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1.
Three one-dimensional zinc complexes, namely, [Zn(pzdc) · 3H2O] · H2O (1), [Zn2(pzdc)· 4H2O] · 2.5H2O (2), and [Zn(pzdc)(phen) · 4H2O]n (3) (H2pzdc, pyrazine-2,3-dicarboxylic acid, phen = 1,10-phenanthroline), have been synthesized successfully under hydrothermal condition. X-ray diffraction analyses reveal that complex 1 is a square-wave-like chain and complex 2 shows a 1D ladder-like infinite chain, while complex 3 has 1D zigzag chain structure. In all cases, the Zn(II) centers have octahedral coordination geometries. Through hydrogen bonding (such as O-H···O, O-H···N and C-H···O) and/or π-π stacking interactions, three-dimensional supramolecular networks are constructed in three complexes. Furthermore, the IR, TGA and luminescent properties are also investigated in this work.  相似文献   

2.
Three ternary zinc complexes of the open chain polycarboxylic acid, tricarballylic (1,2,3-propane-tricarboxylic) acid (PTCH3) have been isolated and characterized with crystallographic and physicochemical techniques. [Zn(PTCH)(phen)(H2O)]2 · 4H2O (1) (where phen = 1,10-phenanthroline) has a unique dinuclear structure, while [Zn(PTCH)(bpy)]n · 3nH2O (2) and [Zn(PTCH)(epy)]n · 4nH2O (3) (where bpy = 4,4′-bipyridine and epy = 1,2-bis(4-pyridine)ethane) have 2D polymeric structures. The bis-deprotonated ligand, in all three complexes, uses for coordination only two oxygen atoms, which belong to the same carboxylate in 1, and to two different carboxylates in 2 and 3.  相似文献   

3.
Four new Cu(II) complexes [Cu(pzda)(2,2′-bpy)(H2O)] · 2.5H2O (1), [Cu(pzda)(phen)(H2O)] · H2O (2), [Cu(pzda)(4,4′-bpy)] · H2O (3) and [Cu(pzda)(bpe)0.5(H2O)] (4) were synthesized by hydrothermal reactions of copper salt (acetate or sulphate) with pyrazine-2,6-dicarboxylic acid (H2pzda), and 2,2′-bipyridine (2,2′-bpy), 1,10-phenanthroline (phen), 4,4′-bipyridine (4,4′-bpy) or 1,2-bis(4-pyridyl)-ethane (bpe), respectively. For 1 and 2, they are both monomeric entities which are further assembled into 3D supramolecular networks by hydrogen bonds and π-π stacking interactions. Complex 3 has a 2D metal-organic framework which is connected into 3D supramolecular network by hydrogen bonds. However, for 4, the bpe ligand bridges two Cu(II) ions into binuclear unit, and then the binuclear molecules are assembled into 3D supramolecular network by hydrogen bonds between the coordination water molecule and the carboxylate oxygen atoms. The thermal decomposition mechanism of complexes 1 and 2 cooperated with powder XRD at different temperatures is discussed. The results reveal that once liberation of water molecules takes place the supramolecular network of 1 and 2 collapses.  相似文献   

4.
Four new heterobimetallic coordination polymers, namely, {[Cu(aeoe)M(H2O)3 · 2H2O]2}n (M = Mn(II) (1), Co(II) (2), Ni(II) (3)) and [Cu(aeoe)Ni(H2O)3]2 (4) (H4aeoe = N′-(2-aminoterephthalic acid)-N′′-(ethylenediamine)oxamidato) have been synthesized and characterized structurally. Complexes 1-3 are allomerism and feature 1-D ladder-like chain structure constructed from neutral tetranuclear complex units through the syn-anti carboxylate bridges, whereas complex 4 is a cyclic neutral tetranuclear complex unit. Their magnetic properties are also investigated based on their structures.  相似文献   

5.
A chiral Schiff base N-(S)-2-(6-methoxylnaphthyl)-propanoyl-N′-(2-hydroxylbenzylidene)hydrazine (H2L) has been synthesized. Reaction of H2L with Cu(OAc)2 · H2O led to the formation of a metal complex {[CuL] · H2O · 2DMF} (1). In complex 1, the potential dinegative tridentate L2− ligand acting as tetradentate bridging ligand coordinate to two metal ions so as to form a novel infinite metal-organic coordination chain structure. The enantiomerically pure ligand H2L presents two different sets of signals in the 1H NMR spectrum either in chloroform solution or in dimethylsulfoxide solution, showing the presence of both (E) and (Z) isomers. The X-ray structural investigations of H2L revealed that it is the fully extended E-configuration in the solid state.  相似文献   

6.
Two Hg(II) complexes [HgL′(ClO4)2] (1) and [HgL(ClO4)]ClO4 (2) derived from the macrocyclic ligands, 4-(pyridin-2-ylmethyl)-1,7-dithia-4,10-diazacyclododecane (L′) and 7-(pyridin-2-ylmethyl)-1,4,10-trithia-7,13-diazacyclopentadecane (L), have been crystallographically characterised. Ligand L and its Hg(II) complex were isolated unexpectedly, and a possible formation pathway of the ligand is proposed. By including weakly bound O atoms from the perchlorate ions, the Hg atoms in both complexes are seven-coordinate and possess capped trigonal prismatic geometries. These uncommon structures for Hg(II) complexes were achieved mainly by the relatively large size of the metal ion and the steric effect from the macrocycles. In both complexes, strong hydrogen bonding between the amine hydrogen atom and a perchlorate ion was observed. For complex 1, the interaction is N(3)-H(15)···O(8) at 2.08(12) Å where O(8) is of the same anion as one of the coordinated O atoms; in complex 2, a similar hydrogen bond, N(7)-H(7)···O(32), with a distance of 2.25 Å, is formed to the coordinated anion, but the second anion remains discrete.  相似文献   

7.
A 1D-coordination polymer [{Mn3(C6H5COO)6(BPNO)2(MeOH)2}(MeOH)2]n (1) having benzoate as the anionic ligand and 4,4′-bipyridyl-N,N′-dioxide (BPNO) as bridging ligand is synthesized by reacting benzoic acid with manganese(II) acetate tetrahydrate followed by reaction with 4,4′-bipyridyl-N N′-dioxide. The bridging bidentate BPNO ligands in this coordination polymer along with the benzoate bridges hold the repeated units. The chain like structure in one dimension by benzoate bridges are connected to each other through the μ321 bridges of BPNO ligands. This coordination polymer can be transformed to a molecular complex [Mn(H2O)6](C6H5COO)2.4BPNO (2). In this complex the BPNO remains outside the coordination sphere but they are hydrogen bonded to water molecules to form self assembled structure. The reaction of 3,5-pyrazoledicarboxylic acid (L1H2) and BPNO with manganese(II) acetate or zinc(II) acetate led to molecular complexes with composition [M2(L1)2(H2O)6].BPNO·xH2O {where M = Mn(II) (3), Zn(II)(4)}. These molecular complexes of BPNO are characterised by X-ray crystallography. The complexes 3-4 are binuclear carboxylate complexes having M2O2 core formed from carboxylate ligands with two metal ions.  相似文献   

8.
A new coordination polymer, [Zn2(mal)(1,10-phen)Cl]n (1), (mal = malate, 1,10-phenanthroline), has been synthesized with malic acid and fumaric acid which are generated from maleic acid under hydrothermal reactions. At about the same condition, we get [Cd(fma)(2,2′-bpy)(H2O)]n (2) (fma = fumarate, 2,2′-bpy=2, 2′-bipyridine). The diverse products illustrate that the carbon-carbon doublebond of the maleic acid has two kinds of reaction trends under different conditions. Complex 1, which displays a two-dimensional (4, 8) lattice-type network, is formed from Zn and maleic through the addition reaction with water molecule. If the Zn is changed by Cd, at the same reaction condition with 1, a two-dimensional supramolecular network complex 2 is formed through the conformation transform reaction. To our knowledge, a lot of coordination polymers have been constructed from malic acid and fumaric acid directly; however, these kinds of complexes have seldom been synthesized from maleic acid under hydrothermal reaction. As is known, the rigid carbon-carbon double bond makes maleic acid lead to some unique structural features which the saturated aliphatic acid does not possess. To illustrate this clearly, a simple one dimensional complex 3, [Cd(glut)(1,10-phen)(H2O)]n (glut = glutarate), is synthesized. Furthermore, complex 1 and complex 3 exhibit intense photoluminescent property at room temperature.  相似文献   

9.
The dinuclear complexes [Pd2(L)2(bipy)2] (1), [Pd2(L)2(phen)2] (2), [Pt2(L)2(bipy)2] (3) and [Pt2(L)2(phen)2] (4), where bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline and L = 2,2′-azanediyldibenzoic dianion) dibridged by H2L ligands have been synthesized and characterized. The binding of the complexes with fish sperm DNA (FS-DNA) were investigated by fluorescence spectroscopy. The results indicate that the four complexes bound to DNA with different binding affinity, in the order complex 4 > complex 3 > complex 2 > complex 1, and the complex 3 binds to DNA in both coordination and intercalative mode. Gel electrophoresis assay demonstrates the ability of the complexes to cleave the pBR 322 plasmid DNA. The cytotoxic activity of the complexes was tested against four different cancer cell lines. The four complexes exhibited cytotoxic specificity and significant cancer cell inhibitory rate.  相似文献   

10.
Three water-soluble zinc complexes, [Zn(Cbp)2Br2] (1) (Cbp = N-(4-carboxybenzyl)pyridinium), {[Zn(BCbpy)2(H2O)4]3Br6·2(BCbpy)·2(4,4′-bipy)} (2) (BCbpy = 1-(4-carboxybenzyl)-4,4′-bipyridinium) and {[Zn4(Bpybc)6(H2O)12](OH)8·9H2O}2n (3) (Bpybc = 1,1′-bis(4-carboxybenzyl)-4,4′-bipyridinium), were synthesized and characterized by IR, elemental analysis and single-crystal X-ray crystallography. In complex 1, the central Zn atom adopts a distorted tetrahedral coordination geometry that is formed from two unidentate Cbp ligands and two Br atoms. For complex 2, the Zn atom in [Zn(BCbpy)2(H2O)4]2+ is strongly coordinated by four water molecules and two N atoms from two BCbpy ligands, hence forming an octahedral geometry. In complex 3, each Bpybc ligand bridges two [Zn(H2O)3]2+ units through two terminal carboxylate groups in a monodentate coordination mode, thus forming a flowerlike two-dimensional network. Agarose gel electrophoresis (GE) and ethidium bromide (EB) displacement experiments indicated that complex 3 was capable of converting pBR322 DNA into open circular (OC) and linear forms, and exhibited high binding affinity toward calf-thymus DNA. MTT assay showed that complex 3 displayed inhibitory activities toward the proliferation of lung adenocarcinoma A549 and mouse sarcoma S-180 cells, with the IC50 values being 27.3 and 48.8 μM, respectively.  相似文献   

11.
By one-pot solvothermal reaction, two 3-D metal(II)-organic coordination polymers [Zn2(SDC)2(L1)] (1) and [Zn(SDC)(L2) · 2DMF] (2) are self-assembled from trans-4,4′-stilbenedicarboxylic acid (H2SDC), 4-(4-((E)-2-(pyridin-4-yl)vinyl)- styryl)pyridine (L1), 4,4′-bipyridine(L2) and zinc salts in the presence of N,N′-dimethylbenzenamine, and characterized by single-crystal X-ray diffraction analyses. The overall structure of 1 with total potential solvent-accessible volume of 44.2% presents a fourfold interpenetrated topology from 6-connected CdO-like nets, while that of 2 with nanosized channels occupied by free DMF molecules displays a fivefold interpenetrated framework of [Zn(SDC)(L2)]n from 4-connected diamondoid networks. The topology types and the multi-fold interpenetrating of 1 and 2 are dependent on the second ligands (L1 and L2). Solid-state 1 and 2 have expected photoluminescence with maximum emission at 484 and 505 nm, respectively.  相似文献   

12.
Four new zinc(II) complexes [Zn(dien)(μ-nic)]2(BPh4)2·2CH3OH (1), {[Zn(dien)(isonic)]BPh4}n (2), [Zn(tren)(nic)]BPh4 (3) and [Zn(tren)(isonic)]BPh4 (4) (dien/tren = diethylenetriamine/triethylenetriamine, nic/isonic = nicotinate/isonicotinate anion) were synthesized and structurally characterized by IR, 1H NMR and single crystal X-ray diffraction. In the zinc(II) complexes of dien, both nicotinate and isonicotinate connect the zinc(II) ions via N,O-bis-monodentate mode. Complex 1 contains a centrosymmetric dinuclear unit bridged by two nicotinate anions in anti-parallel way. Complex 2 is characterized by an infinite one-dimensional zigzag chain bridged by isonicotinate anion in an end-to-end mode. The Zn···Zn distance is 6.782 for 1 and 8.805 Å for 2. While in the complexes of tren, both 3 and 4 are mononuclear complexes with nicotinate and isonicotinate coordinated to zinc(II) ion through only one oxygen atom of their carboxylate groups. The zinc(II) ions in all of the four complexes are in a distorted trigonal bipyramidal geometry. Complex 3 forms a dinuclear unit and complex 4 forms an infinite 2D sheet structure through intermolecular H-bonds. In all of the crystal lattices, the counterions act to balance the electronic charge at the same time to construct different 3D structures through noncovalent interactions such as C-H···π, N-H···π and van der Waals interactions.  相似文献   

13.
Hydrothermal synthesis has afforded a family of four coordination polymers containing divalent nickel or cobalt and pendant-arm pyridylcarboxylate ligands. Utilizing 3-pyridylacetic acid and appropriate metal precursors produced [M(3-pyrac)2(H2O)2] phases (M = Co (1); M = Ni (2)), while 3-pyridylpropionic acid generated [M(3-pyrprop)2(H2O)2] coordination polymers (M = Co (3); M = Ni (4)). Single crystal X-ray diffraction revealed that 1-4 all display discrete 2-D layers with (4,4)-topology, anchored via bridging 3-pyridylcarboxylate ligands bearing monodentate carboxylate termini. Intralamellar hydrogen bonding between the aquo ligands and unligated carboxylate oxygen atoms is observed within 1-4. The pseudo 3-D structures of 1-4 are further assembled via stacking of individual neutral layers by interlayer hydrogen bonding. Thermal properties are also discussed.  相似文献   

14.
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   

15.
Six antimony adducts with N-donor neutral ligands (1,10-phenanthroline, 4,4′-bipyridine) have been obtained following the reaction of antimony halides with phenanthroline and 4,4′-bipyridine. By changing the solvent and stoichiometry, we obtained six different complexes, Sb(phen)Cl3 (1), Sb(phen)Br3 (2), Sb2(phen)4Br8 (3) and Sb(bpy)Cl3 (4), Sb(bpy)2Cl3 (5), Sb(bpyH · bpyH2)Br6 (6) (where phen = 1,10-phenanthroline, bpy = 4,4′-bipyridine). All the complexes have been characterized via elemental analysis, FT-IR and NMR (1H, 13C) spectroscopy. The crystal structures of complexes 2, 3 and 6 have been determined by X-ray single crystal diffraction.The structural analysis show that the coordination sphere around antimony atom in complex 2 is a distorted square pyramid, coordinated by three bromine atoms and two nitrogen atoms from phen. In complex 3, the central antimony atom is six-coordinated through four bromine atoms and two nitrogen atoms forming a distorted octahedral geometry. Besides that, there are also uncoordinated 1,10-phenanthroline bonded by hydrogen bonds and π-π stacking interactions, which is rarely observed in previous reports. The crystal structure of complex 6 consists of bpyH · bpyH2 trications and hexabromoantimonate trianions. The antimony atom in the anion has a distorted octahedral environment. Additionally, all complexes present a 3D framework built up by N-H?Br, C-H?Br and C-H?Cl weak hydrogen bonds interactions.  相似文献   

16.
Three coordination complexes of formula [Ni(L1)2(H2O)4].4H2O (1), [Mn(L2)2(H2O)4] (2) and [Mn(L2)2(H2O)2]n (3) [L1H = 6-methylpyridine-3-carboxylic acid, L2H = 3-(3-pyridyl)acrylic acid] have been synthesized and structurally characterized by X-ray single crystal analysis. A 3D network is achieved through H-bonding in 1 and 2, while crystal packing of complex 3 shows a 3D supramolecular coordination polymer. Thermal properties have been investigated by thermogravimetric analysis. Luminescence study features the presence of LMCT and metal purterbed ligand centered emission bands.  相似文献   

17.
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   

18.
Preparation and characterization of (triphenylphosphine)ruthenium complexes bearing N,O,N′-tridentate ligands, [(L1)RuCl(PPh3)2](BF4) (L1 = 2-[(2-pyridylmethoxy)methyl]pyridine), 1), [(L2)RuCl(PPh3)2](BF4) (L2 = 8-(2-pyridylmethoxy)quinoline, 2) and [(L3)RuCl2(PPh3)] (L3 = 2-[(2-pyridylmethoxy)methyl]quinoline, 3) are described. Complexes 1-3 have been characterized by NMR and elemental analyses. Molecular structures of 2 and 3 have been determined by X-ray crystallography. Both compounds exhibit the octahedral geometry. L2 adopts the facial configuration in 2 while L3 is in a mer-arrangement in 3. Complexes 1-3 have proven to be able to catalyze the transfer hydrogenation of several ketones to alcohols in the presence of KOH and 2-propanol at refluxing, among which complex 3 was found to be the most active.  相似文献   

19.
2,6-Dimethyl-4-phenylpyridine-3,5-dicarboxylic acid (H2mppdc, H2L) is firstly employed in coordination chemistry. Two metal-organic coordination polymers with a general formula of M2L2(4,4′-bpy)x(H2O)4−2x (M = Zn or Co, x = 1 or 2) are assembled from H2L, 4,4′-bipyridine, zinc and cobalt salt under hydrothermal conditions, and characterized by single-crystal X-ray diffraction analyses. Of the crystal structures of title compounds, L ligands, limited in the environment from 4,4′-bipyridine, array in head-to-head and head-to-tail modes which are corresponding to the 1D (1) and 3D (2) polymeric structures, respectively. Interesting disorders occur in the crystal lattice of compound 1. And compound 2 has a 3D 42 · 610 · 83 topology. Solid-state H2L and 1 have expected photoluminescence at room temperature.  相似文献   

20.
Two three-dimensional (3D) novel lanthanide complexes with the H2Lbenzimidazole-5,6-dicarboxylate [Ln2L3(H2O)] [Ln = Eu (1), Tb (2)] and one two-dimensional (2D) novel lanthanide complex [Pr(L)(HL)H2O]·H2O (3) were synthesized by hydrothermal reaction at 180 °C and characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction. The result showed that complexes 1 and 2 are isostructural and build porous 3D networks by L2− groups linking Ln(III) atoms via tetradentate (bridging and bridging) and pentadentate (bridging/chelating and bridging) coordination modes. Complex 3 is a eight-coordinated Pr(III) chain complex, exhibiting a 2D polymeric network with parallel Pr-carboxylate chains along the crystallographic c-axis. In addition, it is found that in these structures, coordination modes of L2− and HL are versatile and can adopt different conformations according to distinct dimensions of polymeric structures. The photoluminescent properties of 1, 2 and thermogravimetric analyses of the three complexes were discussed in detail.  相似文献   

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