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1.
Three Cd (II)-M (II) hetero-nuclear coordination polymers, [FeCd2(Hcit)2(H2O)2]n (1), [CoCd2(BTC)2(H2O)4]n (2) and [Cd3(Hcit)2(H2O)2]n (3) (H4cit = citric acid, H3BTC = 1,3,5-benzenetricarboxyl acid), were synthesized through hydrothermal method. They were characterized through elemental analysis, IR spectra, UV-Vis absorption spectra, X-ray powder diffraction, single-crystal X-ray diffraction and surface photovoltage spectra (SPS). Structural analysis indicates that 1 and 3 possess 2D structures, which are further connected to 3D structures by hydrogen bonds. 2 is a 3D Cd-Co coordination polymer bridged by BTC3− groups. The SPS show that 1 and 2 present positive photovoltage response in 300-550 nm, but the photovoltage response of 3 appears in 300-400 nm. It is indicated that the limits of SPS response bands of polymers 1 and 2 are wider than those of 3 because of introduction of the other transition metal ions. There is a good corresponding relationship between SPS and UV-Vis absorption spectra.  相似文献   

2.
Three novel coordination complexes [Mn(tpha)(phen)]n (1); [Mn(na)2(H2O)2]n (2); {[Mn(phen)2(OH)Cl] · Cl · (OH) · (C9H11NO2) · 2H2O} (3) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction (H2tpha = terephthalic acid, Hna = nicotinic acid, phen = 1,10-phenanthroline). The tpha groups in complex 1 bridge the Mn(II) ions to an infinite 3D framework. Complex 2 exhibits a 2D network structure in which the Mn(II) ions are linked by nicotinic groups. Complex 3 is connected to a 2D coordination supramolecule by hydrogen bonds. The results of surface photovoltage spectra (SPS) of complexes 1-3 indicate that they all exhibit positive surface photovoltage (SPV) responses in the range of 300-800 nm. However, the intensity, position and numbers of SPV responses are obviously different. The distinctions can be mainly attributed to their structures, valences and coordination environments of the manganese ions in the three complexes. Moreover the external field induced surface photovoltage spectra (FISPS) of the three complexes have been measured.  相似文献   

3.
The coordination polymer named {[Co(H2O)4(BPP)][Co(dipic)2]·H2O}n (dipic = 2,6-pyridinedicarboxylate and BPP = 1,3-bis(4-pyridyl)propane) has been synthesized by the diffusion method and characterized by thermal analysis, vibrational spectroscopy and single crystal X-ray diffraction analysis. The compound is formed by an one-dimensional polymeric cationic chain, in which the BPP ligands connect the Co2 sites, and an anionic moiety formed by Co1 center and two dipic2− anions. Both crystallographic independent metal sites adopt a distorted octahedral geometry. Co2 center is coordinated by two nitrogen atoms from BPP ligands and four oxygen atoms from aqua ligands, while Co1 center is coordinated by two nitrogen atoms and four oxygen atoms from two dipic2− anions. The cationic and anionic moieties are connected through hydrogen bonding interactions leading to a 3D supramolecular array.  相似文献   

4.
One new binuclear Co(II) complex of N,N,N',N'-tetrakis(2-benzimidazolylmethyl)-2-hydroxyl-1,3-diaminopropane (HL), [Co(2)L(mu(2)-Cl)](ClO(4))(2) x 3CH(3)CN x C(2)H(5)OC(2)H(5) (1), has been synthesized and its crystal structure and magnetic properties are shown. In 1, each Co(II) atom has a distorted trigonal bipyramidal geometry with a N(3)OCl donor set. The central two Co(II) atoms are bridged by one alkoxo-O atom and one Cl atom with the Co1-Co2 separation of 3.239 A. Susceptibility data of 1 indicate strong intramolecular antiferromagnetic coupling of the high-spin Co(II) atoms. In this paper, the interaction with calf thymus DNA was investigated by UV absorption and fluorescent spectroscopy. Results show the complex binds to ct-DNA with a intercalative mode. The interaction between complex 1 and pBR322 DNA has also been investigated by submarine gel electrophoresis, noticeably, the complex exhibits effective DNA cleavage activity in the absence of any external agents.  相似文献   

5.
A novel one-dimensional heterometallic complex, {Cd2[NiL]2(SCN)4(H2O)}n (1), has been synthesized and characterized by single-crystal X-ray analysis, where L is dianion of 2,3-dioxo-5,6,13,14-dibenzo-9,10-cyclohexyl-7,12-bis(ethoxycarbonyl)-1,4,8,11-tetraazacyclotetradeca-7,11-diene. The most striking feature of 1 is that in the structure there is one type of S-S bond (1.823(13) Å) formed by two thiocyanate groups which has not been reported to our knowledge. The DNA cleavage activity of 1 in the presence of H2O2 was compared with those of nickel(II) ion, cadmium(II) ion and corresponding mononuclear precursor NiL (2). The DNA cleavage kinetics was studied and the corresponding activation parameters of 1 were obtained.  相似文献   

6.
Two new one-dimensional copper(II) polymers with formulae of [Cu2(H2O)2(dmapox)(ipa)2]n (1) and [Cu2(H2O)2(dmapox)(tpa)2]n (2), where dmapox, ipa and tpa stand for the dianion of N,N′-bis[3-(dimethylamino)propyl]oxamide, isophthalic acid and terephthalic acid respectively, have been synthesized and characterized by elemental analysis, conductivity measurement, IR and electronic spectral studies. The crystal structures of the two complexes have been determined by X-ray single-crystal diffraction. The structures of 1 and 2 consist of one-dimensional copper(II) coordination polymeric chain constructed both by the bis-tridentate trans-dmapox and bis-monodentate phenyldicarboxylate bridging ligands. In the two complexes, the environment around the copper(II) atoms can be described as distorted square-pyramid and the Cu···Cu separations through μ-trans-dmapox and phenyldicarboxylato bridging ligands are 5.245(5) Å and 8.212(3) Å for 1, 5.237(8) Å and 11.171(1) Å for 2, respectively. The binding properties of the two copper(II) polymers with herring sperm DNA (HS-DNA) have been investigated by using absorption and emission spectral and electrochemical techniques and viscometry. The results show that the two copper(II) complexes interact with the HS-DNA in the mode of intercalation with the intrinsic binding constants of 1.22(±0.2) × 104 M−1 and 1.45(±0.3) × 104 M−1 for 1 and 2, respectively.  相似文献   

7.
We have prepared and structurally characterized six-coordinate Fe(II), Co(II), and Ni(II) complexes of types [MII(HL1)2(H2O)2][ClO4]2 (M = Fe, 1; Co, 3; and Ni, 5) and [MII(HL2)3][ClO4]2 · MeCN (M = Fe, 2 and Co, 4) of bidentate pyridine amide ligands, N-(phenyl)-2-pyridinecarboxamide (HL1) and N-(4-methylphenyl)-2-pyridinecarboxamide (HL2). The metal centers in bis(ligand)-diaqua complexes 1, 3 and 5 are coordinated by two pyridyl N and two amide O atoms from two HL1 ligands and six-coordination is completed by coordination of two water molecules. The complexes are isomorphous and possess trans-octahedral geometry. The metal centers in isomorphous tris(ligand) complexes 2 and 4 are coordinated by three pyridyl N and three amide O atoms from three HL2 ligands. The relative dispositions of the pyridine N and amide O atoms reveal that the pseudo-octahedral geometry have the meridional stereochemistry. To the best of our knowledge, this work provides the first examples of structurally characterized six-coordinate iron(II) complexes in which the coordination is solely by neutral pyridine amide ligands providing pyridine N and amide O donor atoms, with or without water coordination. Careful analyses of structural parameters of 1-5 along with that reported in the literature [MII(HL1)2(H2O)2][ClO4]2 (M = Cu and Zn) and [CoIII(L2)3] have allowed us to arrive at a number of structural correlations/generalizations. The complexes are uniformly high-spin. Spectroscopic (IR and UV/Vis) and redox properties of the complexes have also been investigated.  相似文献   

8.
Nano-structures of two new Pb(II) coordination polymers, [Pb(DPAcO)2]n (1) and [Pb(MPAcO)2]n (2), HDPAcO = diphenyl acetic acid and HMPAcO = monophenyl acetic acid} were synthesized by a sonochemical method. The new nano-structures were characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. Compound 2 was structurally characterized by single crystal X-ray diffraction. The crystal structure of the compound 2 consists of one-dimensional polymeric units of [Pb(MPAcO)2] and shows the coordination number in the PbII ions is six. The thermal stability of compounds 1 and 2 were studied by thermal gravimetric and differential thermal analyses and shows that nanostructures of compounds 1-2 are somewhat less stable then their bulk materials. PbO nano-powders were obtained by calcinations of the nano-structures of compounds 1 and 2 at 400 °C.  相似文献   

9.
Reaction of pyridine-2,6-dicarboxylic acid (dipicH2) with ammonium ceric nitrate and Cu(II) salts yielded three heterometallic compounds all of which contain [Ce(dipic)3]2− linked to aquo-Cu(II) complex units. Part of the Ce(IV) gets reduced by solvent during the reaction leading to [(Ce(dipic)3Ce(H2O)8)2Cu(H2O)4][Ce(dipic)3]2·12H2O (1). Other lanthanide(III) ions could take the place of Ce(III) as demonstrated by the preparation of [(Ce(dipic)3La(H2O)8)2Cu(H2O)4][Ce(dipic)3]2·12H2O (4), which is isomorphous with compound 1. [Ce(dipic)3Cu(H2O)4]·8H2O (2) is a one-dimensional coordination polymer in which two types of aquo-Cu(II) complex units which differ in the orientation of the tetragonal axis alternate along the chain. The central Cu(H2O)22+ unit in the trinuclear anion of [Cu(H2O)6][Ce(dipic)3Cu(H2O)2Ce(dipic)3]·8H2O (3) is chelated by two carboxylate groups in trans positions in off-axis mode. In all the four complexes, the Cu(II) centres are magnetically isolated leading well-resolved EPR spectra in polycrystalline samples.  相似文献   

10.
A new succinato-bridged copper(II) complex, [{Cu(L)(H2O)2}(H2O)2]n (1) (L, succinate dianion) has been synthesized and characterized by single crystal X-ray diffraction analysis and low temperature magnetic study. The structure determination reveals that the complex 1 is a one-dimensional coordination chain of copper(II), bridged through the succinate dianion approximately along the crystallographic ac diagonal and extended to supramolecular 3D net work by H-bonding. The low temperature magnetic study reveals significant antiferromagnetic interactions between the copper centers corroborating the existence of H-bonding in 1.  相似文献   

11.
In this work we present the synthesis, structural and spectroscopic characterisation of a series of cobalt(II) and zinc(II) coordination compounds with benzimidazole (bz) and its 2-benzimidazole derivatives: 2-aminobenzimidazole (2ab), albendazole (abz) and tris(2-benzimidazolylmethyl)amine (ntb). The compounds were evaluated for their in vitro antimicrobial activity against Staphylococcus aureus, Micrococcus luteus, Salmonella typhi, Pseudomonas aeruginosa, Escherichia coli and Proteus vulgaris. Their cytotoxic activity was also evaluated using human cancer lines, HeLa, HCT-15 and SKLU-1. The halide tetrahedral compounds [Co(bz)2Br2] 3, [Zn(2ab)2Cl2] · 0.5H2O 11, [Co(abz)Cl2(H2O)] · 3H2O 14, [Co(abz)Br2(H2O)] 15, [Zn(abz)Cl2(H2O)] · 3H2O 17 and [Zn(abz)Br2(H2O)] · H2O 18 displayed similar minimal inhibition concentration (MIC) values against Micrococcus luteus and Escherichia coli, comparable to those of amoxicillin and chloramphenicol. Additionally, 11 showed a wide range of activity towards Gram(+) and Gram(−) microorganisms. The tetradentate ntb and its trigonal bipyramidal cobalt(II) and zinc(II) compounds were active, regardless of the anion present in the complex. Compound [Co(abz)Cl2(H2O)] · 3H2O 14 showed promising activity in HeLa cells, while [Co(ntb)Br]Br · H2O 21 inhibited Hela and HCT-15 cell lines.  相似文献   

12.
Two new Mn(II) coordination polymers with bis(5-tetrazolyl)methane (H2btm), [Mn(btm)(phen)(H2O)] · H2O (1) and [Mn(btm)(2,2′-bpy)] · 1.5H2O (2), have been synthesized and their structures determined by X-ray diffraction. In complex 1, the btm ligands assume the μ2-1,1′:4 coordination mode and interlink Mn(II) ions into infinite one-dimensional chains. The chains are assembled into a three-dimensional architecture via hydrogen bonds and π-π interactions. For 2, Mn(II) ions are connected by btm ligands in the μ3-1,1′:2:3′ mode to produce two-dimensional (6,3) coordination network. Magnetic investigations revealed that interactions through the btm bridges in both 1 and 2 are antiferromagnetic.  相似文献   

13.
Hua Tian 《Inorganica chimica acta》2010,363(11):2481-2487
Two new metal-organic coordination polymers with 1,5-dinitronaphthalene-3,7-dicarboxylate (NNDC), [Cu2(NNDC)2(DMF)1.8(DMSO)2.2(H2O)2]·H2O (1) and [Mn3(NNDC)3(DMSO)4]·2DMSO (2) have been synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction and Thermogravimetric Analysis (TGA). The structure of compound 1 consists of one-dimensional chains with copper ions being linked by the dicarboxylate ligands. The coordination chains are associated into ladder-like double chains through O-H?O hydrogen bonds and π-π interactions, and the ladders are packed in a cross fashion through further π-π interactions to give the three-dimensional structure. The Mn(II) compound exhibits a 3D framework with the pcu topology, in which [Mn3(COO)6] clusters as octahedral secondary building blocks are linked by the naphthalene spacers. Magnetic analyses were carried out based on both temperature- and field-dependent data, consistently suggesting relatively weak antiferromagnetic interactions within the carboxylate bridged [Mn3(COO)6] cluster.  相似文献   

14.
Four novel coordination polymers, one-dimensional chains [M(PTE)2(N3)2]n (M = Mn for 1 and Co for 2), and two-dimensional layers [M(PTE)2(dca)2]n (M = Mn for 3 and Co for 4) (PTE = 1-(2,4-difluorophenyl-2-(1H-1,2,4-triazol-1-yl)ethanone, dca = dicyanamide anion, N(CN)2), have been synthesized under mild ambient conditions and structurally characterized by single crystal X-ray diffraction. In all four crystal structures, the metal atoms adopt octahedral coordination geometry with six nitrogen atoms from two monodentate PTE ligands and four azido (or dca) bridging ligands. The crystal structures of 1 and 2 are isostructural 1-D polymeric chains, alternatively linked by double end-on and double end-to-end azido bridges. However, the bent dca ligands as bidentate μ2-1,5 bridging ligands interlink the octahedral metal units to lead to 2-D (4,4) grid networks in 3 and 4. Temperature-dependent magnetic measurements in 2-300 K have been performed for these four polymers, and suggest alternative ferro- and antiferromagnetic couplings for end-on and end-to-end azido bridges in 1, and the dominant ferromagnetic coupling in 2, respectively. Both polymers 3 and 4 show weak antiferromagnetic exchanges through the μ2-1,5-dca bridges. The effects of auxiliary coligands on the structure and the nature of these magnetic exchanges are discussed in the light of the crystal structures in detail.  相似文献   

15.
The rigid, π-conjugated dicarboxylic acid 1,4-bis-[2-(4-carboxyphenyl)ethynyl]-2,5-dihexylbenzene {HO2C[PEP(hexyl)2EP]CO2H} has been used to synthesise the new crystalline coordination polymers {Zn(O2C[PEP(hexyl)2EP]CO2)(DMF)2} (1) and {Zn(O2C[PEP(hexyl)2EP]CO2)(DEF)2} (2) in N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF), respectively, under mild conditions. Single-crystal X-ray crystallography revealed that 1 and 2 are isostructural and consist of uncharged zigzag coordination chains in which [Zn(formamide)2]2+ fragments are bridged by (O2C[PEP(hexyl)2EP]CO2)2− ligands. The zigzag chains possess different intra-chain Zn?Zn?Zn angles due to the different volumes of the coordinating formamide molecules and subtle differences in the hydrophobic inter-chain interactions. Upon heating 1 and 2 to 200 °C, removal of the coordinating formamide molecules occurs, yielding the formamide-free compounds 1-DMF and 2-DEF of composition {Zn(O2C[PEP(hexyl)2EP]CO2)}. According to powder X-ray diffraction and FT-IR spectroscopy studies, these materials are not crystalline but still possess partial ordering of intact, yet modified coordination chains in a structural arrangement which appears to be related to the respective parent compounds. Compounds 1, 2, 1-DMF and 2-DEF exhibit blue photoluminescence. The emission maxima of 1-DMF and 2-DEF are red-shifted by ca. 25 nm with respect to λmax of 1 and 2, respectively.  相似文献   

16.
Two novel Co(II) coordination polymers {[Co(H2O)2(CH3OH)2(4-bpfp)](NO3)2}n1 (4-bpfp=N,N-bis(4-pyridylformyl)piperazine) and [Co(NCS)2(CH3OH)2(3-bpfp)]n2 (3-bpfp=N,N-bis(3-pyridylformyl)piperazine) have been synthesized and characterized by single crystal X-ray diffraction. Both the polymers consist of one-dimensional chains constructed by bridging bpfp ligands and Co(II) ions. The existence of O?H-O hydrogen bond in 1 and S?H-O hydrogen bond in 2 play important roles in creating interesting supramolecular structures. Their third-order nonlinear optical (NLO) properties in DMF solution have been studied by Z-scan technique. The results reveal that polymers 1 and 2 exhibit strong NLO absorption effects (α2=9.00×10−11 m W−1 for 1; 1.41 × 10−10 m W−1 for 2) and self-focusing performance (n2=3.24×10−16 esu for 1; 3.05 × 10−16 esu for 2) in DMF solutions. The corresponding effective NLO susceptibilities χ(3) values are 3.08 × 10−12 esu (1) and 4.70 × 10−12 esu (2). All of the values are comparable to those of the reported good NLO materials. Additionally, the TG-DTA results of the two polymers are in agreement with the crystal structures.  相似文献   

17.
Three new coordination complexes [Mn(L)(H2O)2](1,4-BDC)·2H2O (1), [Mn(L)0.5(1,4-BDC)]CH3OH·H2O (2) and [Mn(L)(H2O)2](1,2-HBDC)2·2H2O (3) were synthesized by solvothermal reactions of 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene (L) and 1,4-benzenedicarboxylic acid (1,4-H2BDC) or 1,2-benzenedicarboxylic acid (1,2-H2BDC) with Mn(II) salt, and characterized by single crystal X-ray diffraction, IR, thermogravimetric and elemental analyses. In complexes 1 and 3, each ligand L links four Mn(II) atoms to form two-dimensional (2D) cationic network with non-coordinated 1,4-BDC2− and 1,2-HBDC anions lying in the voids between the two adjacent layers, respectively. The 2D layers are further connected together by hydrogen bonds to give three-dimensional (3D) supramolecular structures. However, the 1,4-BDC2− in 2 acts not only as counteranion, but also as bridging ligand leading to the formation of 2-fold interpenetrated 3D framework with pcu (primitive cubic unit) topology. The Mn(II) atoms bridged by carboxylate groups in 2 show antiferromagnetic interactions.  相似文献   

18.
The two complexes containing bioactive ligands of the type and [Fe(L)] (PF6)2 (1) (where L = [1-{[2-{[2-hydroxynaphthalen-1-yl)methylidine]amino}phenyl)imino] methyl}naphthalene-2-ol]) and [Co(L1L2)] (PF6)3 (2) (where L1L2 = mixed ligand of 2-seleno-4-methylquinoline and 1,10-phenanthroline in the ratio 1:2, respectively) were synthesized and structurally characterized. The DNA binding property of the complexes with calf thymus DNA has been investigated using absorption spectra, viscosity measurements, and thermal denaturation experiments. Intrinsic binding constant Kb has been estimated at room temperature. The absorption spectral studies indicate that the complexes intercalate between the base pairs of the CT-DNA tightly with intrinsic DNA binding constant of 2.8 × 105 M?1 for (1) and 4.8 × 105 M?1 for (2) in 5 mM Tris-HCl/50 mM NaCl buffer at pH 7.2, respectively. The oxidative cleavage activity of (1) and (2) were studied by using gel electrophoresis and the results show that complexes have potent nuclease activity.  相似文献   

19.
Two luminescent Cd(II) complexes [RBzPy][Cd(SCN)3] for R = Cl (1) and Br (2) have been synthesized and structurally characterized. The Cd atoms are all N3S3 hexa-coordinated with six bridging SCN and form infinite [Cd(SCN)3] polymeric chains. The layer arrangement of the anionic chains was obtained using the larger halogenated benzylpyridyl cations. The luminescent properties of 1 and 2 in the solid state were investigated.  相似文献   

20.
One-dimensional (1-D) helical coordination polymers, [MII(H2O)3(BPDC)]n · nH2O (M = Co (1), Fe (2)), have been prepared by the self-assembly of cobalt(II) and iron(II) ions, respectively, with 2,2′-bipyridyl-3,3′-dicarboxylic acid (H2BPDC) in an aqueous solution. X-ray crystal structures of compounds 1 and 2 show that each metal ion displays a distorted octahedral coordination geometry including three water oxygen atoms, one oxygen atom of the carboxylate of a BPDC2− belonging to the adjacent metal ion and two nitrogen atoms from the BPDC2− acting as a chelating ligand. In 1 and 2, one carboxylate oxygen atom of coordinated BPDC2− binds to the neighboring metal ion, which give rise to 1-D helical coordination polymers. The helical chains of 1 and 2 are linked by the hydrogen bonding interactions between the carboxylate oxygen atom of the BPDC2− ion belonging to a chain and the water molecule of the adjacent helical chain, which lead to 2-D networks extending along the ab plane. The supramolecules 1 and 2 show isomorphous structures regardless of the metal ions.  相似文献   

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