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1.
Three new organic-inorganic hybrid materials with 4,4′-bipy ligands and copper cations as linkers, [CuII(H2O)(4,4′-bipy)2][CuII(H2O)(4,4′-bpy)2]2H[CuIIP8Mo12O62H12] · 5H2O (1), [CuI(4,4′-bipy)][CuII(4,4′-bipy)]2 (BW12O40) · (4,4′-bipy) · 2H2O (2) and [CuI (4,4′-bipy)]3 (PMo12O40) · (pip) · 2H2O (3) (pip = piperazine; 4,4′-bipy = 4,4′-bipyridine), have been hydrothermally synthesized. The single X-ray structural analysis reveals that the structure of 1 is constructed from [Cu(H2O)(4,4′-bipy)2] complexes into a novel, three-dimensional supermolecular network with 1-D channels in which Cu[P4Mo6]2 dimer clusters reside. To the best of our knowledge, compound 1 is the first complex in which the [P4Mo6] clusters have been used as a non-coordinating anionic template for the construction of a novel, three-dimensional supermolecular network. Compound 2 is constructed from the six-supported [BW12O40]5− polyoxoanions and [CuI(4,4′-bipy)] and [CuII(4,4′-bipy)] groups into a novel, 3-D network. Compound 3 exhibits unusual 3-D supramolecular frameworks, which are constructed from tetrasupporting [PMo12O40]3− clusters and [CuI (4,4′-bipy)n] coordination polymer chains. The electrochemical properties of 2 and 3 have been investigated in detail.  相似文献   

2.
The reactions of 4-aminobenzoic acid (4-abaH), 4,4′-bipyridine (4,4′-bipy) and transitional metal ions (ZnII, MnII and CuII) gave rise to four supramolecular architectures, namely, [(4-abaH)2(4,4′-bipy)] (1), {[Zn2(4,4′-bipy)2(4-aba)4] (H2O)5}n (2), {[Mn(4,4′-bipy)2(H2O)4] (4-aba)Br(H2O)3} (3) and {[Cu2(4,4′-bipy)3(H2O)2(4-aba)2](NO3)2(H2O)4}n (4). Their crystal structures were determined by X-ray diffraction and show different structural motifs. 1 is a one-dimensional hydrogen bonding ladder constructed by 4-abaH and 4,4′-bipy. In 2, 4,4′-bipy bridges Zn(4-aba)2 units forming a one-dimensional zigzag chain, which is extended into a three-dimensional framework by crystalline water molecules through hydrogen bonding interactions. Three-dimensional network of 3 is constructed by mononuclear [Mn(4,4′-bipy)2(H2O)4]2+ cations, neutral crystalline water molecules, and 4-aba and Br anions through extensive hydrogen bonding and π-π interactions. However, one-dimensional ladder formed by 4,4′-bipy and Cu(4-aba) units in 4 is extended into a three-dimensional architecture through interpenetration of the lateral 4-aba arms into squares of the adjacent Cu-(4,4′-bipy) ladders and extensive hydrogen bonding interactions.  相似文献   

3.
Hua Jin 《Inorganica chimica acta》2007,360(10):3347-3353
Three new organic-inorganic hybrid compounds [CuI(2,2′-bipy)(4,4′-bipy)0.5]2[CuI(2,2′-bipy)(4,4′-Hbipy)][CuI(4,4′-bipy)]2[P2W18O62] · 3H2O (1), [CuI(2,2′-bipy)(4,4′-bipy)0.5]2[CuI(4,4′-bipy)]2[PW12O40] · 0.25H2O (2), and[CuI(4,4′-bipy)]3[PMo12O40] · en · 3H2O (3) (2,2′- bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), have been hydrothermally synthesized. Compound 1 represents the first 1D ladderlike structure formed by Dawson-type polyoxoanion [P2W18O62]6− and coordination polymer with mixed 4,4′-bipy and 2,2′-bipy ligands. The novel structure of 2 is composed of 1D hybrid zigzag chains linked by chains into a 3D framework. In compound 3, the [PMo12O40]3− clusters are hung on chains to form a new 1D chain.  相似文献   

4.
In our continuing efforts to explore the effects of substituent groups of ligands in the formation of supramolecular coordination structures, seven new CuII complexes formulated as [Cu2(L1)4(DMF)2] (1), {[Cu2(L1)4(Hmta)](H2O)0.75} (2), [Cu2(L2)4(2,2′-bipy)2] (3), [Cu2(L3)4(H2O)2] (4), [Cu2(L3)4(Hmta)] (5), [Cu2(L3)4(Dabco)] (6) and [Cu2(L3)4(Pz)] (7) with three monocarboxylate ligands bearing different substituent groups HL1-HL3 (HL1 = phenanthrene-9-carboxylic acid, HL2 = 2-phenylquinoline-4-carboxylic acid, HL3 = adamantane-1-carboxylic acid, Hmta = hexamethylenetetramine, 2,2′-bipy = 2,2′-bipyridine, Dabco = 1,4-diazabicyclo[2.2.2] octane and Pz = pyrazine), have been prepared and characterized by X-ray diffraction. In 1, 2 and 4-7, each CuII ion is octahedrally coordinated, and carboxylate acid acts as a syn-syn bridging bidentate ligand. While each CuII ion in 3 is penta-coordinated in a distorted square-pyramidal geometry. 1 and 4 both show a dinuclear paddle-wheel block, while 2, 5, 6 and 7 all exhibit an alternated 1D chain structure between dinuclear paddle-wheel units of the tetracarboxylate type Cu2-(RCO2)4 and the bridging auxiliary ligands Hmta, Dabco and Pz. Furthermore, 3 has a carboxylic unidentate and μ1,1-oxo bridging dinuclear structure with the chelating auxiliary ligand 2,2′-bipy. Moreover, complexes 1-6 were characterized by electron paramagnetic resonance (EPR) spectroscopy.  相似文献   

5.
Three new 2D PbII coordination polymers containing 4,4′-bipyridine (4,4′-bipy), 1,2-bis(4-pyridyl)ethane (bpa) and 1,2-bis(4-pyridyl)ethene (bpe) with bromide anions, [Pb(μ-4,4′-bipy)(μ-Br)2]n (1), [Pb(μ-bpa)(μ-Br)2]n (2) and [Pb(μ-bpe)(μ-Br)2]n (3) have been synthesized and characterized by elemental analysis, IR spectroscopy and their structures studied by X-ray crystallography. The thermal stability of compounds 1-3 was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The single-crystal X-ray data shows that the Pb2+-ions have coordination numbers of six and contain the rarely holodirected geometries.  相似文献   

6.
Two new organic-inorganic hybrid compounds, {[Cu(2,2′-bipy)2]2(Hbpy)[α-AlW12O40]}·H2O (1) and {[H2en][CuI(4,4′-bipy)]3(α-AlW12O40)}·4H2O (2) (2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine, py = pyridine, en = ethylene dimine) based on Keggin-type α-[AlW12O40]5− polyoxoaions and transition-metal organoamine subunits, have been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis (TG), and single-crystal X-ray diffraction. In addition, the electrochemical properties and photocatalytic activity of compound 1 were studied. The structural analysis reveals that 1 shows a 1D infinite chain structure constructed from [α-AlW12O40]5− polyoxoanions and {[CuII(2,2′-bipy)2][CuII(2,2′-bipy)(py)]}4+ fragments, in which the remarkable aspect is that [α-AlW12O40]5− polyoxoanion is modified in a fascinating symmetrical mode. Compound 2 displays an unprecedented 2D extended structure constructed from [α-AlW12O40]5− polyoxoanions and 4,4′-bipy-CuI-4,4′-bipy linear chains, in which three - chain belts formed by three linear chains arranged Cu parallel connect alternately with [α-AlW12O40]5− polyoxoanions. As far as we know, compounds 1 and 2 represent the first 1D and 2D extended hybrid materials constructed from 3d transition metals and polyoxotungstoaluminates linked through covalent bonds.  相似文献   

7.
The heteronuclear water-soluble and air-stable compounds [M(H2O)5M′(dipic)2] · mH2O (M/M′ = CuII/CoII (1), CuII/NiII (2), CuII/ZnII (3), ZnII/CoII (4), NiII/CoII (5), m = 2-3; H2dipic = dipicolinic acid) have been prepared by self-assembly synthesis in aqueous solution at room temperature, and characterized by IR, UV-Vis and atomic absorption spectroscopies, elemental and X-ray diffraction single crystal (for 1 and 2) analyses. 1-5 represent the first examples of heteronuclear dipicolinate compounds with 3d metals. Extensive H-bonding interactions involving all aqua ligands, dipicolinate oxygens and lattice water molecules further stabilize the dimetallic units by linking them to form three-dimensional polymeric networks.  相似文献   

8.
Interaction of [Cp*RuCl(μ-Cl)]2 with 2,2′-bipyridine (2,2′-bipy) in the presence of Na[PF6] gave a chloride bridging dinuclear complex [{Cp*Ru(2,2′-bipy)}2(μ-Cl)][PF6] (1). In the crystal structure, the cation [{Cp*Ru(2,2′-bipy)}2(μ-Cl)]+ contains a bent Ru-Cl-Ru linkage with an angle of 141.87(12)°. The tris(μ-hydroxo)diruthenium complex [{(η6-p-cymene)Ru}2(μ-OH)3][BF4] in acetone solution was treated by 4,4′-bipyridine (4,4′-bipy) to give a hydroxo-bridged tetranuclear complex [{(η6-p-cymene)Ru}2(μ-OH)2(μ-4,4′-bipy)]2[BF4]4 (2). Complex 2 consists of four (η6-p-cymene)Ru moieties connected by two 4,4′-bipy and four hydroxo-bridging groups, forming a novel metallomacrocycle with alternating hydroxyl and 4,4′-bipy bridges between the ruthenium atoms. Spectroscopic properties along with electrochemistry of two organoruthenium (II) complexes 1 and 2 are reported.  相似文献   

9.
Four novel metal coordination polymers, [Cd(dpa)(H2O)]n (1), [Cd(dpa)(2,2′-bipy)]n (2), {[Cd2(dpa)2(4,4′-bipy)3](4,4′-bipy)(H2O)2}n (3) and [Cd(dpa)(bim)2(H2O)]}n (4) (H2dpa = 2,4′-biphenyl-dicarboxylic acid, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine, bim = benzimidazole), have been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction. Single-crystal X-ray analyses reveal that the 2,4′-diphenic acids acts as bridging ligands, exhibiting rich coordination modes to link metal ions: bis-monodentate, bidentate chelating, chelating/bridging, monoatomic bridging and monodentate modes. In addition, the luminescent properties for compound 1-4 are also investigated in this work.  相似文献   

10.
Hydrothermal synthesis has afforded a series of divalent copper coordination polymers with substituted glutarate ligands and the rigid rod tether 4,4′-bipyridine (bpy): {[Cu(Hdmg)2(bpy)]·H2O}n (1, dmg = 3,3-dimethylglutarate), {[Cu2(dmg)(bpy)2](ClO4)]n (2), [Cu2(emg)2(bpy)]n (3, emg = 3-ethyl, 3-methylglutarate) and [Cu2(cda)2(bpy)]n (4, cda = 1,1-cyclopentanediacetate). All materials were characterized by single-crystal X-ray diffraction. Compound 1 manifests μ2-oxygen bridged [Cu2(Hdmg)4] “X”-patterns connected into a ribbon motif by bpy linkers. On the other hand, 2 possesses mixed-valence [CuICuIICuIICuI] tetrameric clusters bridged by dmg ligands and pillared into an 8-connected body-centered cubic (bcu) cationic lattice by bpy linkers. Compounds 3 and 4 are structurally very similar, displaying chain motifs with {Cu2(CO2)4} paddlewheels connected by dicarboxylates, in turn conjoined into (4,4)-grid coordination polymer layers by bpy tethers. Variable temperature magnetic data indicate the presence of very strong antiferromagnetic coupling within the {Cu2(CO2)4} paddlewheels in the latter two complexes, with g = 2.30(2) and J = −352(3) cm−1 for 3 and g = 2.35(2) and J = −352(5) cm−1 for 4. Significant structural contrasts are evident when compared to previously reported divalent copper/4,4′-bipyridine coordination polymers with unsubstituted or 2-methyl substituted glutarate ligands.  相似文献   

11.
Six transition-metal complexes, {[Co(4,4′-bipy)(H2O)4](Hbs)2 · 3H2O}n (1), [Mn(4,4′-bipy)2(H2O)4](Hbs)2 · 2H2O (2), {[Mn(HCOO)(H2O)2(4,4′-bipy)]2[Mn(4,4′-bipy)(Hssal)2(H2O)2]}n (3), [Cd(4,4′-bipy)2(H2O)4](Hbs)2 · 2H2O (4), {[Cd3(CH3COO)4(4,4′-bipy)4](Hbs)2 · 10H2O}n (5), and {[Cd(HCOO)(H2O)2(4,4′-bipy)]2[Cd(4,4′-bipy)(Hssal)2(H2O)2]}n (6), have been synthesized by hydrothermal or reflux synthetic method and characterized by single-crystal X-ray diffraction, IR, elemental analysis, thermogravimetric analysis and fluorescence analysis, where Hssal2− is doubly deprotonated 5-sulfosalicylate, Hbs is 4-hydroxybenzenesulfonate and 4,4′-bipy is 4,4′-bipyridine. The structural analyses showed that all of the six complexes are cation-anion species containing in situ synthesized ligands, Hbs or HCOO, and the former arises from the decarboxylation of 5-sulfosalicylic acid under the hydrothermal conditions. The formate anions derived from the hydrolysis of DMF. A series of supramolecular compounds show that the structural diversity is strongly associated with their properties.  相似文献   

12.
Oxalate- or 4,4′-bipyridine-bridged dimeric copper(II) complexes, [Cu2L2(μ-ox)] (1) and [Cu2L2(μ-bipy)](BF4)2 (2) [where ox = oxalate, bipy = 4,4′-bipyridine, HL = N-(1H-pyrrol-2-ylmethylene)-2-pyridineethanamine, L = HL−H+], have been synthesised and characterised by elemental analysis, IR, UV-Vis and single crystal X-ray diffraction. Crystal structure determinations carried out on 1 and 2 reveal that 1 is an oxalate-bridged centrosymmetrical square pyramidal dimeric copper(II) complex while 2 is a 4,4′-bipyridine-bridged non-centrosymmetric square planar dinuclear copper(II) complex. Comparison of the optimised geometries with the corresponding crystal structures suggests that the B3LYP/LANL2DZ level can reproduce the structures of 1 and 2 on the whole. The electronic spectra of 1 and 2 predicted by B3LYP/LANL2DZ method show some blue shifts compared with their experimental data. Thermal analysis carried out on 1 shows that there is only one exothermal peak at about 260 °C and the residue is presumably Cu2O4N6.  相似文献   

13.
One-dimensional {[Cu2(dppa)2(4,4′-bipy)(CH3CN)2](BF4)2 · 2CH3CN}n (1), two-dimensional {[Cu2(dppa)(4,4′-bipy)2(CH3CN)2](BF4)2 · 4CH2Cl2 · 4H2O}n (2) and three-dimensional {[Cu2(dppa)(4,4′-bipy)3](BF4)2 · 2CH2Cl2 · 3CH3CN · 3H2O}n (3) polymeric complexes have been prepared by self-assembly of [Cu(MeCN)4]BF4, Ph2PCCPPh2 (dppa) and 4,4′-bipyridine (4,4′-bipy) in a 2:2:1, 1:1:1 and 2:2:3 molar ratio, respectively. The structures of 1-3, determined by an X-ray diffraction study, reveal a linear spring-like architecture for 1, a planar honeycomb grid for 2 and an interlocked adamantoid network for 3.  相似文献   

14.
To further investigate the solvent effect on the structures of coordination polymers, a series of polymeric CuII complexes have been synthesized and characterized by single-crystal diffraction through combining of 2,3,5,6-tetrachloro-1,4-benzenedicarboxylic acid (H2BDC-Cl4) with CuII perchlorate. The products including {[Cu(BDC-Cl4)(py)3] · H2O}n (py = pyridine) (1), {[Cu(BDC-Cl4)(dioxane)(H2O)2] · dioxane}n (2), and {[Cu2(BDC-Cl4)2(DMF)4] · 2G}n (G = MeOH in 3 and G = EtOH in 4) have been obtained in different mixed solvents systems. With the change of the solvent system from pyridine/H2O (1:1) into dioxane/H2O (1:1), the infinite 1-D CuII-BDC-Cl4 chain motif in 1 is tuned into the 2-D (4,4) layered structure in 2 with the coordination of dioxanes to copper atoms. When the solvent system is changed into DMF/MeOH (1:1), then into DMF/EtOH (1:1), similar 1-D CuII-BDC-Cl4 double chains are afforded in 3 and 4 with different solvents inclusion. Moreover, the judicious choice of binding-guests leads to numerous coordination geometries of CuII centers and final dissimilar supramolecular lattices of 1-4 from 1-D to 3-D via robust hydrogen-bonding interactions. The spectroscopic, thermal, and fluorescent properties of 1-4 have also been investigated.  相似文献   

15.
A new HgII coordination polymer with 4,4′-bipyridine and acetate anions, [Hg(μ-4,4′-bipy)(μ-AcO)(AcO)]n · n/2H2O (1), has been synthesized, characterized by elemental analysis, IR-, 1H NMR-, 13C NMR spectroscopy and its structure determined by single-crystal X-ray diffraction. The thermal stability of compound 1 was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The structural studies of compound 1 show that the structure may be considered as a coordination polymer of mercury(II) consisting of linear double chains formed by a bridging 4,4′-bipy ligand and by connecting acetate-bridged centrosymmetric {Hg2(OAc)2}2+ nodes. Solid-state luminescent spectra of the ligand 4,4′-bipyridine and compound 1 indicate a fluorescent broad emission band with the maximum intensity at ca 468.2 and 446.4 nm upon excitation at 295 nm, respectively. The stability of porous network after removal of guest water molecules is not confirmed by X-ray powder diffraction.  相似文献   

16.
The coordination chemistry of a flexible poly(triazolyl)alkane derivative, fluconazole (HFlu), with a series of transition metal ions and dicyanamide (dca) anionic co-ligand has been explored to afford six new metal-organic coordination polymers. Complexes [M(HFlu)2(dca)2]n (M = MnII for 1, FeII for 2, CoII for 3, ZnII for 5, and CdII for 6) have the isostructural 1-D double-chain array via bridging fluconazole, whereas [Cu3(Flu)2(dca)4(CH3OH)2]n (4) shows an unusual 2-D layered metal-organic framework with dimeric CuII subunits. Notably, both types of coordination patterns are extended into distinct 3-D supramolecular networks via hydrogen-bonding interactions. This result indicates that the choice of metal ion has a significant effect on these polymeric structures as well as the binding modes of the ligands, which is discussed in detail. The ZnII and CdII complexes 5 and 6 display similar fluorescent emissions at 260 nm in the solid state, which essentially are intraligand transitions.  相似文献   

17.
Using the tetracyanometalate precursor [Fe(4,4′-dmbipy)(CN)4]- (4,4′-dmbipy = 4,4′-dimethyl-2,2′-bipyridine) as the building block, two new cyano-bridged one-dimensional heterobimetallic coordination polymers, [M(CH3OH)2Fe2(4,4′-dmbipy)2(CN)8]n (M = Cu, 1; Mn, 2), have been synthesized and structurally characterized. X-ray crystallography reveals that complexes 1 and 2 consist of heterobimetallic chains of squares, and the central MII ion is six-coordinated as an elongated distorted octahedral geometry. Magnetic studies show ferromagnetic coupling between FeIII and CuII ions in complex 1. Complex 2 exhibits ferrimagnetic behavior caused by the noncompensation of the local interacting spins (SMn = 5/2 and SFe = 1/2), which interact antiferromagnetically through bridging cyanide groups. magpack program has been employed to investigate the magnetic nature of squares chain structure.  相似文献   

18.
A new Wells-Dawson polyoxometalate-based compound, [CuII(2,2′-bipy)2(H2O)]3[CuI6(pz)6(P2W18O62)2] (2,2′-bipy = 2,2′-bipyridine, pz = pyrizine) (1), has been hydrothermally synthesized and characterized by routine physical methods. Compound 1 exhibits a [CuII(2,2′-bipy)2(H2O)]2+ complex-templated 3D (3,4)-connected framework with the topology of (63)(6284), which is built up by the cross-linking of porous P2W18-Cu layers and CuI-pz chains with Cu2 atoms as intersections. The transition-metal complex cation [CuII(2,2′-bipy)2(H2O)]2+ acts not only as a template locating in the voids of inorganic layers, but also as a charge-balance complex to make the 3D structure more steady. The electrochemistry property of compound 1 has also been discussed.  相似文献   

19.
By the reactions of Cu(AcO)2·H2O and Cu(HCOO)2·4H2O with 4,4′-dimethyl-2,2′-bipyridine and 5,5′-dimethyl-2,2′-bipyridine the compounds [Cu(AcO)2(4,4′-Me2-2,2′-bipy)]·1/2H2O (1), [Cu(AcO)2(5,5′-Me2-2,2′-bipy)(H2O)] (2), [Cu(HCOO)(μ-HCOO)(4,4′-Me2-2,2′-bipy)]n·nH2O (3) and [Cu(HCOO)(μ-HCOO)(5,5′-Me2-2,2′-bipy)]n·2nH2O (4) were obtained. In the acetate complexes, 1 and 2, the geometry around copper is distorted octahedral and square pyramidal, respectively. Dimeric units of different geometry are formed in both cases through hydrogen bonds in which non-coordinated (in 1) and coordinated (in 2) water molecules are involved. The structures of 3 and 4 consist of polymeric monodimensional chains of square pyramidal copper units linked by axial-equatorial syn-anti (3) or anti-anti (4) bridging formate groups. Water molecules form hydrogen bonds with formate groups of the same chain in compound 3. In compound 4 the water molecules link the polymeric contiguous chains of complex through hydrogen bonds with oxygen atoms of formate groups and they are also linked between them, forming monodimensional water chains which run parallel to the complex chains. Sheets parallel to the ac plane are formed by alternating chains of water and polymeric complex. Magnetic properties and EPR spectra for these compounds have been studied.  相似文献   

20.
Three new o-thioetherphenol ligands have been synthesized: 1,2-bis(3,5-di-tert-butyl-2-hydroxyphenylsulfanyl)ethane (H2bse), 1,2-bis(3,5-di-tert-butyl-2-hydroxyphenylsulfanyl)benzene (H2bsb), and 4,6-di-tert-butyl-2-phenylsulfanylphenol (Hpsp). Their complexes with copper(II) were prepared and investigated by UV-Vis-, EPR-spectroscopy; their electro- and magnetochemistry have also been studied: [CuII(psp)2] (1), [CuII2(bse)2] (2), [CuII2(bsb)2] (3), [CuII(bsb)(py)2] (4). The crystal structures of the ligands H2bse, H2bsb, Hpsp and of the complexes 1, 2, 3, 4 have been determined by X-ray crystallography.  相似文献   

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