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1.
Thiosemicarbazides and their metal complexes have attracted considerable interest because of their biological activities and their flexibility, which allows the ligands to bend and rotate freely to accommodate the coordination geometries of various metal centres. Discrete copper(II) and cadmium(II) complexes have been prepared by crystallization of N‐[2‐(2‐hydroxybenzoyl)hydrazinecarbonothioyl]propanamide (H3L) with Cu(CH3COO)2 or Cd(NO3)2 in a dimethylformamide/methanol mixed‐solvent system at room temperature, affording the complexes di‐μ‐acetato‐bis{μ4‐1‐[(2‐oxidophenyl)carbonyl]‐2‐(propanamidomethanethioyl)hydrazine‐1,2‐diido}tetracopper(II) dimethylformamide disolvate, [Cu4(C11H10N3O3S)2(C2H3O2)2]·2C3H7NO, (I), and bis{μ2‐[(2‐hydroxyphenyl)formamido](propanamidomethanethioyl)azanido}bis[(4,4′‐bipyridine)nitratocadmium(II)] dihydrate, [Cd2(C11H12N3O3S)2(NO3)2(C10H8N2)2]·2H2O, (II). Complex (I) consists of four CuII cations, two μ4‐bridging trianionic ligands and two μ2‐bridging acetate ligands, while complex (II) is composed of two CdII cations, two μ2‐bridging monoanionic ligands, two nitrate ligands and two 4,4′‐bipyridine ligands. These discrete complexes are connected by hydrogen bonds and van der Waals interactions to form a three‐dimensional supramolecular architecture. Compared with (I), the phenolic hydroxy group and hydrazide N atom of the thiosemicarbazide ligand of (II) are not involved in coordination and lead to a binuclear CdII complex. This different coordination mode may be attributed to the larger ionic radius of the CdII ion compared with the CuII ion.  相似文献   

2.
葛春华  张向东  关伟  郭放  刘祁涛 《中国化学》2005,23(8):1001-1006
Three complexes Cu(ppca)2(H2O)2(NO3)2 (1), Cu2(μ-OH)2(ppca)2(H2O)4)·(ClO4)2 (2) and Cu2(μ-CH3COO)4(ppca)2(3) have been synthesized by the reaction of copper(Ⅱ) salts with N-phenyl-4-pyridinecarboxamide (ppca) and characterized. For anions, in complex 1, NO3^- coordinated with copper(Ⅱ), in complex 2 perchlorate anion did not take part in coordination, the copper(Ⅱ) cations were connected by μ-OH to form a dinuclear unit, and complex 3 had a dimeric copper(Ⅱ) carboxylate paddle-wheel core. Noncovalent interactions linked these complexes to form supramolecular networks. Different coordinating modes of anions controlled modes of intennolecular interactions, which resulted in different final structures.  相似文献   

3.
The title dinuclear CuII complex, [Cu2(C7H8NO2)2(C7H9NO2)2](CH3COO)2, has been synthesized by the reaction of Cu(CH3COO)2·H2O with pdmH2 (pdmH2 is pyridine‐2,6‐diyldi­methanol) in the presence of tetra­butyl­ammonium hydro­xide. The title complex contains a centrosymmetric Cu2O2 core and each CuII atom has distorted octahedral geometry. Molecular [Cu2(pdmH)2(pdmH2)]2+ cations are connected by hydrogen bonds involving the CH3COO anions, forming one‐dimensional chains along the a axis.  相似文献   

4.
Pure anhydrous Cu(CH3COO)2 was obtained both, by thermal dehydration of Cu(CH3COO)2 · H2O and by drying a commercially purchased mixture of Cu(CH3COO)2 · H2O and Cu(CH3COO)2 in a nitrogen atmosphere using P2O5 as drying agent. The crystal structure was solved ab initio from synchrotron X‐ray powder diffraction (XRPD) data at 150 °C and from laboratory XRPD data at ambient conditions and found to be isotypic to anhydrous chromium(II), molybdenum(II) and rhodium(II) acetate. Cu(CH3COO)2 crystallizes in space group P1 (no. 2) with lattice parameters of a = 5.1486(3) Å, b = 7.5856(6) Å, c = 8.2832(6) Å, α = 77.984(4)°, β = 75.911(8)°, γ = 84.256(6)° at ambient conditions. Cu2(CH3COO)4 paddle wheels with short (2.6 Å) Cu–Cu distances form chains in a direction, which is the main motif in the crystal structure. Due to their identical structural main motif Cu(CH3COO)2 · H2O and Cu(CH3COO)2 exhibit a similar bluish‐green color, almost identical UV/Vis spectra and comparable magnetic properties. The temperature dependent magnetic susceptibility also indicates only weak inter‐dimer spin exchange between neighbouring Cu2(CH3COO)4 paddle wheels.  相似文献   

5.
The coordinating properties of a new bis(pyridylhydrazone) ligand derived from iminodiacetic acid diethyl ester and 2-pyridinecarboxaldehyde (picolinaldehyde) H3Imdp and of the bis(salicylhydrazone) H5Imds and H4MeImds ligands derived, respectively, from iminodiacetic acid diethyl ester and from methyl-iminodiacetic acid diethyl ester and salicylaldehyde were considered, by means of analytical and spectroscopic methods, towards first row transition metal ions. These ligands showed various coordination modes in complexation with Cu(II), Co(II), Mn(II) and Zn(II) ions. In particular, we have synthesized and characterized, by analytical, 1H NMR and IR techniques, tri-, di- and mononuclear metal complexes of formula Co3(HImdp)(NO3)4·2H2O, Cu3(HImdp)(NO3)4·C2H5OH·H2O, Cu3(HImdp)Cl4, Zn2(H3Imdp)(ClO4)4·2H2O, Co3(HImds)Cl2·CH3OH·H2O, Zn2(H3Imds)Cl2·2H2O, Co(H4Imds)NO3·2H2O, Mn(H4Imds)Cl·CH3OH·H2O, Cu(H3Imds)·CH3OH·H2O and Cu(H2MeImds).CH3OH·3H2O. Antibacterial, antifungal and antiprotozoal properties of H5Imds and H3Imdp together with three copper(II) trinuclear species of H5Imds of formula Cu3(HImds)(NO3)2.2CH3OH·2H2O, Cu3(HImds)(ClO4)2.EtOH·2H2O and Cu3(HImds)SO4·4H2O are also discussed. The H5Imds ligand and their trinuclear copper(II) complexes showed good activities versus Trichomonas vaginalis, Staphylococcus epidermidis and Acanthamoeba castellanii.  相似文献   

6.
1-(2-Pyridyl)benzotriazole (L1) and 1-(4-pyridyl)benzotriazole (L2) with transition metal cations Co(II), Ni(II) and Cu(II) give four coordination complexes, [{Cu(L1)2(H2O)2} · 2NO3] (1), [{Co(L1)2(H2O)2} · 2NO3] (2), [Ni(L2)2(NO3)2(H2O)2] (3), and [Cu2(L2)2(CH3COO)4] (4). In 14, different supramolecular frameworks are formed through hydrogen bonding and/or π–π interactions.  相似文献   

7.
Three new diclofenac‐based copper(II) complexes, namely tetrakis{μ‐2‐[2‐(2,6‐dichloroanilino)phenyl]acetato‐κ2O:O′}bis(methanol‐κO)copper(II), [Cu2(μ‐dicl)4(CH3OH)2] ( 1 ), bis{2‐[2‐(2,6‐dichloroanilino)phenyl]acetato‐κ2O,O′}bis(1‐vinyl‐1H‐imidazole‐κN3)copper(II), [Cu(dicl)2(vim)2] ( 2 ), and bis{2‐[2‐(2,6‐dichloroanilino)phenyl]acetato‐κ2O,O′}bis(1H‐imidazole‐κN3)copper(II), [Cu(dicl)2(im)2] ( 3 ) [dicl is diclofenac (C14H10Cl2NO2), vim is 1‐vinylimidazole (C5H6N2) and im is imidazole (C3H4N2)], have been synthesized and characterized by elemental analysis, FT–IR spectroscopy, thermal analysis and single‐crystal X‐ray diffraction. X‐ray diffraction analysis shows that complex 1 consists of dimeric units in which the dicl ligand exhibits a bidentate syn,syn‐μ2 coordination mode linking two copper(II) centres. Complexes 2 and 3 have mononuclear units with the general formula [Cu(dicl)2L2] (L is vim or im) in which the CuII ions are octahedrally coordinated by two L and two dicl chelating ligands. The L and dicl ligands both occupy the trans positions of the coordination octahedron. The different coordination modes of dicl in the title complexes were revealed by Fourier transform IR (FT–IR) spectroscopy. The spin matching between the copper(II) centres in the dimeric [Cu2(μ‐dicl)4(CH3OH)2] units was also confirmed by magnetic data to be lower than the spin‐only value and electron paramagnetic resonance (EPR) spectra. The thermal properties of the complexes were investigated by thermogravimetric (TG) and differential thermal analysis (DTA) techniques.  相似文献   

8.
A carboxylate-bridged Cu(II)–Gd(III) complex, [GdCu(CH2CH(CH3COO)4(H2O)4] n (NO3) n , was prepared and characterized. Single crystal X-ray analysis reveals the complex as a carboxylate-bridged 1-D Cu(II)–Gd(III) coordination polymer. The magnetic measurement showed this complex exhibiting weak ferromagnetic behavior.  相似文献   

9.
Three Cu(II) complexes: [Cu2(μ-L)2(HCOO)2(H2O)2] (1), [Cu2(μ-L)2(NO3)2] (2), and [Cu4(μ-L)6(CH3COO)2]·2H2O (3) constructed from 2-(1H-pyrazol-3-yl) pyridine (HL) were synthesized and structurally characterized by X-ray single-crystal diffraction. The X-ray analyses revealed that all three complexes feature a di-ligand-bridged Cu2 unit, which is nearly planar. Each deprotonated ligand chelates one copper atom by means of N,N(pyridine-pyrazole) pocket and simultaneously bridges the other one by the N,N(pyrazole) groups. The remaining coordination sites of the Cu(II) centers are either occupied by different anionic coligands to balance the charge, or bridged by another L to develop a tetranuclear structure. Magnetic investigations reveal that the distortion of the Cu(II) coordination geometry (as described by the τ values) and the coplanarity of the Cu–(N=N)2–Cu unit have cooperative effects on the antiferromagnetic strength of these systems.  相似文献   

10.
Three flavonoid copper(II) complexes Cu2(quercetin)(CH3COO)3(CH3OH) ( 1 ), Cu(anthrarufin)(CH3COO)·1/2H2O ( 2 ) and Cu(naringin)(OCH3)(CH3OH)2 ( 3 ) have been synthesized and characterized by elemental analysis, IR, electronic absorption and EPR (X‐band) spectroscopy. The complexes have a strong protective action over the Δsod1 mutant of S. cerevisiae against reactive oxygen radicals generated by an external source of free radicals (H2O2 or the superoxide‐generating, menadione). On the other hand, the complexes cleave DNA efficiently even in the absence of reducing agents. The main reactive oxygen species responsible for the DNA strand cleavage have been determined using radical scavengers. A probably mechanism of the DNA damage is proposed.  相似文献   

11.
5-Ferrocenylpyrimidine (FcPM) reacts with dinuclear copper(II) carboxylates ([Cu2(RCOO)4]; R = C6H5, C5H11, CH3) to produce one-dimensional coordination polymers [Cu2(C6H5COO)4(FcPM)]n (1), [Cu2(C5H11COO)4(FcPM)]n · nCH3CN (2), and a discrete tetranuclear complex [Cu2(CH3COO)4(FcPM)2] (3). Compounds 1 and 2 show similar zigzag chain structures, comprising alternate linking of FcPM and dinuclear copper(II) units, whereas the structure of 3 corresponds to the local structural motifs of 1 and 2. Reaction of FcPM with zinc salts (ZnX2; X = NO3, SCN) affords zinc-centered ferrocenyl cluster complexes, [Zn(NO3)2(FcPM)3] (4) and [Zn(SCN)2(FcPM)2] · 0.5H2O (5), with varying M:L ratios. FcPM acts as a bidentate ligand in 1 and 2, and as a monodentate ligand in the others.  相似文献   

12.
The crystal structures of the title complexes, namely trans‐bis­(iso­quinoline‐3‐carboxyl­ato‐κ2N,O)­bis­(methanol‐κO)cobalt(II), [Co(C10H6NO2)2(CH3OH)2], and the corresponding nickel(II) and copper(II) complexes, [Ni(C10H6NO2)2(CH3OH)2] and [Cu(C10H6NO2)2(CH3OH)2], are isomorphous and contain metal ions at centres of inversion. The three compounds have the same distorted octahedral coordination geometry, and each metal ion is bonded by two quinoline N atoms, two carboxyl­ate O atoms and two methanol O atoms. Two iso­quinoline‐3‐carboxyl­ate ligands lie in trans positions, forming the equatorial plane, and the two methanol ligands occupy the axial positions. The complex mol­ecules are linked together by O—H⋯O hydrogen bonds between the methanol ligands and neighbouring carboxyl­ate groups.  相似文献   

13.
A covalent mononuclear complex, [Cu(p–HOC6H4COO)2(cyclam)] (1), and two ionic mononuclear complexes, [Cu(cyclam)(H2O)2](p–CH3OC6H4COO)2 (2) and [Cu(cyclam)(H2O)2](p–CH3(CH2)15OC6H4COO)2·H2O (3), were formed from reaction of cyclam with [Cu2(p–HOC6H4COO)4(H2O)2], [Cu2(p–CH3OC6H4COO)4(H2O)2] and [Cu2(p-CH3(CH2)15OC6H4COO)4(H2O)2], respectively. These complexes were isolated as purple crystals with molecular structures showing distorted octahedral N4O2 geometry. Complexes 1 and 2 were irreversibly reduced to Cu(I) and oxidized to Cu(III), while 3 was redox inactive. Complex 2 reacted with N-(hexadecyl)isonicotinamide (L) to form [Cu(cyclam)(L)2](p–CH3OC6H4COO)2 (4). These complexes were thermally stable (Tdec > 200 °C for 13 and 174 °C for 4). Complexes 3 and 4 behaved as ionic liquids (melting temperatures lower than 100 °C) and exhibited mesomorphism.  相似文献   

14.
Four new Cu(II) complexes of 4,4??-diaminodiphenyl sulfone (DDS) with different anions (chloride, sulfate, nitrate or acetate) were synthesized and characterized by elemental analysis, electronic absorption, IR, magnetic moment, thermal analysis and powder X-ray diffraction studies. It was found that the pure DDS and complex [Cu2(DDS)2(NO3)2].(NO3)2 (3) crystallize in orthorhombic system while the complexes [Cu2(DDS)2].Cl4 (1), [Cu2(DDS)2].(SO4)2 (2), and [Cu2(DDS)2].(CH3COO)4 (4) crystallize in monoclinic system. The crystallite sizes of complexes have smaller values as compared to pure DDS. Infrared studies suggest that the coordination of NH2 of DDS with Cu(II) ion. The binding of the complexes with calf thymus (CT) DNA was investigated by electronic absorption titration, fluorescence measurements and DNA thermal denaturation. The spectroscopic studies together with the DNA melting studies indicated that the complexes may bind to CT-DNA in a non-intercalative mode.  相似文献   

15.
Four Schiff base complexes, [Cu2(L1)2(μ‐NCS)2] ( 1 ), [Cu2(L2)2(μ‐N3)2] ( 2 ), Cu[Cu(CH3COO)(L3)]2 ( 3 ), and [Zn{Zn(C3H4N2)(L3)}2(NO3)](NO3) ( 4 ) (where L1 = 2‐[(pyridin‐2‐ylmethylimino)methyl]phenol, L2 = 1‐[(pyridin‐2‐ylmethylimino)methyl]naphthalen‐2‐ol, and L3 = bis(salicylidene)‐1, 3‐propanediamine), were synthesized and characterized by elemental analyses, infrared spectroscopy, and single crystal X‐ray determinations. Both 1 and 2 are structurally similar di‐nuclear complexes, which are located at crystallographic inversion centers (with the center of the central Cu2N2 ring). In 1 , each copper atom has a slightly distorted square pyramidal configuration, coordinated by two nitrogen atoms and one oxygen atom from L1 and another two terminal nitrogen atoms from two bridging thiocyanate anions. The Cu···Cu separation is 3.466(3) Å. The structure of 2 is similar to that of 1 , with Cu···Cu separation of 3.368(2) Å. Both 3 and 4 are linear tri‐nuclear complexes. In 3 , the central Cu2+ ion is located on an inversion centre and has a distorted octahedral coordination involving four bridging O atoms from two Schiff base ligands (L3) in the equatorial plane and one O atom from each bridging acetate group in the axial positions. The coordination around the terminal Cu2+ ions is irregular‐square pyramidal, with two O and two N atoms of L3 in the basal plane and one O atom from an acetate group in the apical position. The acetate bridges linking the central and terminal Cu2+ ions are mutually trans. The Cu···Cu separation is 3.009(3) Å. In 4 , the coordination configuration of the central and the terminal zinc atoms are similar to that of the 3 , with Zn···Zn separation of 3.153(4) Å. The three Schiff bases and the corresponding three copper complexes exhibit good antibacterial properties, while the zinc complex 4 has nearly no.  相似文献   

16.
[Cu2(UO2)4(suc)4(pac)4] (1), [(Cu(H2O)2)(4,4′-bipy)2][(UO2)2(H2O)2(Hca)2]·3H2O (2), and [(Cu(H2O)2)(UO2)(bta)]·4H2O (3) were synthesized by the reaction of succinic acid and 3-pyridinecarboxylic acid, citric acid and 4,4′-bipyridine, or 1,2,4,5-benzenetetracarboxylic acid ligands with Cu(NO3)2·3H2O and UO2(CH3COO)2·2H2O. The complexes were characterized by IR and UV–vis spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction, and photoluminescence spectroscopy. Photocatalytic activities of the complexes were also investigated.  相似文献   

17.
The organic ligand (1-methyl-1H-benzo[d]imidazol-2-yl)methanol (HL1) was used to react with Cu(ClO4)2·6H2O and triethylamine at 80°C to afford the complex [Cu4(L1)6]·(ClO4)2·CH3CN ( 1 ). Every four-coordinated Cu(II) ion is surrounded with NO3 coordinated environment, and every five-coordinated Cu(II) ion is surrounded with N2O3 coordinated environment. Changing the metal salt to Zn(NO3)2·6H2O, and after adding CH3COONa, afforded the complex [Zn4(L1)4(NO3)2(CH3COO)2] ( 2 ), in which every five-coordinated Zn(II) ion is surrounded with NO4 coordinated environment. High-resolution electrospray ionization mass spectrometry results revealed that complex 1 broke into the most stable fragment [Cu2(L1)3]+, and it also can assemble high nuclear peaks in solution. For complex 2 , it was found that the complex exhibited different component distribution in solution. Not only were there substitutions between coordinated anions, but the high nuclear peaks could also be detected.  相似文献   

18.
The new mixed ligand complexes with formulae M(4-bpy)(C2H5COO)2·2H2O (where M(II)=Mn, Co, Ni; 4,4'-bpy or 4-bpy=4,4'-bipyridine) and Cu(4-bpy)0.5(C2H5COO)2·H2O were prepared and characterized by VIS (for solid compounds of Co(II), Ni(II), Cu(II) in Nujol), IR spectroscopy, X-ray powder diffraction and molar conductance in MeOH, DMF or DMSO. Thermal behaviour of complexes was studied under static conditions in air atmosphere. Corresponding metal oxides were identified as final products of pyrolysis. A coupled TG-MS system was used to analysis of principal volatile thermal decomposition and fragmentation products of isolated complexes under dynamic air and argon atmosphere. The principal species correspond to: C+, OH+, H2O+, NO+, CO2 + and other; additionally CO+ in argon atmosphere. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

19.
Three new copper(II) complex compounds with chlorhexidine diacetate as a ligand have been prepared and characterized by elemental and thermogravimetrical analyses, molar conductances, magnetic susceptibility measurements, infrared, electronic and EPR spectra. The complexes correspond to the formulas: [Cu2(CHX)Cl4]·2C2H5OH, [Cu2(CHX)Br4]·2C2H5OH and [Cu2(CHX)(CH3COO)2] (CH3COO)2·2C2H5OH, where CHX = chlorhexidine, their composition and stereochemistry depending on the reaction conditions and the metal salt used. Chlorhexidine acts as neutral tetradentate NNNN donor, coordinating through the four imine nitrogen atoms. Investigations on antimicrobial activity in vitro show that all the complexes are active against the tested microorganisms, the complex with chloride being more active against Gram negative bacteria than chlorhexidine diacetate..   相似文献   

20.
Single crystals of 2D coordination network {Cu2 L 2 ⋅ (DMF)3(H2O)3}n ( 1-DMF ) were prepared by reaction of commercial reagents 3-formyl-4-hydroxybenzoic acid (H2 L ) and Cu(NO3)2 in dimethylformamide (DMF). The single-crystal structure shows two distinct Cu(II) coordination environments arising from the separate coordination of Cu(II) cations to the carboxylate and salicylaldehydato moieties on the linker, with 1D channels running through the structure. Flexibility is exhibited on solvent exchange with ethanol and tetrahydrofuran, while porosity and the unique overall connectivity of the structure are retained. The activated material exhibits type I gas sorption behaviour and a BET surface area of 950 m2 g−1 (N2, 77 K). Notably, the framework adsorbs negligible quantities of CH4 compared with CO2 and the C2Hn hydrocarbons. It exhibits exceptional selectivity for C2H2/CH4 and C2H2/C2Hn, which has applicability in separation technologies for the isolation of C2H2.  相似文献   

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