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1.
Synthesis of solid [Cr(nta)(H2O)2] 1, kinetics and equilibrium of ots reaction with pentane-2,4-dione (Hpd) to form [Cr(nta)(pd)] 2 (H3nta is nitrilotriacetic acid), aquation of 2 into 1, and some related reactions have been described. Parallel proton-independent and inverse proton-dependent paths lead from 1 to 2. The [H+]−1 path arises from metal assisted deprotonation of HE, the enol form of Hpd. Aquation of 2 into 1 involves [Cr(Hnta)(pd)(H2O]+ 2H (Hnta is tridentate nta) in addition to 2. The nta comples 1 is considerably more labile and a weaker acid than [Cr(H2O)6]3+.  相似文献   

2.
In this paper, we summarise our recent research interest in the hydrothermal synthesis and structural characterisation of multi-dimensional coordination polymers. The use of N-(phosphonomethyl)iminodiacetic acid (also referred to as H4pmida) in the literature as a versatile chelating organic ligand is briefly reviewed. This molecule plays an important role in the formation of centrosymmetric dimeric [V2O2(pmida)2]4− anionic units, which were first used by us as building blocks to construct novel coordination polymers. Starting with [V2O2(pmida)2]4− in solution, we have isolated [M2V2O2(pmida)2(H2O)10] species (where M2+ = Mn2+, Co2+ or Cd2+) via the hydrothermal synthetic approach, which were then employed for the construction of [CdVO(pmida)(4,4′-bpy)(H2O)2]·(4,4′-bpy)0.5·(H2O), [CoVO(pmida)(4,4′-bpy)(H2O)2]·(4,4′-bpy)0.5, [Co(H2O)6][CoV2O2(pmida)2(pyr)(H2O)2]·2(H2O) and [Cd2V2O2(pmida)2(pyr)2(H2O)4]·4(H2O) by the inclusion of bridging organic ligands in the reactive mixtures, such as pyrazine (pyr) and 4,4′-bipyridine (4,4′-bpy). These materials can contain channel systems, and exhibit magnetic behaviour, not only due to the V4+ centres but also to the transition metal centres which establish the links between neighbouring dimeric [V2O2(pmida)2]4− anionic units. A closely related anionic moiety, [Ge2(pmida)2(OH)2]2−, was engineered to allow the study of such crystalline hybrid materials using one- and two-dimensional high-resolution solid-state NMR.  相似文献   

3.
金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1~5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].  相似文献   

4.
Recently, there has been considerable interest in cyano-bridged lanthanide(Ⅲ) hexacyanometalate(Ⅲ) complexes LnM(CN)6·nH2O (M=Fe, Cr and Co) because of their potential as catalytic, semiconductive, and magnetic materials.[1-8] In this study, we employed N,N-dimethylformamide (DMF) as a hybrid ligand to construct a bimetallic complex[Eu(DMF)4(H2O)2Cr(CN)6]·H2O. It was synthesized as yellow crystals by the self-assembly of anhydrous EuCl3 and (Bu4N)3[Cr(CN)6] in MeOH and DMF. Single-crystal X-ray diffraction analysis shows that it consists of a cyano-bridged chain structure. The Eu atom is eight-coordinate with a distorted bicapped square antiprism geometry. Six oxygen atoms of two water molecules and four DMF molecules and two nitrogen atoms of the bridging CN ligands are bound to Eu with the Eu-O distance ranging from 2.368(7) to 2.447(8) Å. The bridging cyanides coordinate to the Europium(Ⅲ) ion[N(l)-Eu=2.543(9) Å and N(3)-EuA=2.543(8) Å] in a bent fashion with the bond angles of 164.0(9) for C(1)-N(1)-Nd and 155.1(7)。for C(3)-N(3)-EuA (A denotes the symmetry transformation:-x+l,y-l/2,-z+3/2). Each Cr(CN)6 coordinates to two Eu(Ⅲ) ions using two cis cyanide ligands, while each Eu(DMF)4(H2O)2 group connects two Cr(CN)6 moieties in a cis fashion, giving rise to an unprecedented chain structure. Crystal data:monoclinic, space group P21/c, a=13.151(2), b=12.905(2), c=19.186(2) Å, β=109.70(1)°, V=3065.5(7) Å3,Z=4, ρobs=1.531 Mg m-3, S=1.024,R1=0.0540, Rw=0.1616.  相似文献   

5.
The chemistry of metal-oxo compounds has been extensively and intensively studied for over a hundred years because of their theoritical importance and practical application[1]. Recent advance has afforded a study of inorganic or organometallic complexes containing metal-oxo anions[2]. Herein, the synthesis and structural characterization of two heteropolyoxomolybdnum-supported transition metal complexes (H2bpy)0.5Ni(H2O)5[Mo5P2O23]Ni(Hbpy)(H2O)4 (1) and (H2bpy)0.5Co(H2O)5[Mo5P2O23]Co(Hbpy) (H2O)4(2) are reported.  相似文献   

6.
Five transition metal coordination compounds, [Mn2(8-qoac)2(bdc)(H2O)4](1)(8-qoacH=quinoline-8-oxy- acetate acid, H2bdc=benzene-1,4-dicarboxylic acid), [Zn4(8-qoac)4(bdc)2]n(2), {[Cd2(8-qoac)2(Hip)2(H2O)2]· (H2O)4}n(3)(H2ip=benzene-1,3-dicarboxylic acid), [Pb3(8-qoac)2(bdc)1.5(H2O)Cl]n(4) and [Zn2(8-qoac)(8-ql)(bdc)]n (5)(8-Hql=8-hydroxyquinoline), were synthesized by hydrothermal syntheses of metal salts with benzenedicarboxy- lic acid and 8-qoacH. Compound 1 possesses a discrete dimer bridged by bdc2- ligand. Compound 2 presents a 2D layer network constructed from bdc2- linkers and 1D infinite ribbons, in which Zn(II) centers are bridged by 8-qoac- with a tetradentate binding mode. Compound 3 displays a 1D zigzag chain, with adjacent chains further connected via extensive O-H···O hydrogen bonds to generate a 3D supramolecular structure. Compound 4 shows a 3D framework containing trinuclear lead secondary building units and bdc2- linkers, in which a new coordination mode of 8-qoac- ligand is observed. In compound 5, Zn(II) ions are simultaneously bridged by 8-qoac-, 8-ql- and bdc2- ligands to form tetranuclear zinc units, which are further interlinked by bdc2- linkers to yield a 2D wave-like layer. Based on intraligand(IL)(π-π*) fluorescent emission, compounds 1―5 possess strong purple fluorescent emissions. In addition, the thermal stabilities of compounds 1―5 were studied.  相似文献   

7.
A series of chromium(III) complexes [Cr(bipy)(HC2O4)2]Cl·3H2O (1), [Cr(phen)(HC2O4)2]Cl·3H2O (2), [Cr(phen)2(C2O4)]ClO4 (3), [Cr2(bipy)4(C2O4)](SO4)·(bipy)0.5·H2O (4) and [Mn(phen)2(H2O)2]2[Cr(phen)(C2O4)2]3ClO4·14H2O (5) were synthesized (bipy=4,4′-bipyridine, phen=1,10-phenanthroline), while the crystal structures of 1 and 3–5 have been determined by X-ray analysis. 1 and 3 are mononuclear complexes, 4 contains binuclear chromium(III) ions and 5 is a 3D supromolecule formed by complicated hydrogen bonding. 1–3 are potential molecular bricks of chromium(III) building blocks for synthesis heterometallic complexes. When we use these molecular bricks as ligands to react with other metal salts, unexpected complexes 4 and 5 are isolated in water solution. The synthesis conditions and reaction results are also discussed.  相似文献   

8.
Based on a new biscarboxyl-functionalized Schiff base ligand 1,2-cyclohexanediamino-N,N'-bis[3-methoxyl-5-(p-carboxyl-phenylazo)] salicylidene(H4L), four polymers,[(CH3)2NH2]2·[Mn3(L)2(H2O)4]·2DMF(CP1),[Fe2(L)(H2O)(DMF)](CP2),[(CH3)2NH2]·[Cu(HL)]·H2O(CP3) and[Ni2(L)(teta)]·2DMF·H2O(CP4), have been synthesized(teta=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). In CP1, both of the internal[N2O2] pocket and the external carboxylate groups of L4- anion are ligated by Mn2+ ions, and the structure displays a layer. In CP2, the Fe2+ cations are linked by L4- anions to form a binuclear double chain. CP3 displays a[Cu2(HL)2] dimer. In CP4, the Ni2+ ions are connected by L4- anions to form a chain. The structures are further linked by hydrogen bonds to form 2D or 3D supramolecular architectures, respectively. CP1 exhibits adsorption ability to three organic dyes.  相似文献   

9.
取代烟酸、双水杨基缩乙二胺合铬(Ⅲ)配合物的合成及性质研究周保学,尚树川,邹立状,王大庆,张晓凯,朱丽,任建成(山东师范大学化学系,济南,250014)关键词葡萄糖耐量因子,铬(Ⅲ)配合物,合成1974年Mertz[1]等人提出体内活性的葡萄糖耐量因...  相似文献   

10.
Lewis acid/base addition between Ln(NO3)3 · 6H2O (Ln = Pr, Nd, Sm, Eu, Tb and Lu) and H2salen [H2salen = N,N′-ethylenebis(salicylideneimine)] gives rise to an array of coordination polymeric structures. Crystal structural analysis reveals that Salen effectively functions as a bridging ligand in these compounds. The size of the lanthanide ions controls the structures of these Salen lanthanide complexes. Two representative structures with one dimensional and two dimensional topologies, viz. [Pr(H2salen)(NO3)3(CH3OH)2]n (1) and [Ln(H2salen)1.5(NO3)3]n [Ln = Pr (2), Nd (3), Sm (4), Eu (5), Tb (6) and Lu (7)] are reported. Luminescent spectra of complexes 4 and 5 exhibit characteristic metal-centered emission lines. However, the characteristic luminescence of the terbium(III) ion is not observed either in solution or in the solid state of complex 6.  相似文献   

11.
Three new gallium complexes formulated as [Ga(PDA)2][Ga(H2O)(PDA)(phen)]·4H2O(1), [Ga(PDA)2]· (H2IN)·2H2O(2) and [Ga(OH)(PDA)(H2O)]2(3)(H2PDA=pyridine-2,6-dicarboxylic acid; phen=1,10-phenanthroline; HIN=isonicotinic acid) have been synthesized under hydrothermal conditions. In the mixed-ligand system of complex 1, PDA2? and phen are connected to the central Ga3+ cation as tri- and bi-dentate ligands, respectively. In complex 2, each Ga3+ cation is six-coordinated by two PDA2? anions octahedrally. Complex 3 shows a binuclear structure, with the bond distance of Ga1-Ga2 being 0.30061(3) nm. The 3D supramolecular structures of the three complexes are constructed via hydrogen bonds and aromatic π-π packing interactions. All the three complexes exhibit intense blue emission at room temperature in the solid state, which are attributed to π*-π transition centered on the ligands.  相似文献   

12.
Mononuclear copper(II) complexes of a family of pyridylmethylamide ligands HL, HLMe, HLPh, HLMe3 and HLPh3, [HL = N-(2-pyridylmethyl)acetamide; HLMe = N-(2-pyridylmethyl)propionamide; HLPh = 2-phenyl-N-(2-pyridylmethyl)acetamide; HLMe3 = 2,2-dimethyl-N-(2-pyridylmethyl)propionamide; HLPh3 = 2,2,2-triphenyl-N-(2-pyridylmethyl)acetamide], were synthesized and characterized. The reaction of copper(II) salts with the pyridylmethylamide ligands yields complexes [Cu(HL)2(OTf)2] (1), [Cu(HLMe)2](ClO4)2 (2), [Cu(HL)2Cl]2[CuCl4] (3), [Cu(HLMe3)2(THF)](OTf)2 (4), [Cu(HLMe3)2(H2O)](ClO4)2 (5a and 5b), [Cu(HLPh3)2(H2O)](ClO4)2 (6), [Cu(HL)(2,2′-bipy)(H2O)](ClO4)2 (7), and [Cu(HLPh)(2,2′-bipy)(H2O)](ClO4)2 (8). All complexes were fully characterized, and the X-ray structures vary from four-coordinate square-planar, to five-coordinate square-pyramidal or trigonal-bipyramidal. The neutral ligands coordinate via the pyridyl N atom and carbonyl O atom in a bidentate fashion. The spectroscopic properties are typical of mononuclear copper(II) species with similar ligand sets, and are consistent their X-ray structures.  相似文献   

13.
Structural comparison of a new compound[(bpp)3H6]Fe2IIIFe2IIMo24V(H2PO4)8(HPO4)4(PO4)4O48(OH)12· (H2O)4·2H2O(1)[bpp=1,3-di(4-pyridyl)propane] with our previously reported two compounds[(bpy)3FeII]3· Fe2IIIFe2IIMo24V(H2PO4)8(HPO4)4(PO4)4O48(OH)12(H2O)4·12H2O(2) and[(bpy)3FeII]2FeIIFeIIIMo12V(H2PO4)2(H2-xPO4)·(H1+xPO4)(HPO4)2(PO4)2O24(OH)6(H2O)2·9H2O(x=0―1)(3)(bpy=2,2'-bipyridine), which all exhibit one-dimensional mixed-valence iron molybdophosphate anionic chains constructed by alternating connection of FeIII ions and magic[FeII(Mo6P4O31)2] units, reveals that the non-hydrogen atomic ratios of Mo:Fe:P:O within the polymeric anionic chains are the same for all the three compounds, while the polymeric anionic chains of the different compounds bear different numbers of negative charges. And therefore there exist different numbers of counter cations per {Fe2III[Fe2II(P16Mo24VO124)]} unit found in the titled compounds. It discloses that not only are the spatial assembling of counter cations and polymeric inorganic chains of three compounds quite different, but also the O―FeIII―O bond angles and FeIII―O bond lengths of the three different inorganic chains exhibit small differences. What is more important is that such small changes in bond length and bond angle in the assemblage of FeIII―O bonds lead to the considerable fluctuations of inorganic chains in their structural conformation within the three compounds, reflecting an interesting phenomenon of “flexibility" in the pure inorganic one dimensional mixed-valence iron molybdophosphate chains.  相似文献   

14.
通过使用氧化锌代替传统的金属无机盐为锌源,制备了手性金属-有机骨架(CMOF)[Zn(L-mal)(H2O)2]n并对其手性分离性能进行了考察。将ZnO和L-苹果酸按物质的量之比1:1溶于水中,在室温下静置24 h即可得到[Zn(L-mal)(H2O)2]n。以100 mg[Zn(L-mal)(H2O)2]n为吸附剂,将250 μL 1 g/L的联糠醛外消旋体加入其中,并以4.5 mL异丙醇和1 mL甲醇为萃取剂和洗脱剂进行选择性吸附实验,最终滤液使用高效液相色谱仪(HPLC)进行分析。结果表明,[Zn(L-mal)(H2O)2]nR-联糠醛具有较好的选择性吸附,其对映体过量(ee)值为20%。该工作为CMOF的绿色制备提供了一定的方法和经验并拓展了其在手性分离领域的应用。  相似文献   

15.
Three novel compounds, [Co(en)3]2[Zr2(C2O4)7]·2H20(HNU-2, en=ethylenediamine), [Co(NH3)6]· [Ce(CzO4)3(H2O)]·H2O(HNU-3) and [Co(dien)2][Gd(C2On)3]·0.75H2O(HNU-4, dien=dethylenetriamine) were hydro- thermal synthesized based on the templates of [Co(en)3]C13, [C0(NH3)6]C13 and [Co(dien)2]C13, respectively. The Zr4+ Ce3+ and Gd3+ cations are all coordinated by four oxalates to form [M(C2O4)n(H2O)n]m (M=Zr, Ce or Gd; n=0 or 1; m=4 or 5), which are similar to [In(C2O4)4]5- in NKB-1, and can be regarded as 4-connected building units. The [M(C2O4)a(H2O)n]m units are connected via sharing the bis-bidentate bridging oxalate ligands to form binuclears in HNU-2 and 1D "zigzag" chains in HNU-3 and HNU-4. cular building units to design 3D open frameworks with It is suggested that these compounds could be used as mole- zeolite topologies.  相似文献   

16.
Peter C. Junk  Jonathan W. Steed   《Polyhedron》1999,18(27):4646-3597
[Co(η2-CO3)(NH3)4](NO3)·0.5H2O and [(NH3)3Co(μ-OH)2(μ-CO3)Co(NH3)3][NO3]2·H2O were prepared by prolonged aerial oxidation of a solution of Co(NO3)2·6H2O and ammonium carbonate in aqueous ammonia. The formation of these side products highlights the richness of the chemistry of these systems and the possibility of by products if methods are not strictly adhered to. The X-ray crystal structures of [Co(η2-CO3)(NH3)4][NO3]·0.5H2O and [(NH3)3Co(μ-OH)2(μ-CO3)Co(NH3)3][NO3]2·H2O reveal a monomeric octahedral cobalt center with η2-bound CO32− in the former, while the latter consists of a dimeric array where the two cobalt centers are bridged by two OH and one μ2-CO32− groups with three terminal NH3 ligands for each Co center. In both complexes extensive hydrogen bonding interactions are evident.  相似文献   

17.
We synthesized three new Ni(II) coordination polymers [Ni(LXHLPXH2O)2]- H2O(CP1),[Ni(LXNIP)]-2H2O(CP2) and [Ni(LXNDCXH20)2](CP3)[L=N,N′-bis(pyridme-3-yl)thiophene-2,5-dicarboxamide, H2HIP=5-hydroxyisophthalic acid, H2NIP=5-nitroisophthalic acid, H2NDC=2,6-naphthalenedicarboxylie acid] by hydrothermal method, which were characterized by means of infrared spectra(IR), TG analyses, PXRD and single-crystal X-ray diffraction. The CPI is a ID tubular structure based on [Ni-HIP]2 loops and pairs of L ligands. CP2 is a 2D 3,5-connected architecture, which consists of Ni-L linear chains and (Ni-NIP)2 double chains. CP3 is a 2D network, which features 4-connected topology. Solid-state luminescent behaviours of CP-P3 were investigated. The CPI can detect Fe^3+ ions through luminescence quenching. The electrochemical properties of CPI buk-modified carbon paste electrode(CP1-CPE) has also been investigated, which has bifunctional electrocatalytic activity for oxidation of ascorbic acid and reduction of NO2^-.  相似文献   

18.
The X-ray crystallographic studies are reported for the water-soluble trivalent lanthanide complexes of the macrocyclic p-sulfonatothiacalix[4]arene [Gd(H2O)6((CH3)2SO)(p-sulfonatothiacalix[4]arene)]·H3O+·5H2O (1) and Na[Nd(H2O)6((CH3)2SO)(p-sulfonatothiacalix[4]arene)]·3H2O (2). The complexes are isostructural and belong to monoclinic system, C2/m space group. The Ln3+ metal ion is coordinated by the thiacalixarene ligand via the sulfonato group, and also ligated by an oxygen atom of a dimethyl sulfoxide (DMSO) molecule that occupies the cavity of the thiacalixarene and six aqua ligands. The thiacalixarenes are linked by the coordinated water molecules through hydrogen bonding to form a 2D polymer. The p-sulfonatothiacalixarenes maintain the clay-like bi-layer structure in the coordination network.  相似文献   

19.
The compound [Zn(H2O)4]2[H2As6V15O42(H2O)]·2H2O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) Å, c=33.970(7) Å, γ=120°, V=4278.8(12) Å3, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H2As6V15O42(H2O)]4− anions and [Zn(H2O)4]2+ cations linked through hydrogen bonds into a network. The [H2As6V15O42(H2O)]6− cluster consists of 15 VO5 square pyramids linked by three As2O5 handle-like units.  相似文献   

20.
以5-氨基四氮唑(HATz)、1,4-对苯二甲酸(H2BDC)和Zn(NO32为反应物,在水热条件下得到了1个二维层结构的Zn(Ⅱ)配位聚合物{[Zn2(ATz)2(BDC)(H2O)2] ·H2O}n(1),而在N,N’-二甲基甲酰胺(DMF)溶剂热条件下得到了1个三维结构的Zn(Ⅱ)配位聚合物{[Zn2(ATz)2(BDC)(DMF)2] }n(2). 通过元素分析、红外光谱、单晶X射线衍射和粉末X射线衍射等对它们的组成和结构进行了表征. 单晶结构分析结果表明,配合物1是以Zn(Ⅱ)离子作连接点、μ2-ATz-和μ2-BDC2-作连接子形成的3-连接(6,3)蜂窝型二维层结构,二维层之间再通过氢键作用形成三维超分子结构. 配合物2是以两羧基桥连的双核Zn(Ⅱ)单元[Zn2(CO)2] 作连接点、μ2-ATz-和μ4-BDC2-作连接子形成的6-连接简单立方格子的三维金属-有机框架结构. 室温固体荧光实验表明,在350 nm的光激发下,配合物1和2分别在451和466 nm处出现强烈的荧光发射.  相似文献   

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