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1.
Three Co(II) and Ni(II) complexes, namely [Co(bpdc)(H2O)2] (1), [Ni(bpdc)(H2O)2] (2), and [Co2(bpdc)2(prz)0.5(H2O)3]·0.5H2O (3) (H2bpdc = 2,2′-bipyridine-6,6′-dicarboxylic acid and prz = piperazine), have been synthesized from H2bpdc and the corresponding metal salts under hydrothermal conditions. The complexes were characterized by physico-chemical and spectroscopic methods, as well as by X-ray crystallography. Compounds 1 and 2 both consist of neutral mononuclear molecules, of [Co(bpdc)(H2O)2] and [Ni(bpdc)(H2O)2], respectively. Compound 3 consists of a mononuclear molecule of [Co(bpdc)(H2O)2] and a binuclear molecule of [Co2(bpdc)2prz (H2O)2]. The discrete neutral complexes 13 further extend their structures into three-dimensional supramolecular architectures by intermolecular O–H⋯O and C–H⋯O hydrogen bonds as well as π–π stacking interactions. Magnetic susceptibility measurements show that complex 3 exhibits weak ferromagnetic interactions between the two Co(II) ions bridged by the prz ligand, with C = 5.41 cm3 mol−1 K and θ = +27.6 K, respectively.  相似文献   

2.

Abstract  

Four complexes of 3,3-diphenylpropanoate (L) and 4,4′-bipyridine as auxiliary bridging ligands were synthesized and characterized, namely [Zn(L)2(4bpy)(EtOH)2] (1), [Co(L)2(4bpy)(EtOH)2] (2), [Ni(L)2(4bpy)(EtOH)2] (3), and [Cu(L)2(4bpy)(H2O)] (4) (4bpy = 4,4′-bipyridine). X-ray single-crystal diffraction analyses show that complexes 14 all take one-dimensional (1D) fishbone-like structures incorporating bridging 4bpy ligands. The complexes show different supramolecular frameworks interlinked via intermolecular hydrogen bonds, π···π stacking, and/or C–H···π supramolecular interactions. Complex 3 only has a simple one-dimensional fishbone-like chain, whereas complexes 1 and 2 show two-dimensional supramolecular structures by interchain C–H···O hydrogen bonds. Complex 4 is assembled into two-dimensional layers and then an overall three-dimensional framework by a combination of interchain O–H···O hydrogen bonds and C–H···π supramolecular interactions. The luminescent properties of the ligands and their complexes were investigated.  相似文献   

3.
Two new Cu(II) complexes, [Cu(L1)2] (1) and [Cu(L2)2] (2) (HL1 = (E)-3-bromo-5-chloro-2-hydroxy benzaldehyde O-methyl oxime; HL2 = (E)-3-bromo-5-chloro-2-hydroxy benzaldehyde O-ethyl oxime), have been synthesized and characterized by physicochemical and spectroscopic methods. X-ray crystallographic analyses show that complexes 1 and 2 have similar structures, consisting of one Cu(II) atom and two L units. In both complexes, the Cu(II) atom, lying on an inversion center, is four-coordinated in a trans-CuN2O2 square-planar geometry by two phenolate O and two oxime N atoms from two symmetry-related N,O-bidentate oxime ligands. Moreover, both complexes form an infinite three-dimensional supramolecular structure involving intermolecular C–H···Br hydrogen bonds and π···π stacking interactions between the metal chelate rings and aromatic rings. Substituent effects in the two complexes are discussed.  相似文献   

4.
Two new copper(II) complexes, [Cu(p-FBA)2(2,2′-bpy)]·(H2O) (1) and [Cu(p-FBA)(2,2′-bpy)2]·(p-FBA)2 (2) {p-FBA = p-fluorobenzoic acid, 2,2′-bpy = 2,2′-bipyridine} have been obtained from an identical starting mixture using temperature as the only independent variable and characterized by X-ray single crystal diffraction as well as with infrared spectroscopy, elemental analysis, and thermogravimetric analysis. The results reveal that 1 has 1D infinite chain structure formed by O–H···O hydrogen bonds, while 2 features a 0D structure. Additionally, there exist C–H···O hydrogen bonds and π–π stacking interactions in 1, forming 2D supramolecular structure. Furthermore, density functional theory (DFT) calculations of the structures, stabilities, orbital energies, composition characteristics of some frontier molecular orbitals and Mulliken charge distributions of the [Cu(p-FBA)2(2,2′-bpy)] of 1 and [Cu(p-FBA)(2,2′-bpy)2]+ cation of 2 were performed by means of Gaussian 03W package and taking B3LYP/lanl2dz basis set.  相似文献   

5.
Two two-dimensional coordination complexes, {[Cu4(BTM)6(OPA)4] · 4DMF · 3H2O} n (1) and {[Cu(BDTM)(OH)](ClO4) · 2H2O} n (2) (BTM = bis(1,2,4-triazol-1-yl)methane, BDTM = bis(3,5-dimethyl-1,2,4-triazol-1-yl)methane, OPA2− = ortho-phthalic dianion, DMF = N,N-dimethylformamide), were synthesized and structurally characterized. Each Cu(II) ion locates in a distorted square pyramidal geometry in 1, in which OPA2− ligands bridge Cu2+ ions along a axis to form a magnetic transmission chain and BTM ligands act as flexible spacers to construct the two-dimensional layer structure. In 2, each Cu2+ ion adopts tetra-coordination geometry to two hydroxyl groups and two triazolyl nitrogen atoms from two different BDTM ligands. Two hydroxyl groups bridge two Cu2+ ions to form a rhombic diamond, and four BDTM ligands connect four diamonds to form a 36-membered macrocyclic structure with large channels along a axis. Magnetic properties revealed that both OPA2− and OH mediate anti-ferromagnetic interactions between Cu2+ ions with J = − 0.06(3) and −301.9(2) cm−1 for 1 and 2, respectively. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

6.
Four novel organic–inorganic hybrid compounds [Cu5 I(4,4′-bpy)3(2,2′-bpy)4][BW12O40] · H2O (1), [Ni0.5(2,2′-bpy)1.25][Ni(2,2′-bpy)3][Ni(2,2′-bpy)2(H2O)(SiW11VIWVO40)] · 0.5H2O (2), [H2bpy]2[Zn(2,2′-bpy)3]2[Si2W18O62] · 1.5H2O (3) and [CuII(2,2′-bpy)2]2[SiW12O40] · 2H2O (4) (2,2′-bpy = 2,2′-bipyridine, 4,4′-bpy = 4,4′-bipyridine) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, electrochemical measurements and single-crystal X-ray diffraction. Compound (1) is a novel [BW12O40]5− polyoxoanion bisupported by copper(I) coordination cations with mixed 2,2′-bpy and 4,4′-bpy ligands. Compound (2) is constructed from the [SiW11VIWVO40]5− polyoxoanions supported by [Ni(2,2′–bpy)2]2+. Compound (3) is composed of a novel [Si2W18O62]8− cluster and [Zn(2,2′–bpy)3]2+ complexes, which held together into a three-dimensional (3D) supramolecular network through hydrogen-bonding interactions. Compound (4) shows a 2D layer framework constructed from a bisupporting Keggin polyoxoanion cluster and [Cu(2,2′–bpy)2]2+ coordination polymer fragments, resulting in 3D networks via supramolecular interactions. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

7.
Two new supramolecular metal–organic complexes have been synthesized under hydrothermal conditions. Complex 1 exhibits a three-dimensional supramolecular network, constructed from [Co2(H3BPTC)2(phen)2] (H4BPTC = 3,3′4,4′-benzophenone tetracarboxylate acid, phen = 1,10-phenanthroline) discrete units. Complex 2 similarly exhibits discrete [Cu2(DPA)2(bipy)2(H2O)2] (DPA = 1,1′-biphenyl-2,2′-dicarboxylate acid, bipy = 2,2′-bipyridine) units, which are linked to form a three-dimensional supramolecular network through π–π interactions. It is interesting that during the synthesis of complex 1, the H4BPTC ligands undergo partial decomposition to give 1,2,4-benzenetricarboxylate (H3BTC) ligands, which react with Co to form [Co3(BTC)2]n (3). Complex 3 shows a three-dimensional covalent network. The magnetic properties of complexes 1 and 2 have been studied.  相似文献   

8.
The sandwich-type [Na(UO2)2(H2O)4(BiW9O33)2]13− uranium (VI) has been synthesized by reacting the trivacant species of B-α-[BiW9O33]9− with and investigated by IR and UV–Vis spectroscopy, and elemental analysis. The X-ray single crystal analysis was carried out on Na13[Na(UO2)2(H2O)4(BiW9O33)2] · 33H2O (I) which crystallizes in the orthorhombic system, space group Pna21 with a = 33.8454(19) ?, b = 21.1484(12) ?, c = 13.2403(7) ?, α = 90°, β = 90°, γ = 90°, and Z = 4. The polyanion consists of two lacunary B-α-[BiW9O33]9− groups which sandwich two uranyl cations and one sodium cation. The uranium atoms adopt distorted pentagonal–bipyramidal coordination, achieved by two equatorial bonds to each BiW9O33 unit and one external water ligand. The coordination of each uranium atom is evident by the shift of νas(W–Ob–W) and νas(Bi–O) stretching vibrational bonds. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

9.
The crystal structures of two copper(II) complexes of the cyclohexanecarboxylate ligand, namely [Cu(C6H11CO2)2(H2O)2]·H2O (1) and [Cu(dpyam)2(C6H11CO2)](NO3)·H2O (2) (C6H11CO2H = cyclohexanecarboxylic acid; dpyam = di-2-pyridylamine), have been determined by single-crystal X-ray analysis. Complex 1 contains the square-planar trans-CuO4 chromophore, while 2 shows the square pyramidal cis-distorted octahedral CuN4OO′ chromophore. Both complexes were found to show strong inhibitory activity against jack bean urease (IC50 = 1.75 and 8.57 μM for 1 and 2, respectively), when compared with acetohydroxamic acid (IC50 = 63.12 μM).  相似文献   

10.
Abstract  Reactions of monovacant Dawson-/Keggin-polyoxoanions, formed in situ from trivacant Dawson-/Keggin-precursors, with copper complexes under hydrothermal conditions lead to three inorganic–organic hybrid polyoxotungstates [Cu(en)2(H2O)]2{[Cu(en)2(H2O)]2[Cu(en)2]4[Cu(en)2][α2-P2W17CuO61]2}·(OH)2·12H2O (1), [Cu(dap)2][Cu(dap)2(H2O)]2[α-PW11CuO39]·(OH)·2H2O (2) and (H2en)2[α-PW11CuO39][Cu(en)2(H2O)2]0.5·1.5H2O (3) (en = ethylenediamine and dap = 1,2-diaminopropane). X-ray structural analyses demonstrate that 1 exhibits the first zigzag 1-D chain arrangement constructed from mono-copperII-substituted Dawson dimeric polyoxoanions [α2-P2W17CuO61]216− linked by [Cu(en)2]2+ bridges, whereas 2 and 3 display 1-D linear chain architectures made up of mono-copperII-substituted Keggin polyoxoanions [α-PCuW11O39]5− linked together via corner-sharing MO6 octahedra (M = Cu or W). Graphical Abstract  Reactions of monovacant Dawson or Keggin polyoxoanions with copper complexes under hydrothermal conditions lead to three novel 1-D chain-like inorganic- organic hybrid polyoxotungstates.   相似文献   

11.
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   

12.
The reaction of N-benzoylphosphoramidic dichloride with amines afforded some new N-benzoylphos-phoric triamides with formula C6H5C(O)NHP(O)(X)2, X=NH–CH(CH3)2 (1), NH–CH2–CH(CH3)2 (2), NH–CH2–CH(OCH3)2 (3), N(CH3)[CH2CH(OCH3)2] (4) and N(CH3)(C6H11) (5) that were characterized by 1H,13C,31P NMR, IR spectroscopy and elemental analysis. The structures have been determined for compounds 4 and 5 by X-ray crystallography. These compounds contain one amidic hydrogen atom and form centrosymmetric dimmers via intermolecular –P–OH–N–hydrogen bonds besides weak C–H⋯O hydrogen bonds that lead to three-dimensional polymeric clusters in the crystalline lattice.  相似文献   

13.

Abstract  

New phosphoramidates with formula 3-NC5H4C(O)NHP(O)XY (X=Y=Cl (1), X=Y=NH–C(CH3)3 (2a,2b), X=Y=N(C4H9)2 (3), X=Cl, Y=N(C2H5)2 (4) were synthesized and characterized by IR, 1H-, 13C-, 31P-NMR spectroscopy and CHN elemental analysis. Surprisingly, the reaction of compound 2a with LaCl3, 7H2O in 3:1 M ratio leads to a polymorph of this compound (2b). NMR spectra indicate that 2 J(PNHamide) in 2b (7.0 Hz) is very much greater than in 2a (4.1 Hz), while δ(31P) values are identical for both of them. In IR spectra, υ(P=O) is weaker but υ(C=O) is stronger in 2a than in 2b. The structures of 2a, 2b were determined by X-ray crystallography. These compounds form centrosymmetric dimers via two intermolecular P=O……H–N hydrogen bonds. Strong intermolecular N–H…N, N–H…O and weak C–H…O hydrogen bonds lead to a three-dimensional polymeric cluster in the 2a while intermolecular strong N–H……N and weak C–H……O hydrogen bonds form a two-dimensional polymeric chain in 2b.  相似文献   

14.
Three new binuclear vanadium(V) complexes of bis(aryl)adipohydrazones (H4L1 = bis((2-hydroxynaphthalen-1-yl)methylene)adipohydrazide, H4L2 = bis(5-bromo-2-hydroxybenzylidene)adipohydrazide, and H4L3 = bis(2-hydroxy-3-methoxybenzylidene)adipohydrazide) were synthesized by direct reaction of [VO(acac)2] with the hydrazone ligands. The ligands and complexes were characterized by FT–IR, UV–Vis, and NMR spectroscopic methods. The crystal structures of the complexes of L1 and L3 were determined by X-ray analyses. The solid-state structure of the complex of L1 features a 1D hydrogen-bonded chain from N⋯H–O hydrogen bonding. The catalytic activities of these complexes have been tested in the oxidation of various hydrocarbons using H2O2 as the terminal oxidant. Generally, good to excellent conversions have been obtained.  相似文献   

15.
Two hexacoordinated mononuclear Co(III) compounds of the type cis-[Co(L)(N3)2] X [1, X = ClO4; 2, X = PF6; L = N,N′-(bis(pyridine-2-yl)benzylidine)-1,4-butanediamine] have been synthesized and characterized by physicochemical and spectroscopic methods. The crystal structures of complexes 1 and 2 both have distorted octahedral geometry with two terminal azides in mutual cis orientations. In the crystalline state, two mononuclear units of 1 are associated by weak C–H…π interactions to produce a dimeric unit, which packs through C–H…O hydrogen bonds and π…π interactions leading to a 2-D continuum. The mononuclear units in 2 are engaged in weak cooperative intermolecular C–H…π interactions and multiple C–H…F hydrogen bonds giving rise to a 3-D network structure. These diamagnetic compounds are redox active and show luminescence in DMF solutions.  相似文献   

16.
Four copper complexes with similar trinuclear copper units, [Cu6(Bmshp)2(SO4)2(H2O)7]·2H2O (1), [Cu3(Bmshp)(ClO4)2(H2O)4]·5H2O (2), [Cu3(Bmshp)(DMF)4(H2O)2]·H2O·2DMF·2ClO4 (3) and [Cu3(H2Bcshp)(ClO4)2(H2O)4]·3H2O (4) (H4Bmshp = 2,6-bis[(3-methoxysalicylidene)hydrazinocarbonyl]pyridine, H6Bcshp = 2,6-bis[(3-carboxylsalicylidene)hydrazinocarbonyl]pyridine), were synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction analysis. Due to the different anions, solvents and ligands used in the syntheses, complexes 14 exhibit diverse supramolecular structures constructed from the corresponding trinuclear copper units via H-bonds.  相似文献   

17.
Two new Mn(II) coordination polymers formed with molecular formula [Mn(H2O)2(HBTC)·(H2O)] 1 and [Mn(H2O)2(4,4′bipy)(HBTC)2]·(H4,4′bipy)2 2, where BTC = 1,2,4-benzenetricarboxylate and 4,4′bipy = 4,4′bipydine, have been synthesized via hydrothermal approach and characterized by single crystal X-ray diffraction techniques. 1 is composed of Mn–H2O–Mn 1D chains and further the chains are linked by HBTC ligands to form a 2D network in the ab plane; 2 is constructed by Mn–4,4′bipy–Mn 1D chains along the b direction with Mn2+ ions coordinated to H2BTC and water as terminal ligands to form a 2D network. We also prepared a third compound with the molecular formula of [Mn(H2O)(HBTC)·(H2O)] which has been recently structurally reported elsewhere. The magnetic properties of the three compounds have been studied in detail under variable temperatures.  相似文献   

18.

Abstract  

Three copper(II), one zinc(II), and one ferrous(II) complexes having 3-bromo or 3,8-dibromo-1,10-phenanthroline ligand with different metal/ligand molar ratios, formulated as [Cu(3-bromo-phen)(ClO4)(C3H7NO)2(H2O)](ClO4) (1), [Cu(3,8-dibromo-phen)(ClO4)(C3H7NO)2(H2O)](ClO4) (2), [Cu(3,8-dibromo-phen)(ClO4)(H2O)3](ClO4)(H2O)3 (3), [Zn(3,8-dibromo-phen)2(H2O)2](ClO4)2(H2O)2 (4), and [Fe(3,8-dibromo-phen)3](ClO4)2(H2O)(CH4O)(C3H6O)2 (5) (phen = 1,10-phenanthroline), have been synthesized and characterized in this paper. X-ray single-crystal diffraction studies reveal the different crystallographic symmetry and packing fashions between neighboring phen rings in 1:1 Cu(II) complexes 13 due to the alteration of bromo substituent 1,10-phenanthroline ligands and coordinated or free solvent molecules. Additionally, in 1:2 Zn(II) and 1:3 Fe(II) complexes 4 and 5, continuous π–π stacking and alternating π–π and dimeric p–π stacking are found.  相似文献   

19.
A series of lanthanide–transition metal (Ln–M) complexes, namely, {[Ln2Cu(pydc)4(H2O)3]·H2O} n (Ln = Tb, Eu, Sm or Gd) (H2pydc = 2,5-pyridinedicarboxylic acid) have been synthesized hydrothermally by self-assembly of the lanthanide ions, copper(II) ions and 2,5-pyridinedicarboxylic acid. All the complexes were characterized by physicochemical and spectroscopic methods; in addition, structural analyses revealed that all four complexes crystallized in monoclinic space group P21 /c. The molecular structure contains both Cu and Ln atoms, with pydc ligands bridging the four coordinate Cu(II) centers and eight coordinate lanthanide centers to form a 3-D net structure. Hence, copper is oxidized from Cu(I) to Cu(II) during the preparation. In addition, the thermogravimetric analysis of 1 is discussed. Contrary to expectations, compounds 13 show no photoluminescent properties. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

20.
Three new reduced amino-acid Schiff base complexes, [Co(HL)2(H2O)2] · 4H2O (1), [Cu(HL)2(H2O)2] · 2H2O (2), and [Cd(HL)2(H2O)3] · 2H2O (3), where H2L is the reduced Schiff-base ligand derived from the condensation of N-(4-hydroxybenzaldehyde) with L-glycine, have been synthesized and characterized by physico-chemical and spectroscopic methods. In these complexes, the two bidentate monoanionic Schiff base ligands coordinate the metal center through the secondary amine N atom and the carboxylate O atom. Water ligands complete a distorted octahedral (1, 2) or a pentagonal bipyramidal coordination geometry (3) around each metal center. The binding interactions of the complexes with CT-DNA have been investigated by UV–visible spectrophotometry and fluorescence quenching methods. The results show that these complexes bind to CT-DNA with an intercalative mode. In addition, DNA cleavage experiments have been also investigated by agarose gel electrophoresis. Complexes 13 show oxidative DNA cleavage activity in the presence of H2O2/sodium ascorbate and the reactive oxygen species responsible for the DNA cleavage is most likely singlet oxygen. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

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