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1.
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   

2.
Three novel complexes [Mn(atza)2(H2O)4] (1), [Mn(nptza)2(CH3OH)4] (2), and [Mn(a4-ptz)2(H2O)2]n · 2nH2O] (3) [atza = 5-aminotetrazole-1-acetato, nptza = 5-[(4-nitryl)phenyl] tetrazole-1-acetato, a4-ptz = 5-[N-acetato(4-pyridyl)] tetrazole] containing carboxylate-tetrazolate ligands have been synthesized and characterized by element analysis. X-ray crystallography shows that complexes 1 and 2 both contain mononuclear structure. The complex 3 is a 1D polymeric chain structure. Compounds 1-3 are self-assembled to form supramolecular structures through hydrogen bonds interactions.  相似文献   

3.
Two structurally related flexible imidazolyl ligands, bis(N-imidazolyl)methane (L1) and 1,4-bis(N-imidazolyl)butane (L2) reacted with Mn(II) salts of aliphatic dicarboxylic acids resulted in the formation of a number of novel metal-organic coordination architectures. All complexes have been structurally characterized by X-ray diffraction analysis. The different coordination modes of dicarboxylate anions due to their chain length, rigidity and diimidazolyl functionality lead to a range of different coordination structures. The coordination polymers exhibit 1D single chain, 2D sheet and 3D network structures. The aliphatic dicarboxylates can adopt chelating μ2, bridging μ2, and chelating-bridging μ3 coordination modes, or act as uncoordinated counter anions. The central metal ions are coordinated in N2O4 and N4O2 fashions depending on the ancillary ligands. The topology of [Mn(male)(L1)(H2O)2] (1, male = maleate) gives rise to singly bridged 1D chains, whereas compound [Mn(mal)(L1)(H2O)] · H2O (2, mal = malonate) exhibits 2D sheets in which the metal centers are bridged by both imidazolyl ligands and dicarboxylates. Compounds [Mn(L1)2(H2O)2](suc) · 6H2O (3, suc = succinate) and [Mn(L1)2(H2O)2](fum) · 6H2O (4, fum = fumarate) show doubly bridged 1D chains, and the dicarboxylate groups are not coordinated but form 2D corrugated sheets with water molecules intercalated between the cationic layers. Compound [Mn(suc)(L2)(H2O)2] (5, suc = succinate) was built from very flexible succinate and 1,4-bis(N-imidazolyl)butane which yielded three-dimensional interpenetrate networks, both succinate anion and the imidazolyl ligand act as bidentate bridging.  相似文献   

4.
A series of new coordination polymers of Cu(II) have been prepared in a reaction between copper(II) perchlorate or tetrafluoroborate salt and a novel ligand 1,4-di(1,2,3,4-tetrazol-2-yl)butane (bbtz). The compounds were characterised by an elemental analysis, TG measurements, IR, EPR and UV-Vis spectroscopy. Crystal structures of bbtz and five complexes of Cu(II) were determined by a single crystal X-ray diffraction measurement performed at 100 K. The composition and architecture of the obtained complexes strongly depend on the reaction conditions especially on the kind of solvent. Investigated complexes are composed of polymeric macrocations and non-coordinated anions. In all cases the bbtz molecules act as the bidentate ligand coordinated to metal(II) ions via N4, N4 nitrogen atoms from tetrazole rings. The complexes {[Cu(bbtz)2(MeOH)2]X2} (X=ClO4, BF4) crystallise from methanol as 2D coordination polymers. In these compounds central metal ions are coplanar linked by molecules of bbtz and a coordination sphere is completed by axially coordinated solvent molecules. The complexes {[Cu(bbtz)3]X2} (X=ClO4, BF4) were synthesised in EtOH/H2O solvent system and posses a common network topology. In this group of complexes each central atom is linked by ligand molecules to six other in plane arranged central atoms resulting in 2D networks. Reactions between Cu(II) salts and bbtz performed in absolute ethanol resulted in the formation of the next type of product. In {[Cu(bbtz)3](ClO4)2·2EtOH} neighboured copper(II) ions are linked by ligand molecules in the three directions what leads to the formation of 3D net. A crystal of this complex is composed of two mutually interpenetrated 3D networks.  相似文献   

5.
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   

6.
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   

7.
A novel 2-fold interpenetrating layered complex [Zn(4-PTA)2·2H2O]n (1) has been synthesized by hydrothermal reactions of ZnBr2 and 4-PTN (or 4-PTA and 4-CCP), and characterized by single crystal X-ray diffraction, elemental analysis, IR, XRD and TGA (where 4-PTA = 2-(5-(pyridin-2-yl)-2H-tetrazol-2-yl)acetic acid, 4-PTN = 2-(5-(pyridin-2-yl)-2H-tetrazol-2-yl)acetonitrile and 4-CCP = 4-cyano-1-(cyanomethyl)pyridinium bromide). The tetrahedral Zn(II) centers are bridged by 4-PTA ligands into a 2D (4, 4)-connected topology net. Then the adjacent nets were intertwined to result in a 2D-2D parallel interpenetrating layer. The H-bonding weak interactions further stabilized the complex. Furthermore, solid-state fluorescence spectrum of complex 1 exhibits intense broad emissions at 413 nm at room temperature, which is red-shifted by 32 nm relative to that of free 4-PTA ligand. This synthesis provides a new impetus about applying in situ hydrothermal reaction chemistry to a new system.  相似文献   

8.
Two novel photoluminescent coordination polymers of formula [Cd(atpt)(H2O)2] · 2H2O (1) and [Zn(atpt)(H2O)2] (2) (H2atpt = 2-aminoterephthalic acid), in which the amino group of the atpt ligand coordinates to the metal(II) ions for the first time, have been synthesized through the self-assemblies of H2atpt and N-containing ligands [nicotiamide for 1 and imidazole for 2, respectively] with the metal(II) ions in the presence of NaOH. These complexes were characterized by FT-IR spectroscopy, thermogravimetric analysis (TG), elemental analysis and X-ray analysis. X-ray crystallographic studies of the complexes reveal that complex 1 is a double stranded one-dimensional chain, which further assembles into a three-dimensional supramolecular network via the interchain π-π stacking interaction and strong hydrogen bonds, while complex 2 exhibits a two-dimensional porous architecture. The extensively strong hydrogen bonds in complex 2 lead to the formation of three-dimensional supramolecular framework. Photoluminescence properties of the compounds 1 and 2 have been examined in solid state at room temperature. These compounds have been found to exhibit blue photoluminescence and may be good candidates for photoactive materials.  相似文献   

9.
In our efforts to investigate the factors that affect the formation of coordination architectures, such as secondary coordination donors and pendant skeletons of the carboxylic acid ligands, as well as H-bonding and other weak interactions, two kinds of ligands: (a) 3-(2-pyridyl)pyrazole (L1) with a non-coordinated N atom as a H-bonding donor, a 2,2′-bipyridyl-like chelating ligand, and (b) four carboxylic ligands with different secondary coordination donors and/or pendant skeletons, 1,4-benzenedicarboxylic acid (H2L2), 4-sulfobenzoic acid (H2L3), quinoline-4-carboxylic acid (HL4) and fumaric acid (H2L5), have been selected to react with Mn(II) salts, and five new complexes, [Mn(L1)2(SO4)]2 (1), [Mn(L1)2(L2)] (2), [Mn(L1)(HL3)2] (3), Mn(L1)2(L4)2 (4), and [Mn(L1)2(L5)] (5), have been obtained and structurally characterized. The structural differences of 1-5 can be attributed to the introduction of the different carboxylic acid ligands (H2L2, H2L3, HL4, and H2L5) with different secondary coordination donors and pendant skeletons, respectively. This result also reveals that the typical H-bonding (i.e. N-H?O and O-H?O) and some other intra- or inter-molecular weak interactions, such as C-H?O weak H-bonding and π?π interactions, often play important roles in the formation of supramolecular aggregates, especially in the aspect of linking the multi-nuclear discrete subunits or low-dimensional entities into high-dimensional supramolecular networks.  相似文献   

10.
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   

11.
Assemblies of 5-amino-2,4,6-triiodoisophthalic acid (H2ATIBDC) with Cd(II) and Zn(II) in the presence of N-donor auxiliary ligand, 1,4-bis(1,2,4-triazol-1-yl)butane (btb), at ambient conditions yield two new supramolecular complexes, [Cd(ATIBDC)(btb)(H2O)2]·3H2O (1), and [Zn(ATIBDC)(btb)]·2H2O (2). Generally, these two complexes display 1D ATIBDC2−-bridged coordination arrays. Distinct extended 3D network architectures are further constructed with the help of weak secondary interactions especially aromatic stacking, halogen bonding, and hydrogen bonding as supramolecular driving forces. It is worthy to mention that halogen bonds (C-I?π and C-I?N/O) play important roles in the supramolecular assembly. The pentameric cluster (H2O)5 in 1 assembles into highly ordered helical infinite chains. Complex 2 exhibits the fascinating single-walled tube-like chain structure. It loses crystallinity rapidly in the air and leads to the formation of [Zn(ATIBDC)(btb)]·H2O (2A). Thermal stabilities and solid state fluorescent properties of complexes 1 and 2A have been studied.  相似文献   

12.
Using the principle of crystal engineering, six metal-organic coordination polymers, [Cd(bdc)(3-pytpy)]n · 2nH2O (1), [Cd(bdc)0.5(3-pytpy)]n · n(ClO4) (2), Cd(ndc)0.5(3-pytpy)]n · n(ClO4) (3), [Zn(ndc)(3-pytpy)]n (4), [Cd(bqdc)(3-pytpy)]n (5), and [Zn(pam)(3-pytpy)]n · 2nH2O (6) (H2bdc = benzene-1,4-dicarboxylic acid, H2ndc = naphthalene-2,6-dicarboxylic acid, H2bqdc = 2,2′-biquinoline-4,4′-dicarboxylic acid, H2pam = pamoic acid), were synthesized and structurally characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction analyses. Compounds 1-6 crystallize in the presence of organic-acid linkers as well as multi-functional N-donor ligand 4′-(3-pyridyl)-2,2′:6′,2′′-terpyridine (3-pytpy). In complexes 1, 4, 5, and 6, the dicarboxylate as bridging ligand connects metal atoms to form the main body of 1D zigzag chains for 1 and 4, nearly linear chain for 5 and helical chain for 6, while 3-pytpy as tridentate chelating ligand is just like lateral arm grafting on both sides of these chains. In complexes 2 and 3, both the dicarboxylate and 3-pytpy as bridging ligands connect metal atoms into 2D polymeric structure for 2 and 1D chain of alternating loops and rods for 3. The weak interactions such as hydrogen bonding and π···π stacking were investigated on the formation of superamolecular structures and the influence of organic acid on the formation of the final structures was discussed. In addition, the photoluminescent properties of 1-6 were also determined.  相似文献   

13.
In our efforts to investigate the relationships between the structures of ligands and their complexes, two structurally related ligands, 1-(2-pyridylmethyl)-1H-benzimidazole (L1) and 1-(4-pyridylmethyl)-1H-benzimidazole (L2), and their four complexes, [Zn(L1)2Cl2] (1), [Hg(L1)Br2] (2), {[Zn(L2)Cl2](CH3CN)} (3) and [Hg(L2)Br2]2(CH3CN)2 (4) were synthesized and structurally characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction analysis. Structural analyses show that 1 has a mononuclear structure, and 2 and 3 both take 1D structure. While 4 takes a dinuclear structure. 1, 2 and 4 were further linked into higher-dimensional supramolecular networks by weak interactions, such as C-H?Cl and C-H?Br H-bonding, C-H?π, and π?π stacking interactions. The structural differences of 1-4 may be attributed to the difference of the spatial positions of the terminal N donor atoms in the pendant pyridyl groups in L1 and L2, in which the pyridine rings may act as the directing group for coordination and the benzimidazole rings act as the directing group for π?π stacking and C-H?π interactions. The luminescent properties of the corresponding complexes and ligands have been further investigated.  相似文献   

14.
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   

15.
Two 1D coordination polymers, [Cu(mal)(Hdpa)]n (1) and {[Cu(mal)(tpy)] · 4H2O}n (2) (mal = maleate, Hdpa = 2, 2′-dipyridylamine and tpy = 2,2′:6′,2″-terpyridine), have been synthesized and their crystal structures, IR spectra, thermal analyses, magnetic properties were determined. In 1 and 2, the maleate ligands link adjacent metal centers to form 1D coordination polymeric chains. Furthermore, the carboxylate oxygen atoms and the aromatic chelate ligands provide potential supramolecular recognition sites for noncovalent interactions to form higher dimensionality. In 1, each pair of 1D chains recognize each other through strong hydrogen bond formed by active amine (-NH-) hydrogen and aromatic π-π stacking interactions to generate a zipperlike double-stranded chain. In contrast, when the substitutions of tpy for dpa further enhance the π-π aromatic stacking interactions, complex 2 is directly constructed into 2D zipperlike layers by the unprecedented aromatic π-π stacking interactions that same orientated aromatic chelate ligands are simultaneously attached to both sides of the chain and the significant C-H?O hydrogen bonds. These layers are constructed through hydrogen bonds and result in a 3D supramolecular network with 1D open channels, in which exists an unprecedented one-dimensional water chain. Both were magnetically characterized, showing weak ferromagnetic behavior.  相似文献   

16.
Two new Co(II) coordination polymers with mixed ligands, {[Co(BTA)0.5(DBI)2]·DBI·H2O}n (1) and [Co(PDA)(DBI)(H2O)]n (2) (H4BTA = benzene-1,2,4,5-tetracarboxylic acid; H2PDA = 2,2′-(1,2-phenylene)diacetic acid; DBI = 5,6-dimethyl-1H-benzoimidazole) have been synthesized under hydrothermal conditions, respectively. Both of them are characterized by elemental analyses, powder X-ray diffraction, thermogravimetric analysis, single-crystal X-ray diffraction, and magnetic susceptibilities. In 1, the Co(II) ions are four-coordinated and lie in distorted tetrahedron coordination environment. 1D ladder-like chain structure is formed by the bridging BTA4− ligand. In 2, the Co(II) ions are in slightly distorted octahedral coordination geometry, and linked by PDA2− ligand exhibiting a 2D layer structure. Temperature-dependent magnetic susceptibility measurements of 1 and 2 revealed that there are antiferromagnetic interactions between Co(II) ions.  相似文献   

17.
Three new coordination polymers [M(Pht)(1-MeIm)2]n (where M=Cu (1), Zn (2), Co (3); Pht2−=dianion of o-phthalic acid; 1-MeIm=1-methylimidazole) and two compounds [M(1-MeIm)6](HPht)2 · 2H2O (M=Co (4), Ni (5)) have been synthesized and characterized by X-ray crystallography. The structures of 1-3 (2 is isostructural to 3) consist of [M(1-MeIm)2] building units connected by 1,6-bridging phthalate ions to form infinite chains. In complex 1, each copper(II) center adopts a square coordination mode of N2O2 type by two O atoms from different phthalate ions and two N atoms of 1-MeIm, whereas in 3 two independent metal atoms are tetrahedrally (N2O2) coordinated to a pair of Pht ligands and a pair of 1-MeIm molecules. There are only van der Waals interactions between the chains in 1, while the three-dimensional network in 3 is assembled by C-H?O contacts. In contrast to polymers 1-3 the structures of 4 and 5 (complexes are also isostructural) are made up of the [M(1-MeIm)6]2+ cation, two hydrogen phthalate anions (HPht) and two H2O solvate molecules. The coordination around each metal(II) atom is octahedral with six nitrogen atoms of 1-MeIm. Extended hydrogen bonding networks embracing the solvate water molecules and a phthalate residue as well as the weak C-H?O interactions stabilize the three-dimensional structures. Magnetic studies clearly show that the magnetic ions do not interact with each other. Furthermore, in compound 4 we have another example of a highly anisotropic Co2+ ion with a rhombic g-tensor and large zero-field-splitting. The complexes were also characterized by IR and 1H NMR spectroscopy, thermogravimetric analysis, and all data are discussed in the terms of known structures.  相似文献   

18.
Two Cd(II) and Zn(II) coordination polymers based on 3,3′,5,5′-azobenzenetetracarboxylic acid (H4abtc): [Cd2(abtc)(H2O)6]·DMF·0.5H2O (1) and [Zn2(abtc)(bpy)(H2O)2]·DMF·H2O (2) are synthesized and structurally characterized. Both 1 and 2 are 2D polymers but interconnected by solvent molecules to generate 3D suprastructures. Solvent expulsion leads to rupture of both structures, but upon re-exposure to the solvent mixture they exhibit remarkable ability to regain the original structure reversibly from the almost amorphous solvent-expelled form. Compounds with such structural flexibility and reversibility are expected to have some useful functionality.  相似文献   

19.
One-dimensional organic/inorganic composite coordination polymer has been synthesised by the reaction of manganese(II) chloride with the chelating bidentate ligand, 1,10-phenanthroline (1,10-phen). X-ray single crystal analysis shows a doubly chloride bridged 1-D polymer, [Mn(μ-Cl)2(phen)]n (1), where manganese(II) ions possess octahedral environment. The complex is characterised by elemental analysis, different spectroscopic, electrochemical and low temperature magnetic susceptibility measurements. 1 exhibits strong fluorescence emission band at 410 nm and can serve as potential photoactive material as indicated from the characteristic fluorescence properties. Magnetic susceptibility measurements reveal a weak ferromagnetic interaction between the two high-spin Mn(II) ions of J = 0.017 cm−1.  相似文献   

20.
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   

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