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1.
A series of new complexes of oxovanadium(IV) [VO(L)(B)] and ruthenium(II) [Ru(CO)(PPh3)2(L)] ( 1.1- 1.3,  2.1–2.3 ) (H2L = dehydroacetic acid Schiff base of S‐methyldithiocarbazate, H2smdha ( 1 ) or S‐benzyldithiocarbazate, H2sbdha ( 2 ); B = 2,2′‐bipyridine (bpy) or 1,10‐phenanthroline (phen)) have been synthesized. The structure of these complexes was authenticated using elemental analyses and spectroscopic techniques, and their magnetic properties and electrochemical behaviour were studied. The molecular structures of oxovanadium(IV) complexes [VO(smdha)(bpy)]?CH2Cl2 ( 1.1 ) and [VO(sbdha)(phen)]?2H2O ( 2.2 ) were confirmed using single‐crystal X‐ray crystallography. Analytical data showed that the ligands 1 and 2 are chelated to the metal centres in a bi‐negative tridentate fashion through azomethine N, thiol S and deprotonated hydroxyl group. The antioxidant activity of the synthesized compounds was tested against 2,2‐diphenyl‐1‐picrylhydrazyl) radical, which showed that the complexes demonstrate a better scavenging activity than their corresponding ligands. The cupric ion reducing antioxidant capacity method was also employed and the total equivalent antioxidant capacity values were found to be higher for the oxovandium(IV) complexes. DNA binding affinity of the compounds was determined using UV–visible and fluorescence spectra, revealing an intercalation binding mode. Higher cytotoxicity for the complexes compared to their ligands was found against human liver hepatocellular carcinoma (HepG2) and breast adenocarcinoma (MCF7) cell lines using MTT assay.  相似文献   

2.
Six coordination compounds constructed by two structurally related flexible nitrogen-containing polycarboxylate ligands 2,2′-(2,2′-(ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(methylene)bis(azanediyl)dibenzoic acid (H2L1) and 5,5′-(2,2′-(ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(methylene)bis(azanediyl)diisophthalic acid (H4L2) have been synthesized: [Ni(H2O)6]?·?L1?·?(C2H5OH)0.5?·?H2O (1), [Co(L1)(L3)]?·?CH3OH (2), [Ni(L1)(L3)]?·?CH3OH (3), [Zn(L1)(L3)]?·?CH3OH (4), [Cd(L1)(L3)]?·?CH3OH (5), and [Zn(L2)0.5(phen)]?·?C2H5OH (6), where L3?=?3,4?:?9,10?:?17,18?:?23,24-tetrabenzo-1,12,15,26-tetraaza-5,8,19,22-tetraoxacyclooctacosan and phen?=?1,10-phenanthroline. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 displays a discrete structure, which is further linked by hydrogen bonds to form a 2-D supramolecular layer. Compounds 25 display similar structures. These compounds possess 1-D meso-chain structures linked by L1 and metals. The C–H?···?π interactions from neighboring chains extend the chains in different directions, giving a 3-D plywood network. Compound 6 possesses 2-D layers, which are further linked by hydrogen-bonding interactions to generate a 3-D supramolecular architecture.  相似文献   

3.
Three new polymeric frameworks, [Cd(bbbi)(ita)(H2O)]?·?H2O (1), [Cd(bbbi)(fma)] (2), and [Cd(bbbi)(fma)(H2O)]?·?2H2O (3) (bbbi?=?1,1-(1,4-butanediyl)bis-1?H-benzimidazole, H2ita?=?itaconic acid, and H2fma?=?fumaric acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 is a 2-D (4,4) network containing infinite 1-D zigzag Cd(II)-bbbi chains linked by auxiliary ita ligands. In the structure of 2, infinite 1-D linear Cd(II)-bbbi chains are linked by fma ligands to generate an undulated 2-D (4,4) network. In 3, an in situ ligand transformation occurred with malate converted to H2fma by dehydration. Thus, a 2-D (4,4) grid network constructed from bbbi and fma was obtained. The carboxylates with different substituents play an important role in the formation of the final frameworks and coordination modes of Cd(II). Thermal stability and luminescent properties of 1–3 were investigated.  相似文献   

4.
Potentiometric (PT) and conductometric (CT) titration methods have been used to determine the stoichiometry and formation constants in water for a series of ternary complexes of Co(II) and Ni(II) involving the oxydiacetate anion (ODA) and 1,10-phenanthroline (phen) or 2,2′-bipyridine (bipy) ligands, namely [Co(ODA)(phen)(H2O)], [Co(ODA)(bpy)(H2O)], [Ni(ODA)(phen)(H2O)] and [Ni(ODA)(bpy)(H2O)]. The ternary complex formation process was found to take place in a stepwise manner in which the oxydiacetate ligand acts as a primary ligand and the phen or bipy ligands act as auxiliary ones. The stability of the ternary complexes formed is discussed in the relation to the corresponding binary ones. Furthermore, the kinetics of the substitution reactions of the aqua ligands in the coordination sphere of the Ni-ODA and Co-ODA complexes to phen or bipy were studied by the stopped-flow method. The kinetic measurements were performed in the 288–303 K temperature range, at a constant concentration of phen or bipy and at seven different concentrations of the binary complexes (4–7 mM). The influence of experimental conditions and the kind of the auxiliary ligands (phen/bipy) on the substitution rate was discussed.   相似文献   

5.
Four new anthraquinone-1,5-disulfonate (L)-based metal complexes with N,N-bidentate chelating coligands, {[Pb(phen)2(L)]?·?4H2O} n (1), {[Mn2(2,2′-bipy)2(H2O)6(L)]?·?L?·?6H2O} (2), [Co(phen)2(H2O)(L)] (3), and [Zn(phen)2(H2O)(L)] (4) (phen = 1,10-phenanthroline and 2,2′-bipy?=?2,2′-bipyridine), have been hydrothermally synthesized and were structurally characterized by single-crystal X-ray diffraction, elemental analyses, FT-IR spectra, thermogravimetric curves, and solid luminescence spectra. Structural analysis suggests that 1 is a polymeric 1D zigzag chain bridged by dianionic L. In contrast, the other three complexes have discrete centrosymmetric binuclear structure for 2 and isolated isomorphic mononuclear entities for 3 and 4, which are further assembled into 3D supramolecular networks by abundant hydrogen-bonding and/or π–π stacking interactions. Additionally, 2 and 4 exhibit favorable luminescent emissions, suggesting they are potential candidates for light emission materials.  相似文献   

6.
Two new ZnII complexes, {[Zn(L)(phen)(H2O)]?·?H2O} (1) and {[Zn(L)(4bpy)(H2O)]?·?H2O} (2) (L?=?5,6-dihydro-1,4-dithiin-2,3-dicarboxylate, phen?=?1,10-phenanthroline, and 4bpy?=?4,4′-bipyridine), have been prepared by in situ reaction of Zn(ClO4)2?·?6H2O with 5,6-dihydro-1,4-dithiin-2,3-dicarboxylic anhydrate in the presence of lithium hydroxide, together with incorporating chelating phen or bridging 4bpy as co-ligands. Their structures were determined by single-crystal X-ray diffraction. Complex 1 takes a 1-D helical structure that is further assembled into a 2-D network by O–H?···?O, C–H?···?O hydrogen bonds, and weak S?···?S interactions, and then an overall 3-D supramolecular framework was formed by π?···?π stacking interactions. Complex 2 possesses a 2-D (4,4)-layered structure. The structural difference between 1 and 2 can be attributed to the different N-donor auxiliary co-ligands. Both 1 and 2 are photoluminescent materials whose emission properties are closely related to their intrinsic structure.  相似文献   

7.
The role of ancillary ligands, namely imidazole (im), pyridine (py), 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) in the assembly of copper(II) dipicolinate complexes are presented. Mononuclear complexes are observed in the case of monodentate ligands. The mononuclear complex [Cu(im)3L]·4H2O (1) (L = dipicolinate anion) has a distorted octahedral structure with Z′ = 2, whereas [CuL(py)(H2O)]·2H2O (2) adopts distorted square pyramidal geometry. The bidentate ligands bpy and phen favor the formation of dinuclear complexes. The dinuclear complex [CuL(bpy)(μ-L)Cu(bpy)(H2O)]·9H2O (3) has one carbonyl oxygen atom of a carboxylate group of dipicolinate acting as a bridging ligand to the copper site that is devoid of a coordinated water molecule. The complex has an angle of 83.55° between the plane of L and bpy attached to one copper site, whereas it has an angle of 78.13° between the plane L and bpy attached to the other copper site. A 1,10-phenanthroline containing dinuclear copper(II) dipicolinate complex, [Cu(phen)(H2O)(μ-L)Cu(phen)2][CuL2]·12H2O (4), has been structurally characterized. It has an unusual carboxylate bridge.  相似文献   

8.
Six complexes, [VO(L1-H)2]?·?5H2O (1), [VO(OH)(L2,3?H)(H2O)]?·?H2O (2,3), [VO(OH)(L4,5?H)(H2O)]?·?H2O (4,5), [VO(OH)(L6?H)(H2O)]?·?H2O (6), were prepared by reacting different derivatives of 5-phenylazo-6-aminouracil ligands with VOSO4?·?5H2O. The infrared and 1H NMR spectra of the complexes have been assigned. Thermogravimetric analyses (TG, DTG) were also carried out. The data agree quite well with the proposed structures and show that the complexes were finally decomposed to the corresponding divanadium pentoxide. The ligands and their vanadyl complexes were screened for antimicrobial activities by the agar-well diffusion technique using DMSO as solvent. The minimum inhibitory concentration (MIC) values for 14 and 6 were calculated at 30°C for 24–48?h. The activity data show that the complexes are more potent antimicrobials than the parent ligands.  相似文献   

9.
Three new copper(II) complexes with isonicotinic acid N-oxide (HL) and 1,10-phenanthroline (phen) as ligands, [Cu(L)(phen)(H2O)]2(NO3)2···2H2O (1), [Cu(L)(phen)(H2O)]2(ClO4)2···2H2O (2), and [Cu(L)(phen)Br]2- [Cu(L)(phen)(H2O)]2Br2···6H2O (3) have been synthesized and structurally characterized. The structures of all three complexes feature a Cu2 dimer formed by two Cu(II) ions interconnected by two bridging ligands. Each copper(II) ion has a distorted square pyramidal coordination geometry with elongated axial coordination by an aqua ligand or halogen anion. The isonicotinic acid N-oxide anion is bidentate, being coordinated to two Cu(II) ions through its N-O oxygen and one of its carboxylate oxygen atoms. Magnetic susceptibility measurements show a Curie–Weiss paramagnetic behavior characteristic of one unpaired electron for a copper(II) ion for all three complexes.  相似文献   

10.
Two new CdII complexes, [Cd( ces )(phen)] ( 1 ) and {[Cd( ces )(bpy)(H2O)](H2O)}2 ( 2 ), were prepared by slow solvent evaporation methods from mixtures of cis‐epoxysuccinic acid and Cd(ClO4)2 · 6H2O in the presence of phen or bpy co‐ligand ( ces = cis‐epoxysuccinate, phen = 1,10‐phenanthroline, and bpy = 2,2′‐bipyridine). Single‐crystal X‐ray diffraction analyses show that complex 1 has a one‐dimensional (1D) helical chain that is further assembled into a two‐dimensional (2D) sheet, and then an overall three‐dimensional (3D) network by the interchain C–H ··· O hydrogen bonds. Complex 2 features a dinuclear structure, which is further interlinked into a 3D supramolecular network by the co‐effects of intermolecular C–H ··· O and C–H ··· π hydrogen bonds as well as π ··· π stacking interactions. The structural differences between 1 and 2 are attributable to the intervention of different 2,2′‐bipyridyl‐like co‐ligands. Moreover, 1 and 2 exhibit intense solid‐state luminescence at room temperature, which mainly originates from the intraligand π→π* transitions of aromatic co‐ligands.  相似文献   

11.
Eight new palladium(II) complexes with 4-toluenesulfonyl-L-amino acid dianion and 1,4-dab/1,3-dap, [Pd(1,4-dab)(TsglyNO)]?·?H2O (1), [Pd(1,4-dab)(TsvalNO)] (2), [Pd(1,4-dab)(TsleuNO)] (3), [Pd(1,4-dab)(TsileNO)] (4), [Pd(1,4-dab)(TsserNO)]?·?0.5H2O (5), [Pd(1,4-dab)(TspheNO)]?·?0.5H2O (6), [Pd(1,4-dab)(TsthrNO)]?·?H2O (7), and [Pd(1,3-dap)(TsserNO)] (8), have been synthesized and characterized by elemental analysis, IR, UV, 1H NMR, and mass spectrometry. Crystal structure of 8 has been determined by X-ray diffraction. The cytotoxicities were tested by MTT assay. The results indicate the complexes exert cytotoxic effects against HL-60 and Bel-7402. The structure–activity relationship suggests that both amino acids and N-containing ligands have important effects on cytotoxicity, but the IC50 values do not show definite correlation with variation of these ligands.  相似文献   

12.
Four new transition metal coordination polymers, [Co(bpndc)(phen)(H2O)]n ( 1 ), [Co3(bpndc)3(2,2′‐bpy)2]n·0.5n(i‐C3H7OH) ( 2 ), and [M(bpndc)(2,2′‐bpy)2]n (M = Zn, 3 ; Cu, 4 ; H2bpndc = benzophenone ‐4,4′‐dicarboxylic acid; phen = 1,10‐phenanthroline; 2,2′‐bpy = 2,2′‐bipyridine) have been synthesized by the hydrothermal reactions and characterized by single crystal X‐ray diffraction, elemental analysis, and IR spectrum. Because of the introduction of different terminal auxiliary ligands, bpndc ligands in complexes 1 and 2 adopt different coordination modes. In complex 1 , bpndc ligands act as tridentate ligand and bridge CoII ions into 1D double‐stranded chains; while complex 2 possesses 2D (4,4) grids, where bpndc ligands adopt tetradente and pentadentate modes. Two such grids interpenetrate to form a novel catenane‐like layer. Complexes 3 and 4 are isostructural. Bpndc ligands adopt tetradentate mode and bridge metal ions forming 1D helical chains.  相似文献   

13.
Four new coordination compounds, [Zn(dba)(bpy)]n (1), {[Zn(dba)(phen)]·2H2O}n (2), [Cd(dba)(bpy)(H2O)2] (3) and [Cd2(dba)2(phen)2]n (4) (H2dba = 2,5-dihydroxy-p-benzenediacetic acid, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) have been prepared via solvothermal method and characterized by sin-gle-crystal X-ray diffraction, infrared spectroscopy, elemental analysis and powder X-ray diffraction. 1 and 2 possess 1D infinite chain structures. Complex 3 exhibits a mononuclear structure. Complex 4 owns bi...  相似文献   

14.
Two new copper(II) complexes of [Cu(Ofloxacin)(phen)(H2O)] · (NO3) · 2H2O and [Cu(Levofloxacin)(phen)(H2O)] · (NO3) · 2H2O were obtained and their structures were studies. Both ligands and complexes were assayed against gram-positive and gram-negative bacteria by the in vitro doubling dilutions method. The inhibitory effect of the ligands and complexes on the leukemia HL-60 cell line were measured with the MTT assay method and the liver cancer HePG-2 cell line measured by the SRB method. The results indicated that the complexes have stronger inhibitory effect on HL-60 than on HePG-2. The complex [Cu(Levofloxacin)(phen)(H2O)] · (NO3) · 2H2O (I) has stronger effect on HL-60 than the complex (Cu(Ofloxacin)(phen)(H2O)] · (NO3) · 2H2O (II). The text was submitted by the authors in English.  相似文献   

15.
Reactions of cadmium(II) with 5-(4-carboxybenzylamino)isophthalic acid (H3L) in the presence of 2-(pyridin-2-yl)-1H-benzo[d]imidazole (pybim) and 2,2′-bipyridine (bpy) by hydrothermal method lead to two complexes, [Cd(HL)(pybim)]·H2O (1) and [Cd2(L)(HCOO)(bpy)2(H2O)]·H2O (2). Complexes 1 and 2 have been characterized by single-crystal and powder X-ray diffraction, Infrared spectra, and elemental and thermogravimetric analyses. 1 has a double-chain structure while 2 consists of uninodal 3-connected 2-D hcb networks with (63) topology. Luminescence and sorption properties of 1 and 2 were also investigated.  相似文献   

16.
To explore the coordination possibilities of anthracene‐based ligands, three cadmium(ιι) complexes with anthracene‐9‐carboxylate ( L ) and relevant auxiliary chelating or bridging ligands were synthesized and characterized: Cd2( L )4(2bpy)2(μ‐H2O) ( 1 ), Cd2( L )4(phen)2(μ‐H2O) ( 2 ), and {[Cd3( L )6(4bpy)]} ( 3 ) (2bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, and 4bpy = 4,4′‐bipyridine). Structural analyses show that complexes 1 and 2 both take dinuclear structures by incorporating the chelating 2bpy or phen ligand, which are further interlinked by intermolecular hydrogen‐bonding, π ··· π stacking, and/or C–H ··· π supramolecular interactions to generate higher‐dimensional supramolecular frameworks. Complex 3 has a one‐dimensional (1D) ribbon‐like structure, which is further assembled into a two‐dimensional (2D) layer, and a three‐dimensional (3D) framework by the co‐effects of interchain C–H ··· O hydrogen‐bonding and C–H ··· π supramolecular interactions. Moreover, the luminescent properties of these complexes were further investigated in detail.  相似文献   

17.
Redox active mononuclear and binuclear copper(II) complexes have been prepared and structurally characterized. The complexes have planar N-donor heterocyclic bases like 1,10-phenanthroline (phen), dipyridoquinoxaline (dpq) and dipyridophenazine (dppz) ligands that are suitable for intercalation to B-DNA. Complexes studied for nuclease activity have the formulations [Cu(dpq)2(H2O)] (ClO4)2.H2O (1), [CuL(H2O)2(μ-ox)](ClO4)2 (L = bpy,2; phen,3; dpq,4; and dppz,5) and [Cu(L)(salgly)] (L = bpy,6; phen,7; dpq,8; and dppz,9), where salgly is a tridentate Schiff base obtained from the condensation of glycine and salicylaldehyde. The dpq complexes are efficient DNA binding and cleavage active species. The dppz complexes show good binding ability but poor nuclease activity. The cleavage activity of thebis-dpq complex is significantly higher than thebis-phen complex of copper(II). The nuclease activity is found to be dependent on the intercalating nature of the complex and on the redox potential of the copper(II)/copper(I) couple. The ancillary ligand plays a significant role in binding and cleavage activity.  相似文献   

18.
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   

19.
A series of transition metal coordination polymers [Co(H3L)2(4,4′- bpy)(H2O)2]n?n(4,4′-bpy) (1), [Ni(H2L)(4,4′-bpy)(H2O)2]n (2), [Co2(L)(phen)2(H2O)4]n?(H2O)2n (3), and [Ni2(L)(phen)2(H2O)4]n?(H2O)2n (4) have been assembled from a semirigid multicarboxylate ligand 3,3′-(1,4-phenylenebis(oxy))diphthalic acid (H4L) with the help of 4,4′-bipyridine (4,4′-bpy) ligand or 1,10-phenanthroline (phen) ligand. X-ray single crystal diffraction analysis reveals that complex 1 crystallizes in the space group of P − 1 and displays a one-dimensional (1D) chain structure constructed from 4,4′-bpy ligand and H3L ligand, which was further interlinked to form a three-dimensional network via hydrogen bonds. In complex 2, Ni(II) atoms are coordinated by L ligand in monodentate fashion to form alternate left- and right-helices, which are further bridged together by the coordination interactions between Ni(II) atoms and 4,4′-bpy, leading to a 2-fold (4, 4)-connected interpenetrating network. Isostructural complexes 3 and 4 belong to the space group P − 1 and display a 1D chain structure constructed from phen and L ligands, which was further interlinked to form a 2D plane via π–π interactions. In addition, their thermal and luminescent properties were also investigated.  相似文献   

20.
Five new palladium(II) complexes with 4-toluenesulfonyl-L-amino acid dianion and en, [Pd(en)(TsserNO)] (1), [Pd(en)(TsglyNO)] (2), [Pd(en)(TsalaNO)]?·?1.5H2O (3), [Pd(en)(TsleuNO)]?·?H2O (4), and [Pd(en)(TspheNO)]?·?2H2O (5), have been synthesized and characterized by elemental analysis, IR, UV, 1H NMR, and mass spectrometry. Crystal structure of 1 has been determined by X-ray diffraction analysis. The cytotoxicity was tested by MTT and SRB assays. The results indicate 15 exert cytotoxic effects against HL-60, Bel-7402, BGC-823, and KB cell lines and 5 displays the best cytotoxicity. The structure–activity relationships suggest that both amino acid and N-containing ligands have important effects on cytotoxicity.  相似文献   

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