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1.
Two sulfato CuII complexes [Cu2(bpy)2(H2O)(OH)2(SO4)]· 4H2O ( 1 ) and [Cu(bpy)(H2O)2]SO4 ( 2 ) were synthesized and structurally characterized by single crystal X—ray diffraction. Complex 1 consists of the asymmetric dinuclear [Cu2(bpy)2(H2O)(OH)2(SO4)] complex molecules and hydrogen bonded H2O molecules. Within the dinuclear molecules, the Cu atoms are in square pyramidal geometries, where the equatorial sites are occupied by two N atoms of one bpy ligand and two O atoms of different μ2—OH groups and the apical position by one aqua ligand or one sulfato group. Through intermolecular O—H···O and C—H···O hydrogen bonds and intermolecular π—π stacking interactions, the dinuclear complex molecules are assembled into layers, between which the hydrogen bonded H2O molecules are located. The Cu atoms in 2 are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two H2O molecules and two sulfato groups with the sulfato O atoms at the trans positions and are bridged by sulfato groups into 1[Cu(bpy)(H2O)2(SO4)2/2] chains. Through the interchain π—π stacking interactions and interchain C—H···O hydrogen bonds, the resulting chains are assembled into bi—chains, which are further interlinked into layers by O—H···O hydrogen bonds between adjacent bichains.  相似文献   

2.
Six new coordination complexes, [Cd(η 2-OOCCH=(CH3)CFc)2(bix)]2·(CH3OH)0.5 (1), [Zn(η 2-OOCCH=(CH3)CFc)(η 1-OOCCH=(CH3)CFc)(bix)]2·(H2O)0.5 (2), [Zn(η 2-OOCCH=(CH3)CFc)2(pbbm)]2·(CH3OH)2 (3), {[Mn(η 1-OOCCH=(CH3)CFc)2(bbbm)(H2O)2]·(CH3OH)3}n (4), {[Cd(η 1-OOCCH=(CH3)CFc)2(bbbm)]·(CH3OH)2}n (5), and [Cd(η 2-OOCCH=(CH3)CFc)2(pmbbm)]n (6) {Fc?=?(η 5-C5H4)Fe(η 5-C5H4), bix?=?1,4[bis(imidazol-1-ylmethyl)benzene], pbbm?=?1,1′-[(1,4-propanediyl)bis-1H-benzimidazole], bbbm?=?1,1′-[(1,4-butanediyl)bis-1H-benzimidazole)], pmbbm?=?1,1′-[(1,4-pentanediyl)bis-1H-benzimidazole]}, were prepared and characterized. X-ray crystallographic analysis reveals that 1–3 are dimers bridged by bix and pbbm. Complexes 4–6 are one-dimensional (1-D) structures bridged by bbbm and pmbbm, respectively. Various ππ interactions were discovered in 1–6 that make significant contributions to molecular self-assembly. Solution differential pulse voltammetry of 1–6 indicates that the half-wave potentials of the ferrocenyl moieties in these complexes shift to positive potential compared with that of 3-ferrocenyl-2-crotonic acid.  相似文献   

3.
The reaction between fluorenyllithium and Mo(η3‐C3H5)Cl(NCMe)2(CO)2 led to the isolation of di‐μ3‐chlorido‐di‐μ3‐hydroxido‐tetrakis[(η3‐allyl)dicarbonylmolybdenum(II)]–9‐fluorenone–tetrahydrofuran (1/1/1), [Mo4(C3H5)4Cl2(OH)2(CO)8]·C4H8O·C13H8O. The tetrametallic Mo4 unit constitutes the first example of a complex containing simultaneously two μ3‐OH groups and two μ3‐Cl anions capping the metallic trigonal prism. The four crystallographically independent Mo2+ centres exhibit distorted octahedral geometry with the η3‐allyl groups being trans‐coordinated to a μ3‐OH group and the carbonyl groups occupying the equatorial plane. Space‐filling tetrahydrofuran and 9‐fluorenone molecules are engaged in strong O—H...O hydrogen‐bonding interactions with Mo43‐allyl)4Cl2(OH)2(CO)8 complexes.  相似文献   

4.
Two metal-organic coordination polymers [Cu(bpy)2(H2O)2](NO3)2·4.5C2H5OH (1) and [Cu2(bpy)(H2O)(L-pha) 2](NO3)2·H2O (2) (L-Hpha = L-phenylalanine, bpy = 4,4′-bipyridyl) are prepared by slow evaporation of an aqueous alcoholic solution of copper nitrate, L-phenylalanine, and 4,4′-bipyridyl. The structure and composition of the obtained compounds are determined by single crystal XRD. The framework of compound 1 is positively charged and forms two types of intersecting channels. Compound 2 is a homochiral metal-organic coordination polymer whose structure contains L-phenylalanine anions.  相似文献   

5.
The blue tetranuclear CuII complexes {[Cu(bpy)(OH)]4Cl2}Cl2 · 6 H2O ( 1 ) and {[Cu(phen)(OH)]4(H2O)2}Cl4 · 4 H2O ( 2 ) were synthesized and characterized by single crystal X‐ray diffraction. ( 1 ): P 1 (no. 2), a = 9.240(1) Å, b = 10.366(2) Å, c = 12.973(2) Å, α = 85.76(1)°, β = 75.94(1)°, γ = 72.94(1)°, V = 1152.2(4) Å3, Z = 1; ( 2 ): P 1 (no. 2), a = 9.770(3) Å, b = 10.118(3) Å, c = 14.258(4) Å, α = 83.72(2)°, β = 70.31(1)°, γ = 70.63(1)°, V = 1252.0(9) Å3, Z = 1. The building units are centrosymmetric tetranuclear {[Cu(bpy)(OH)]4Cl2}2+ and {[Cu(phen)(OH)]4(H2O)2}4+ complex cations formed by condensation of four elongated square pyramids CuN2(OH)2Lap with the apical ligands Lap = Cl, H2O, OH. The resulting [Cu42‐OH)23‐OH)2] core has the shape of a zigzag band of three Cu2(OH)2 squares. The cations exhibit intramolecular and intermolecular π‐π stacking interactions and the latter form 2D layers with the non‐bonded Cl anions and H2O molecules in between (bond lengths: Cu–N = 1.995–2.038 Å; Cu–O = 1.927–1.982 Å; Cu–Clap = 2.563; Cu–Oap(OH) = 2.334–2.369 Å; Cu–Oap(H2O) = 2.256 Å). The Cu…Cu distances of about 2.93 Å do not indicate direct interactions, but the strongly reduced magnetic moment of about 2.74 B.M. corresponds with only two unpaired electrons per formula unit of 1 (1.37 B.M./Cu) and obviously results from intramolecular spin couplings (χm(T‐θ) = 0.933 cm3 · mol–1 · K with θ = –0.7 K).  相似文献   

6.
[Cd2(C7H3NO5)2 · 4(H2O)] n · 3nH2O · 0.5n(CH3OH) (1) and [Cd3(C7H2NO5)2 · 10(H2O)] · 2H2O ·0.5CH3OH (2) were synthesized and characterized by X-ray single-crystal diffraction. The crystal structure of 1 reveals that both Cds are seven-coordinate with pentagonal bipyramid geometries. Coordination polyhedra are interlinked into a 1-D chain, further linked by hydrogen bonds into a 3-D network. Complex 2 is a discrete structure, then independent [Cd3(C7H2NO5)2 · 10(H2O)] are linked by hydrogen bonds into a 3-D network. The optical properties of 1 and 2 were investigated with fluorescent spectra; both exhibit strong green luminescence probably originating from π–π* transition of the ligand.  相似文献   

7.
Three kinds of trinuclear metal string complexes, [Ni3(dpa)4(L1)2]?·?H2O?·?C2H5OH (L1?=?(E)-3-(2-hydroxyl-phenyl)-acrylic acid) (1), [Ni3(dpa)4(L2)2]?·?2C2H5OC2H5 (L2?=?(E)-3-(3-hydroxyl-phenyl)-acrylic acid) (2) and [Ni3(dpa)4(L3)2]?·?3CH2Cl2?·?1.5CH3OH (L3?=?(E)-3-(4-hydroxyl-phenyl)-acrylic acid) (3). (dpa??=?bis(2-pyridyl)amido), have been synthesized. The structures of 1 and 2 have been analyzed by the X-ray single-crystal diffraction showing hydrogen-bonded networks.  相似文献   

8.
Hydrothermal reactions of Pb(NO3)2 and 3-fluorophthalic acid (H2Fpht) in the absence or presence of 2,2′-bipyridine (bpy) gave two coordination polymers: Pb5(Fpht)4(Fba)2 (1) and [Pb2(Fpht)2(bpy)(H2O)]·3H2O (2). The 3-fluorobenzoic acid (HFba) results from an in situ decarboxylation of H2Fpht. Solid 1 displays a 2-D structure, comprising center-related hexanuclear [Pb3(COO)6]2 units. There are three crystallographically different Pb(II) ions and two different ligands, Fpht and Fba. The Fpht ligands adopt μ6?:?η5η3 and μ6?:?η3η4 unusual bridging coordination modes. A 3-D supramolecular architecture is formed via C–H?F hydrogen bonds. Solid 2 possesses a 1-D chain structure, comprising center-related tetranuclear [Pb2(COO)4]2 units. There are two crystallographically different Pb(II) ions. The Fpht ligands adopt μ3?:?η2η3 and μ4?:?η3η3 bridging coordination. The free water molecules form (H2O)3 clusters to link the 1-D chain by hydrogen bonds. A 3-D supramolecular assembly is constructed via hydrogen bonds between the free water and the F of Fpht ligands. Fluorescence of the complexes originates from π*–π transitions of the ligands.  相似文献   

9.
New Co(II), Ni(II), and Cu(II) complexes with 4-(3-hydroxyphenyl)-1,2,4-triazole (L) with the compositions [Co3L6(H2O)5(C2H5OH)](NO3)6 · 2H2O · C2H5OH (I), [Ni3L6(H2O)6](NO3)6 · 2H2O (II), and [M3L6(H2O)6](ClO4)6 · nH2O (M = Co2+, n = 2 (III); Ni2+, n = 2 (IV); Cu2+, n = 0 (V)) are synthesized. The complexes are studied by X-ray structure analysis, X-ray diffraction analysis, UV and IR spectroscopy, and the statistical magnetic susceptibility method. All compounds have the linear trinuclear structure. Ligand L is coordinated to the metal ions by the N(1) and N(2) atoms of the heterocycle according to the bidentate bridging mode. In all compounds the coordination polyhedron of the metal atom is a distorted octahedron. The molecular and crystal structures of compound I, [Co3L6(H2O)6](ClO4)6 · 8C2H5OH (IIIa), and [Ni3L6(H2O)6](ClO4)6 · 8C2H5OH (IVa) are determined.  相似文献   

10.
《Fluid Phase Equilibria》1999,166(2):245-258
Excess molar volumes VmE and viscosities η have been measured as a function of composition at atmospheric pressure and 298.15 K for nine {an alkoxyethanol+dimethyl carbonate (C3H6O3), diethyl carbonate (C5H10O3), or propylene carbonate (C4H6O3)} mixtures. The alkoxyethanols were 2-methoxyethanol (CH3OCH2CH2OH), 2-(2-methoxyethoxy)ethanol {CH3(OCH2CH2)2OH}, and 2-{2-(2-methoxyethoxy)ethoxy}ethanol {CH3(OCH2CH2)3OH}. The VmE for each of the carbonate mixtures studied decrease in magnitude as the polar head group of the alkoxyethanol increases. From the experimental results, deviation in the viscosity (Δlnη) have been calculated. The experimental results have been correlated using the Redlich–Kister equation to estimate the coefficients and standard errors. The experimental and calculated quantities are used to discuss the mixing behaviour of the components.  相似文献   

11.
Reactions of cadmium(II) with 5-(4-carboxybenzylamino)isophthalic acid (H3L) in the presence of 2-(pyridin-2-yl)-1H-benzo[d]imidazole (pybim) and 2,2′-bipyridine (bpy) by hydrothermal method lead to two complexes, [Cd(HL)(pybim)]·H2O (1) and [Cd2(L)(HCOO)(bpy)2(H2O)]·H2O (2). Complexes 1 and 2 have been characterized by single-crystal and powder X-ray diffraction, Infrared spectra, and elemental and thermogravimetric analyses. 1 has a double-chain structure while 2 consists of uninodal 3-connected 2-D hcb networks with (63) topology. Luminescence and sorption properties of 1 and 2 were also investigated.  相似文献   

12.
13.
Chemistry of Polyfunctional Molecules. 119 [1]. Tetracarbonyl-dicobalt-tetrahedrane Complexes with the Ligands Bis(diphenylphosphanyl)-amine, 2-Butin-1,4-diol, and tert.-Butylphosphaacetylene — Crystal Structure of the Phosphaalkyne Derivative Co2(μ-CO)2(CO)4(μ-Ph2P? NH? PPh2P,P′) · 1/2C6H5CH3 ( 4 · 1/2C6H5CH3) reacts with 2-butine-1,4-diol, HOCH2? C?C? CH2OH ( 5 ), to the dark-red tetrahedrane complex Co2(CO)4(μ-η22-HOCH2? C?C? CH2OH? C2, C3) · (μ-Ph2P? NH? PPh2? P,P′) · THF (6 · THF). With t-butyl-phosphaacetylene, tBu? C?P ( 7 ), 4 · THF forms Co2(CO)4(μ-η22-tBu? C?P)(μ-Ph2P? NH? PPh2? P,P′) ( 8 ), which also belongs to the tetrahydrane type. The compounds were characterized by their mass, IR, 31P{1H} NMR, 13C{1H} NMR, and1H NMR spectra. Crystals suitable for X-ray structure analyses have been obtained for 8 from dioxane. The dark red blocks crystallize in the monoclinic P21/c space group with the lattice constants a = 1404,1(5), b = 1330,0(7), c = 2578,8(10)pm; β = 90,82(3)°.  相似文献   

14.
Reaction of CuCl2 · 2H2O, phenanthroline, maleic acid and NaOH in CH3OH/H2O (1:1 v/v) at pH = 7.0 yielded blue {[Cu(phen)]2(C4H2O4)2} · 4.5H2O, which crystallizes in the monoclinic space group C2/c (no. 15) with cell dimensions: a = 18.127(2)Å, b = 12.482(2)Å, c = 14.602(2)Å, β = 103.43(1)°, U = 3213.5(8)Å3, Z = 4. The crystal structure consists of the centrosymmetric dinuclear {[Cu(phen)]2(C4H2O4)2} complex molecules and hydrogen bonded H2O molecules. The Cu atoms are each square‐pyramidally coordinated by two N atoms of one phen ligand and three carboxyl O atoms of two maleato ligands with one carboxyl O atom at the apical position (d(Cu‐N) = 2.008, 2.012Å, equatorial d(Cu‐O) = 1.933, 1.969Å, axial d(Cu‐O) = 2.306Å). Two square‐pyramids are condensed via two apical carboxyl O atoms with a relatively larger Cu···Cu separation of 3.346(1)Å. The dinuclear complex molecules are assembled via the intermolecular π—π stacking interactions into 1D ribbons. Crossover of the resulting ribbons via interribbon π—π stacking interactions forms a 3D network with the tunnels occupied by H2O molecules. The title complex behaves paramagnetically between 5—300 K, following the Curie‐Weiss law χm(T—θ) = 0.435 cm3 · mol—1 · K with θ = 1.59 K.  相似文献   

15.
通过配体1,2-环己二胺缩邻香兰素(H2L)和不同的镱盐反应,合成了4个镱稀土配合物[Yb(H2L)2](ClO43·2CH3OH·H2O(1),[Yb4(L)4(NO32(H2O)2](PF62·4CH3CN(2),[Yb4(L)4(H2O)2Cl2](PF62·2CH2Cl2·2H2O(3)和[Yb4(L)4(NO32(H2O)2][Yb(NO33(H2O)2(CH3OH)](NO32 ·4CH2Cl2·6CH3OH(4)。X射线单晶衍射分析表明配合物1为零维的单核结构,配合物2~4均为四核结构。研究了4个配合物的近红外发光性能。  相似文献   

16.
合成了3种金属配合物{[Cd(pztc)(H2O)2]·(H2bpy)·3(H2O)}n1),{[Zn3(pztc)2(Hbpy)2(bpy)(H2O)4]·7H2O}n2),[Cu6(pztc)4(Hbpy)4(bpy)2(H2O)8]·17H2O(3)(bpy=4,4’-联吡啶,H4pztc=吡嗪-2,3,5,6-四甲酸),并对其进行了红外光谱分析、元素分析、热重分析、荧光光谱分析和X-射线单晶衍射分析。其中13中存在丰富的氢键,2为3D网状结构,存在金鱼状(H2O)10水簇。3为由化学键连接成的1D链状结构,由氢键连接成3D超分子结构。当激发光波长为320nm时,12的最大荧光发射峰分别在496nm和494nm。  相似文献   

17.
One nonlinear and one linear trinuclear copper(II) complex [Cu3(dien)2(pdc)2CH3OH]2?·?6CH3OH (1) and [Cu3(pdc)2(CH3OH)6(H2O)4] (2) were prepared and characterized structurally, where dien is diethylenetriamine and pdc3? the trianion of 3,5-pyrazoledicarboxylic acid. Both complexes consist of 3,5-pyrazoledicarboxylato-bridged trinuclear copper(II) centers. In 1, copper(II) ions are five-coordinate in distorted square pyramids with bond angles 164.78° for Cu(1)–Cu(2)–Cu(3) and 164.51° for Cu(4)–Cu(5)–Cu(6). In 2, the three copper(II) ions are six-coordinate with elongated octahedral geometry. The trinuclear units of 1 and 2 interact through hydrogen bonds to form 3-D and 2-D supramolecular networks, respectively. Variable temperature magnetic susceptibility measurements show that 1 and 2 are antiferromagnetically coupled with J values of ?11.2 and ?13.3?cm?1.  相似文献   

18.
Three Cu(II) complexes constructed from 4-(2-pyridyl)-1H-1,2,3-triazole (L), namely, [CuL2Cl2]·H2O, [CuL2(CH3OH)(NO3)]NO3 and [CuL2(H2O)]SO4, have been synthesized and characterized. X-ray crystal structure analyses revealed that [CuL2Cl2]·H2O and [CuL2(CH3OH)(NO3)]NO3 have octahedral geometries, whilst [CuL2(H2O)]SO4 adopts a square-pyramidal coordination geometry. In all three complexes, the Cu(II) atoms are chelated by two L ligands in the basal plane, whilst the apical positions are occupied by Cl?, NO3?, CH3OH or H2O. The bandgaps between the HOMO and LUMO were estimated by cyclic voltammetry (CV) and diffuse reflectance spectroscopy (DRS) to be 3.43, 3.12, and 3.74 eV, respectively. Theoretical calculations on each structure gave similar results to the experiments. Frontier molecular orbital analyses showed that the higher electron density on the apical ligand, the lower the bandgap.  相似文献   

19.
Crystals of mononuclear tris[bis(2,6‐diisopropylphenyl) phosphato‐κO]pentakis(methanol‐κO)lanthanide methanol monosolvates of lanthanum, [La(C24H34O4P)3(CH3OH)5]·CH3OH, ( 1 ), cerium, [Ce(C24H34O4P)3(CH3OH)5]·CH3OH, ( 2 ), and neodymium, [Nd(C24H34O4P)3(CH3OH)5]·CH3OH, ( 3 ), have been obtained by reactions between LnCl3(H2O)n (n = 6 or 7) and lithium bis(2,6‐diisopropylphenyl) phosphate in a 1:3 molar ratio in methanol media. Compounds ( 1 )–( 3 ) crystallize in the monoclinic P21/c space group and have isomorphous crystal structures. All three bis(2,6‐diisopropylphenyl) phosphate ligands display a κO‐monodentate coordination mode. The coordination number of the metal atom is 8. Each [Ln{O2P(O‐2,6‐iPr2C6H3)2}3(CH3OH)5] molecular unit exhibits four intramolecular O—H…O hydrogen bonds, forming six‐membered rings. The unit forms two intermolecular O—H…O hydrogen bonds with one noncoordinating methanol molecule. All six hydroxy H atoms are involved in hydrogen bonding within the [Ln{O2P(O‐2,6‐iPr2C6H3)2}3(CH3OH)5]·CH3OH unit. This, along with the high steric hindrance induced by the three bulky diaryl phosphate ligands, prevents the formation of a hydrogen‐bond network. Complexes ( 1 )–( 3 ) exhibit disorder of two of the isopropyl groups of the phosphate ligands. The cerium compound ( 2 ) demonstrates an essential catalytic inhibition in the thermal decomposition of polydimethylsiloxane in air at 573 K. Catalytic systems based on the neodymium complex tris[bis(2,6‐diisopropylphenyl) phosphato‐κO]neodymium, ( 3′ ), which was obtained as a dry powder of ( 3 ) upon removal of methanol, display a high catalytic activity in isoprene and butadiene polymerization.  相似文献   

20.

The three-dimensional network of lanthanide (III) complexes with isophthalato (IPT) ligand, (Eu[C6H4(COO?)2-1,3](CH3COO?)(H2O)2}·H2O 1 and {Sm[C6H4(COO?)2-1,3](CH3COO?) (H2O)2} H2O 2, has been prepared by the hydro(solvo)thermal reaction of Eu(C1O4)3·6H2O or Sm(C1O4)3·6H2O, 1,3-dicyanobenzene and acetic acid in the presence of ethanol and H2O. In the reaction, 1,3-dicyanobenzene was hydrolyzed to give IPT ligand. Single crystal x-ray analysis revealed that crystals 1 and 2 are isomorphous with the isostructural {M[C6H4(COO?)2-1,3](CH3COO?)(H2O)2}·H2O unit. In 1 and 2, IPT acts as a bridging ligand to connect three adjacent metal atoms, forming a network like an undulating sheet paralleling the bc plane. The carboxylate from acetate bridges two adjacent metal atoms in a tridentate mode between the different sheets to extend the structure into a three-dimensional network.  相似文献   

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