oxidation of ternary complexes, [CoII(nta)(S)(H2O)2]3? and [CoII(nta)(M)(H2O)]3? (nta = nitrilotriacetate acid, S = succinate dianion, and M = malonate dianion), by periodate in aqueous medium has been studied spectrophotometrically over the (20.0–40.0) ± 0.1°C range. The reaction is first order with respect to both [IO4?] and the complex, and the rate decreases over the [H+] range (2.69–56.20) × 10?6 mol dm?3 in both cases. The experimental rate law is consistent with a mechanism in which both the hydroxy complexes [CoII(nta)(S)(H2O)(OH)]4? and [CoII(nta)(M)(OH)]4? are significantly more reactive than their conjugate acids. The value of the intramolecular electron transfer rate constant for the oxidation of the [CoII(nta)(S)(H2O)2]3?, k1 (3.60 × 10?3 s?1), is greater than the value of k6 (1.54 × 10?3 s?1) for the oxidation of [CoII(nta)(M)(H2O)]3? at 30.0 ± 0.1°C and I = 0.20 mol dm?3. The thermodynamic activation parameters have been calculated. It is assumed that electron transfer takes place via an inner‐sphere mechanism. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 103–113, 2008  相似文献   

11.
Summary: A novel coordination polymer[{Cu(en)2}(V10O28)]n · 2n[Cu(en)2(H2O)] · 2n(H3BO3) · 2n(H2O) was obtained by hydrothermal reaction. The compound crystallizes in the monoclinic crystal system, in the C2/c space group, with a = 26.490 (3) Å; b = 11.6558 (11) Å; c = 19.8426 (19) Å; β = 124.011 (1)°; V = 5078.6(8) Å3. The solid structure is formed by polymeric chains, [Cu(en)2(H2O)]2+ cations, and boric acid and water solvate molecules, stabilized through a multiple hydrogen bond network.  相似文献   

12.
A new TbIII complex of 5-fluorouracil-1-acetate (5-FUA) and 1,10-phenanthroline(phen), [Tb(phen)(5-FUA)3] n ?· H2O, has been synthesized, characterized by elemental analysis, IR spectroscopy, XRD powder diffraction, thermal analysis and its structure has been determined by X-ray crystallography. The structural studies show that compound to be a two-dimensional coordination polymer and the Tb atoms to have ten-coordinate geometry, TbN2O8. Self-assembly of this compound in the solid state is likely caused by N–H·?·?·O, O?–?H·?·?·O and O–H·?·?·F hydrogen bonding.  相似文献   

13.
Two coordination complexes, [Co2L2(4,4′-bpy)2(H2O)4]?·?6H2O (1) and [CoL(4,4′-bpy)] (2) (H2L?=?4,6-bis(4-methylbenzoyl)isophthalic acid and 4,4′-bpy?=?4,4′-bipyridine), have been synthesized with the same starting materials under conventional and hydrothermal condition, respectively. Their structures have been characterized by X-ray diffraction, elemental analysis, IR spectra, and thermogravimetric analysis. Complex 1 features a 2-D sheet structure (space group C2/c) with (4,4) grid units. The non-covalent interactions (O–H?·?·?·?O, C–H?·?·?·?π, and weak π??·?·?·?π interactions) extend 1 into a 3-D supramolecular network. Complex 2 displays a (3,5)-connected network (space group P 1) with a (42?·?6)(42?·?68) topology.  相似文献   

14.
M(H2O)2(4,4′‐bipy)[C6H4(COO)2]·2H2O (M = Mn2+, Co2+) – Two Isotypic Coordination Polymers with Layered Structure Monoclinic single crystals of Mn(H2O)2(4,4′‐bipy)[C6H4(COO)2]·2H2O ( 1 ) and Co(H2O)2(4,4′‐bipy)[C6H4(COO)2]· 2H2O ( 2 ) have been prepared in aqueous solution at 80 °C. Space group P2/n (no. 13), Z = 2; 1 : a = 769.20(10), b = 1158.80(10), c = 1075.00(10) pm, β = 92.67(2)°, V = 0.9572(2) nm3; 2 : a = 761.18(9), b = 1135.69(9), c = 1080.89(9) pm, β = 92.276(7)°, V = 0.9337(2) nm3. M2+ (M = Mn, Co), which is situated on a twofold crystallographic axis, is coordinated in a moderately distorted octahedral fashion by two water molecules, two oxygen atoms of the phthalate anions and two nitrogen atoms of 4,4′‐biypyridine ( 1 : M–O 219.5(2), 220.1(2) pm, M–N 225.3(2), 227.2(2) pm; 2 : Co–O 212.7(2), 213.7(2) pm, Co–N 213.5(3), 214.9(3) pm). M2+ and [C6H4(COO)2)]2? build up chains, which are linked by 4,4′‐biyridine molecules to yield a two‐dimensional coordination polymer with layers parallel to (001).Thermogravimetric analysis in air of 1 indicated a loss of water of crystallization between 154 and 212 °C and in 2 between 169 and 222 °C.  相似文献   

15.
A series of water‐soluble semirigid thermoresponsive polymers with well‐defined molecular weights based on mesogen‐jacketed liquid crystal polymers (MJLCPs), poly[bis(N‐hydroxyisopropyl pyrrolidone) 2‐vinylterephthalate] (PHIPPVTA) have been synthesized via reversible addition fragmentation chain transfer (RAFT) polymerization. Dynamic light scattering (DLS) revealed that the novel monomer and polymers have thermoresponsive properties with cloud point in the range between 10 and 90 °C. The cloud point was increased by 56.2 °C when the polymer molecular weight increased from 0.47 × 104 g mol?1 to 3.69 × 104 g mol?1. In addition, the cloud point of PHIPPVTA was decreased by 18.8 °C with the increase of polymer concentration from 5 to 10 mg mL?1. A slight increase (0.1–3.5 °C) of cloud point has been observed after knocking off the end‐groups of PHIPPVTA. Moreover, the cloud point of polymer increased with increasing of its molecular weight with or without the trithiocarbonate end‐groups, which showed the opposite trend comparing with other thermoresponsive polymers with flexible backbones. These polymers show a dramatic solvent isotopic effect that the cloud point in D2O was lower than in H2O. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

16.
Complexes with Aromatic Carboxylic Acids. V. On the Layer Structure of Cd[C6H4(COO)2] · H2O Single crystals of Cd[C6H4(COO)2] · H2O were grown in aqueous silica gel. According to differential thermal analysis the dehydration commences at 160°C, and decomposition to CdO occurs between 380 and 420°C. Cd2+ is surrounded by one water molecule and six oxygen atoms stemming from carboxylate groups (Cd? O: 225.4–247.0 pm). One carboxylate group chelates Cd2+. Two carboxylate oxygen atoms are bound to two Cd2+ each. The coordination polyhedra are interlinked by a common edge and two common corners. Further connection is established by the phthalate dianions. This leads to layers parallel (010). The COO? groups are titled differently against the plane of the C6 ring (40° and 71°). The C? O bond lengths reach from 125.9 to 128.3 pm, the C? C bonds of the C6 ring from 136.7 to 140.3 pm.  相似文献   

17.
The kinetics of oxidation of the chromium(III) complexes, [Cr(Ino)(H2O)5]3+ and [Cr(Ino)(Gly)(H2O)3]2+ (Ino?=?Inosine and Gly?=?Glycine) involving a ligands of biological significance by N-bromosuccinimide (NBS) in aqueous solution to chromium(VI) have been studied spectrophotometrically over the 25–45°C range. The reaction is first order with respect to both [NBS] and [Cr], and increases with pH over the 6.64–7.73 range in both cases. The experimental rate law is consistent with a mechanism in which the hydroxy complexes [Cr(Ino)(H2O)4(OH)]2+ and [Cr(Ino)(Gly)(H2O)2(OH)]+ are significantly more reactive than their conjugate acids. The value of the intramolecular electron transfer rate constant, k 1, for the oxidation of the [Cr(Ino)(H2O)5]3+ (6.90?×?10?4?s?1) is lower than the value of k 2 (9.66?×?10?2?s?1) for the oxidation of [Cr(Ino)(Gly)(H2O)2]2+ at 35°C and I?=?0.2?mol?dm?3. The activation parameters have been calculated. Electron transfer apparently takes place via an inner-sphere mechanism.  相似文献   

18.
Thiosemicarbazide and 4-phenylthiosemicarbazide react in ethanol with 2,4-pentanedione in the presence of manganese, cobalt, nickel, copper, and zinc acetates hydrates and streptamin (Sf1), sulfaethidole (Sf2), and sulfadimidine (Sf3) to form coordination compounds of the composition M(Sf1–3)(L1–2) · nH2O (M = Mn, Co, Ni, Cu, Zn; H2L1 is 2,4-pentanedione bis-thiosemicarbazone, H2L2 is 2,4-pentanedione bis-4-phenylthiosemicarbazone; n = 0–6). All the complexes synthesized are monomeric. Thiosemicarbazones (H2L1 and H2L2) behave as twice deprotonated S,N,N,S-tetradentate ligands, while sulfanylamides (Sf1–3) act as monodentate ones. Thermolysis of these substances proceeds through the stages of dehydration (65–95°C) and complete thermal decomposition (430–560°C). It is found that the complex [Cu(Sf2)(L1)] · 4H2O in the concentration 10?5 M inhibits the growth and fission of 100% cancer cells of the human myeloid leukemia (HL-60).  相似文献   

19.
A porous metal–organic framework (MOF), [Ni2(dobdc)(H2O)2]?6 H2O (Ni2(dobdc) or Ni‐MOF‐74; dobdc4?=2,5‐dioxido‐1,4‐benzenedicarboxylate) with hexagonal channels was synthesized using a microwave‐assisted solvothermal reaction. Soaking Ni2(dobdc) in sulfuric acid solutions at different pH values afforded new proton‐conducting frameworks, H+@Ni2(dobdc). At pH 1.8, the acidified MOF shows proton conductivity of 2.2×10?2 S cm?1 at 80 °C and 95 % relative humidity (RH), approaching the highest values reported for MOFs. Proton conduction occurs via the Grotthuss mechanism with a significantly low activation energy as compared to other proton‐conducting MOFs. Protonated water clusters within the pores of H+@Ni2(dobdc) play an important role in the conduction process.  相似文献   

20.
Six complexes, [VO(L1-H)2]?·?5H2O (1), [VO(OH)(L2,3?H)(H2O)]?·?H2O (2,3), [VO(OH)(L4,5?H)(H2O)]?·?H2O (4,5), [VO(OH)(L6?H)(H2O)]?·?H2O (6), were prepared by reacting different derivatives of 5-phenylazo-6-aminouracil ligands with VOSO4?·?5H2O. The infrared and 1H NMR spectra of the complexes have been assigned. Thermogravimetric analyses (TG, DTG) were also carried out. The data agree quite well with the proposed structures and show that the complexes were finally decomposed to the corresponding divanadium pentoxide. The ligands and their vanadyl complexes were screened for antimicrobial activities by the agar-well diffusion technique using DMSO as solvent. The minimum inhibitory concentration (MIC) values for 14 and 6 were calculated at 30°C for 24–48?h. The activity data show that the complexes are more potent antimicrobials than the parent ligands.  相似文献   

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