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1.
Three cadmium(II) coordination polymers, [CdBr2(L1)] n (1), [CdI2(L2)] n (2), and Cd2Br4(L3)2 (3), where L1?=?1,3-bis(5,6-dimethylbenzimidazole)propane, L2?=?1,4-bis(5,6-dimethylbenzimidazole)butane, and L3?=?1,6-bis(5,6-dimethylbenzimidazole)hexane, have been synthesized by hydrothermal methods and characterized by elemental analyses, IR spectra, TGA, PXRD, and X-ray crystallographic diffraction. Complex 1 contains a 1-D helical chain in which CdBr2 units are linked by L1. For 2, each CdI2 is connected by two different conformations of L2 to form a 1-D zigzag chain. For 3, each CdBr2 is linked by L3 bridges to afford a binuclear structure. These results indicate that the spacer length of the ligands play important roles in assembly of Cd(II) coordination polymers. Thermogravimetric analyses and solid-state luminescent properties of the complexes have also been investigated.  相似文献   

2.
Two Cd(II) coordination polymers have been synthesized with derivatives of pyrazine-1,4-dioxide and thiocyanate anion as bridging ligands and structurally determined by X-ray crystallography. Complex 1, [Cd(μ1,3-SCN?)21,6-L1)] n (L1?=?2,5-dimethylpyrazine-1,4-dioxide), belongs to the triclinic, space group P 1 with a?=?5.7627(18)?Å, b?=?7.182(2)?Å, c?=?7.509(2)?Å, α?=?74.042(3)°, β?=?84.766(4)°, γ?=?88.162(4)°; complex 2, [Cd21,3-SCN?)44-L2)] n (L2?=?2,3,5,6-tetramethylpyrazine-1,4-dioxide), crystallizes in a monoclinic system with space group C2/m with a?=?10.194(4)?Å, b?=?13.491(6)?Å, c?=?8.140(3)?Å, β?=?120.372(4)°. Complex 1 shows a two-dimensional sheet structure, and in a direction the Cd(II) ions were coordinated by μ1,3-SCN? forming the one-dimensional chain and the L1 bridging ligand made the chains connect in the c direction leading to formation of a two-dimensional sheet on the ac plane. For 2 the one-dimensional chains in the a axis were constructed by coordination of μ1,3-SCN? bridging ligands with the Cd(II) ions, and in b and c directions the chains were joined by L2 bridging ligands leading to a three-dimensional structure. In 2 L2 displays a μ4-bridging coordination mode. Both complexes exhibit strong fluorescence emission.  相似文献   

3.
Two new cadmium(II) complexes [Cd1.5(L)Cl2(H2O)]2 n (1) and [CdL2] n (2) with a multidentate N-donor building block 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole (HL) have been prepared and characterized by elemental analysis, infra-red spectra, powder X-ray diffraction (XRD), and single-crystal XRD. 1 is a 2-D layered coordination polymer constructed from linkage of [Cd3(μ-Cl)4] trinuclear units with HL spacers, while 2 shows a 2-D layer structure. 3-D supramolecular architectures are further assembled in 1 and 2 via hydrogen-bonding contacts. Both 1 and 2 are thermally stable to 450?°C, and 2 showed strong fluorescent emission bands.  相似文献   

4.
Four dinuclear cadmium(II) complexes, [Cd2(L1)(μ2-Cl)Cl2] (1), [Cd2(L2)(μ2-Cl)Cl2] (2), [Cd2(L3)(μ2-Cl)Cl2] (3), and [Cd2(L4)3ClO4] (4), where HL1 = 4-methyl-2,6-bis(1-(2-piperidinoethyl)iminomethyl)-phenol, HL2 = 4-methyl-2,6-bis(1-(2-pyrrolidinoethyl)iminomethyl)-phenol, HL3 = 4-methyl-2,6-bis(1-(2-morpholinoethyl)iminomethyl)-phenol and HL4 = 4-methyl-2,6-bis(cyclohexylmethyl)iminomethyl)-phenol, were synthesized. They were characterized by elemental analysis, FT-IR, UV–Vis, fluorescence and electronspray ionization mass spectroscopy. Complexes 1 and 4 were also characterized by single crystal X-ray analysis. The cadmiums atoms in 1 are linked by μ2-chloride in a distorted square pyramidal geometry, whereas cadmium atom in 4 is in a distorted octahedral environment. The complexes show emission bands around 500 nm with excitation at 395 nm.  相似文献   

5.
Two novel Cd(II)-citrate complexes were obtained with different metal/ligand ratios through hydrothermal method. Their structures were determined by single-crystal X-ray diffraction analysis. Although their topological structures are both 2-D layer network assemblies, both central Cd(II) ions and Hcit3− ligands display completely different coordination modes. In polymeric complex 1, Hcit3− serves as a μ10-bridged and central Cd(II) ions adopt 6- and 8-coordinated configurations. In contrast, a μ9-bridged and 6- and 7-coordinated environments between Cd(II) and Hcit3− are established in the polymeric complex 2. Two Complexes remain stable up to approximately 300 °C. The complex 1 exhibits strong fluorescent emission band at 450 nm (λ=346 nm) as well as complex 2 exhibits strong fluorescent emission band at 430 (λ=346 nm).  相似文献   

6.
Five structually distinct coordination polymers [Cd(bte)3](NO3)2 n (1), [Cd(bte)2(H2O)2](NO3)2 n (2), [Cd(bte)(NO2)2] n (3), [Cd(bte)2(H2O)2](H2O)2(ClO4)2 n (4) and [Cd(bte)(NCS)2]n (5) (bte = 1,2-bis(1,2,4-triazol-1-yl)ethane) have been synthesized and characterized. The structures of 1, 2, 3, 4 and 5 consist of a double interpenetrating three-dimensional -poloniumn cubic network, a two-dimensional (4,4) network, a two-dimensional rhombic network, a one-dimensional double chain containing 18-membered [Cd2(bte)2] rings and a two-dimensional rhombic network containing eight-membered [Cd2(SCN)2] rings, respectively.  相似文献   

7.
Five iron(II) coordination polymers, {[Fe(bte)2(NCS)2][Fe(bte)(H2O)2(NCS)2]}n (1), [Fe(bime)(NCS)2]n (2), [Fe(bime)(dca)2]n (3), [Fe(bime)2(N3)2]n (4) and [Fe(btb)2(NCS)2]n (5), were synthesized using the flexible ligands 1,2-bis(1,2,4-triazol-1-yl)ethane (bte), 1,2-bis(imidazol-1-yl)ethane (bime) and 1,4-bis(1,2,4-triazol-1-yl)butane (btb), together with NCS, dicyanamide (dca) and N3. The compound 1 contains two kinds of motifs (double chain and single chain) and forms a three-dimensional hydrogen bonded network; 2 and 3 contain one-dimensional triple chains; and 4 and 5 form two-dimensional (4, 4) networks. The coordination anions (NCS, dca and N3) and the structural characteristics of the ligands (bte, bime and btb) play an important role in the assembly of the topologies. Magnetic studies reveal that 1-5 remain in the high-spin state over the whole temperature range 2-300 K and no detectable spin-crossover is observed.  相似文献   

8.
A two-dimensional coordination complex [Cd(μ1,3-SCN)22-mpdo)] n (mpdo?=?4-methylpyridine N-oxide) has been synthesized and structurally determined by X-ray crystallography. The complex crystallizes in the triclinic space group of with a?=?8.2589(14)?Å, b?=?8.5409(14)?Å, c?=?9.7947(16)?Å, α?=?70.022(2)°, β?=?74.338(2)°, γ?=?71.530(2)°. Each Cd(II) is coordinated by four μ1,3-SCN? forming a zigzag chain and then two μ2-mpdo monodentate ligands coordinate to two adjacent Cd(II) ions leading to a two-dimensional sheet structure along the ab plane, and in the c direction the sheets stack parallel through π–π interactions and giving a three-dimensional structure. The complex exhibits a strong fluorescent emission spectrum in the solid state.  相似文献   

9.
One-pot reactions of cadmium(II) perchlorate/nitrate, Schiff bases (pbap/pfap) and pseudohalides (sodium azide/ammonium thiocyanate) in a 2:1:4 molar ratio in MeOH–MeCN solvent mixtures at room temperature result in a dinuclear compound [Cd2(pbap)(OH2)2(N3)4] (1) [pbap = N-(1-pyridin-2-ylbenzylidene)-N-[2-(4-{2-[(1-pyridin-2-ylbenzylidene)amino]ethyl}piperazin-1-yl)ethyl]amine] and a polymeric compound [Cd2(pfap)(μ1,3-NCS)(μ1,3-SCN)(NCS)2]n (2) [pfap = N-(1-pyridin-2-ylformylidene)-N-[2-(4-{2-[(1-pyridin-2ylformylidene)amino]ethyl}piperazin-1-yl)ethyl]-amine]. X-ray crystal structural analyses reveal a bis(tridentate) congregation behaviour of the hexadentate blocker (pbap/pfap) encapsulating two metal centers. Each cadmium(II) center in 1 and 2 is in a distorted octahedral geometry with CdN5O and CdN5S chromophores, respectively. In 1, the dinuclear units participate in intermolecular O–H?N hydrogen bonding between bound water O atoms and terminal azide N atoms, in combination with C–H?π interactions, resulting in a 3D supramolecular network with an intramolecular Cd?Cd distance of 6.473(2) Å. In the crystal lattice, the covalent 1D chain of 2 is further engaged in face-to-face π?π interactions from two terminal pyridine rings, which stabilizes the chain with an intradimer Cd?Cd separation of 6.640(5) Å. Both the complexes display intraligand 1(π–π) fluorescence and intraligand 3(π–π) phosphorescence in glassy solutions.  相似文献   

10.
The novel mixed ligand complexes [M(bpy)(phen-dione)](PF6)2 (M?=?Zn(II), Cd(II) and Hg(II), bpy?=?2,2-bipyridine and phen-dione?=?1,10-phenanthroline-5,6-dione) have been synthesized and characterized by elemental analysis, IR, 1H NMR and electronic absorption spectroscopies. The ν(C=O) of coordinated phen-dione in these complexes are very similar to the free phen-dione ligand showing that phen-dione is not coordinated to metal ion from its C=O sites. Absorption spectra of the complexes show two absorption bands for intraligand transitions. These absorption bands show dependence to the dielectric constant of solvent. These complexes exhibit an intensive fluorescence band around 535?nm in DMF when the excitation wavelength is 260?nm at room temperature. The fluorescence intensity of these complexes is larger than that of the free ligand.  相似文献   

11.
Reactions of Cd(NO3)2?·?4H2O with NH4SCN, ppz (ppz?=?piperazine) and bpa (bpa?=?bis(4-pyridyl)ethane) in CH3OH afforded the cavity-containing rectangular grids {Cd(SCN)2(ppz)} n (1) and {Cd(NCS)2(bpa)} n (2). The ppz ligand in 1 is coordinated to the metal through both nitrogen atoms to form the 1-D zig-zag chain structure and distorted {CdN4S2} octahedral coordination geometry at each Cd center is completed by pairs of bidentate thiocyanato ligands. Complex 2 has the 2-D arrangement constructed through 1-D double μ(N,S) end-to-end bridging thiocyanato groups bridging Cd(II) chains interconnected through disordered bpa ligands.  相似文献   

12.
Reactions of fresh M(OH)2 (M = Zn2+, Cd2+) precipitate and (RS)-2-methylglutaric acid (H2MGL), 2,2′-bipyridine (bipy), or 1,10-phenanthroline (phen) in aqueous solution at 50°C afforded four new metal–organic complexes [Zn2(bipy)2(H2O)2(MGL)2] (1), [Zn2(phen)2(H2O)(MGL)2] (2), [Cd(bipy)(H2O)(MGL)] · 3H2O (3), and [Cd(phen)(H2O)(MGL)] · 2H2O (4), which were characterized by single crystal X-ray diffraction, IR spectra, TG/DTA analysis as well as fluorescence spectra. In 1, the [Zn(bipy)(H2O)]2+ moieties are linked by R- and S-2-methylglutarate anions to build up the centrosymmetric dinuclear [Zn2(bipy)2(H2O)2(MGL)2] molecules. In 2, the 1-D ribbon-like chains [Zn2(phen)2(H2O)(MGL)2] n can be visualized as from centrosymmetric dinuclear [Zn2(phen)2(H2O)2(MGL)2] units sharing common aqua ligands. Both 3 and 4 exhibit 1-D chains resulting from [Cd(bipy)(H2O)]2+ and [Cd(phen)(H2O)]2+, respectively, bridged alternately by R- and S-2-methylglutarate anions in bis-chelating fashion. The intermolecular and interchain π···π stacking interactions form supramolecular assemblies in 1 and 1-D chains in 24 into 2-D layers. The hydrogen bonded lattice H2O molecules are sandwiched between 2-D layers in 3 and 4. Fluorescence spectra of 14 exhibit LLCT π → π* transitions.  相似文献   

13.
Three novel coordination polymers [Cd3(L)2(μ-Br)(μ-Cl)Br3Cl] (1), [Cd3(L)2(μ-Cl)2Cl4] (2) and [Cd(L)Cl]2[CdCl4]·H2O (3) were obtained by reactions of an imidazole-containing tripodal ligand N1-(2-aminoethyl)-N1-(2-imidazolethyl)-ethane-1,2-diamine (L) with Cd(II) salts. Their structures were determined by X-ray crystallography. Crystal data for 1, monoclinic system, P21/c, a=7.752(4) Å, b=31.70(2) Å, c=14.012(7) Å, β=109.439(7)°, V=3247(3) Å3, Z=4. 2, monoclinic system, P21/c, a=7.6564(15) Å, b=31.433(6) Å, c=13.925(3) Å, β=109.89(3)°, V=3151.1(11) Å3, Z=4. 3, orthorhombic system, Pbcn, a=22.950(2) Å, b=8.435(7) Å, c=17.360(2) Å, V=3360.3(51) Å3, Z=4. Complexes 1 and 2 have similar one-dimensional (1D) branched-chain structure while complex 3 features a 1D zigzag cationic chain with [CdCl4]2− serving as counter anion. The photoluminescent measurements reveal that all the complexes exhibit blue fluorescence at room temperature in the solid state.  相似文献   

14.
Two novel Cd(II) coordination polymers [Cd4(C6H4O2N)8(H2O)4]n (1) and [Cd2(C10H2O8)(H2O)6]n (2) have been synthesized under hydrothermal condition and structurally characterized. Crystal data: (1), orthorhombic, Pbca, a=11.4494(19) Å, b=12.0969(6) Å, c=17.4073(8) Å, V=2410.9(4) Å3, Z=8, D calc=2.064 g·cm−3; (2), triclinic, P , a=5.5962(7) Å, b=7.7758(6) Å, c=9.6975(10) Å, α=111.981(5)°, β=101.649(6)°, γ=98.240(5)°, V=371.95(7) Å3, Z=2, D calc=2.603 g·cm−3. Complex (1) possesses three-dimensional infinite structure, while complex (2) adopts two-dimensional layers and the layers are connected by the many types of hydrogen bonds, forming three-dimensional network. Study results of the photophysical properties show that both complexes can emit strong blue fluorescence and complex (1) also emits phosphorescence (λ pl max=511 nm, τ=32 ms) in the solid state at room temperature.  相似文献   

15.
An unexpected dinuclear Cu(II) complex, [Cu2(L2)2] (H2L2?=?3-methoxysalicylaldehyde O-(2-hydroxyethyl)oxime), has been synthesized via complexation of Cu(II) acetate monohydrate with H4L1. Catalysis by Cu(II) results in unexpected cleavage of two N–O bonds in H4L1, giving a dialkoxo-bridged dinuclear Cu(II) complex possessing a Cu–O–Cu–O four-membered ring core instead of the usual bis(salen)-type tetraoxime Cu3–N4O4 complex. Every complex links six other molecules into an infinite-layered supramolecular structure via 12 intermolecular C–H?···?O hydrogen bonds. Furthermore, Cu(II) complex exhibits purple emission with maximum emission wavelength λmax?=?417?nm when excited with 312?nm.  相似文献   

16.
Two Co(II) coordination polymers, [CoL(npa)]·2H2O (1) and [CoL(Hnpa)2] (2) (L = 1,4-bis(5,6-dimethylbenzimidazole-1-yl)benzene, H2npa = 5-nitroisophthalic acid), have been synthesized in different solvent systems and characterized by Infrared (IR) spectroscopy, elemental analysis, and powder and single crystal X-ray diffraction. Compound 1 was synthesized under solvothermal conditions with DMF as solvent and had a pair of L ligands adopting a μ2-bridging mode and connecting two Co2+ cations to generate a 26-membered Co2L2 loop. The npa2? link adjacent Co2L2 loops via a bis(monodentate) bridging mode to create a 1-D channel-like chain structure. Compound 2 was obtained under hydrothermal conditions, and the carboxylate of the monodeprotonated Hnpa? adopt a μ1-η0?:?η1 coordination to connect adjacent Co2+ cations into a 2-D polymeric layer. The μ2-bridging L ligands connect adjacent 2-D [Co(Hnpa)]n polymeric layers into a 3-D NaCl-like framework. The Co2+ cations and the L ligands in compounds 1 and 2 exhibit different coordination geometries and conformations. Effects of solvents on the construction of Co(II) coordination polymers were investigated. In addition, the electrochemical behavior of carbon paste electrodes containing 1 and 2 and the thermal stabilities of 1 and 2 were investigated.  相似文献   

17.
Two polymeric complexes, [Cu2(btec)(phen)2]n·(H2O)n (1) and [Cd4(btec)2(phen)4(H2O)4]n (2) (H4btec=1,2,4,5-benzenetetracarboxylic acid; PHEN=1,10-phenanthroline), were synthesized by solvothermal reactions at 140 °C. Both complex 1 and 2 possess infinite double-chain structures, in which each Cu(II) center has a tetrahedral configuration and the Cd(II) centers adopt triangular prismatic and square-based pyramidal configurations simultaneously. The inter-chain face to face π–π interactions among the aromatic rings of phen and the hydrogen bond interactions between aqua molecules and carboxyl O atoms result in 3-D networks in the two complexes. The ESR spectra study of complex 1 shows that there is negligibly small long-range super-exchange interactions between the Cu(II) atoms via benzenecarboxylate bridging.  相似文献   

18.
Two complexes, [Cd(ip–OH)(H2biim)(H2O)][Cd(ip–OH)(H2biim)(H2O)3]·8(H2O) (1) and [Cd(Himdc)(H2biim)] n (2) (H2ip–OH?=?5-hydroxylisophthalic acid, H2biim?=?2,2’-biimidazolate, H3imdc?=?4,5-imidazoledicarboxylic acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. 1 is a 3-D supramolecular network constructed by 0-D and 1-D motifs through hydrogen bonds and π?π interactions. Complex 2 is a 1-D zigzag polymeric coordination chain and the chains are connected to form a 3-D supramolecular network by hydrogen bonds. The complexes were characterized by elemental and thermogravimetric analyses. Fluorescence was also investigated.  相似文献   

19.
Coordination polymers, {[Cd(2-mBIM)3](ClO4)2} n (1) and [Cd(BIM)2(NO3)2] n (2), have been prepared from the reaction of bis(2-methylimidazol-1-yl)methane(2-mBIM) with Cd(ClO4)2 and bis(imidazol-1-yl)methane (BIM) with Cd(NO3)2 in ethanol and water, respectively. Their structures were characterized by single crystal X-ray diffraction and IR spectroscopy. Compound 1 crystallizes in the rhombohedral space group R-3c with a = b = 12.3617(5) Å, c = 38.896(3) Å, γ = 120°, V = 5147.5(5) Å3, z = 6. The CdII occupies a crystallographic inversion center and is coordinated by six N atoms from six distinct 2-mBIM ligands to form a slightly distorted octahedral geometry. Each 2-mBIM is coordinated to two CdII cations, linking alternatively four CdII cations, resulting in a 32-membered M4L4 macrometallacycle. Compound 2 crystallizes in the monoclinic space group C2/m with a = 14.400(3) Å, b = 9.3894(18) Å, c = 8.6926(17) Å, β = 123.499(2)°, V = 980.1(3) Å3, z = 2. The Cd coordinates to four nitrogen atoms from four different BIM and two nitrates to form a slightly distorted octahedral geometry. The BIM ligands bridge to form a 1-D infinite double-bridged chain structure with 16-membered M2L2 macrometallacyclic structural units.  相似文献   

20.
Yanhong Zhou  Li Guan  Hong Zhang   《Polyhedron》2009,28(13):2667-2672
Four new coordination polymers of cobalt(II) and nickel(II) with functionalized dicarboxylate ligands, namely, [CoIIL1(2,2′-bpy)(H2O)] (1), [NiIIL1(2,2′-bpy)(H2O)]·H2O (2), [CoII2(L2)2(2,2′-bpy)2(H2O)] (3) and [NiII2(L2)2(2,2′-bpy)2(H2O)] (4), where H2L1 = 2,5-dibenzoylterephthalic acid, H2L2 = 4,6-bis(4-methylbenzoyl)isophthalic acid and 2,2′-bpy = 2,2′-bipyridine, were synthesized and characterized by elemental analysis, IR spectra and thermogravimetric analysis. Complex 1 exhibits a zigzag chain with a C–Hπ interaction between the phenyl ring proton and the phenyl ring of an adjacent chains to form a 2D supramolecular sheet. Complex 2 contains two helical chains which extend into 2D via a C–Hπ interaction between the pyridine ring proton and the pyridine ring. Complexes 3 and 4 are isomorphous with helical chains that extend in the same direction and further link to one another by supramolecular forces into a 2D structure. Moreover, magnetic and luminescence properties have been investigated for 1 and 2, respectively.  相似文献   

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