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1.
The stoichiometric reaction of copper(II) hydroxycarbonate, iminodiacetic acid (H2IDA = HN(CH2CO2H)2) and α‐picolinamide (pya) in water yields crystalline samples of (α‐picolinamide)(iminodiacetato)copper(II) dihydrate, [Cu(IDA)(pya)] · 2 H2O ( 1 ). The compound was characterised by thermal (TG analysis with FT‐IR study of the evolved gasses), spectral (IR, electronic and ESR spectra), magnetic and single crystal X‐ray diffraction methods. It crystallises in the triclinic system, space group P1, a = 8.8737(4), b = 10.23203(5), c = 15.7167(11) Å, α = 77.61(1)°, β = 103.89(1)°, γ = 80.32(1)°, Z = 4, final R1 = 0.056. The asymmetric unit contains two crystallographic independent molecules but chemically very similar ones. The CuII atom exhibits a square base pyramidal coordination (type 4 + 1). pya acts as N,O‐bidentate ligand supplying two among the four closest donor atoms of the metal [averaged bond distances (Å): Cu–N = 1.982(2), Cu–O(amide) = 1.972(2)]. IDA plays a N,O,O′‐terdentate chelating role [averaged bond distances (Å): Cu–N = 2.004(3), Cu–O = 1.941(2) and Cu–O = 2.242(2)]. The coordinating behaviour of pya in 1 is discussed on the basis of its N,O‐bidentate chelating role and the preference of the ‘Cu‐iminodiacetato' moiety [Cu(IDA)] to link the N‐heterocyclic donor of pya in trans versus the Cu–N(IDA) bond. Consistently the ligand pya is able to impose a fac‐chelating configuration to IDA one around the copper(II) as previously has been reported to mixed‐ligand complexes having a 1/1/2 CuII/IDA/N(heterocyclic) donor ratio or a closely related 1/1/1/1 CuII/IDA/N(heterocyclic)/N(aliphatic) one.  相似文献   

2.
Pyridyl bis(N(4)‐substituted thiosemicarbazones), in which the substituents replacing the NH2 group on the thiosemicarbazone moieties are piperidyl, H2Plpip; hexamethyleneiminyl, H2Plhexim; diethylamino, H2Pl4DE; and dipropylamino, H2Pl4DP, have been synthesized. These bis(thiosemicarbazones) and their nickel(II) complexes have been characterized with IR, electronic, mass, and 1H and 13C NMR spectra. Crystal structures have been solved for H2Plpip and all four nickel(II) complexes. H2Plpip does not possess hydrogen bonding between the thiosemicarbazone moieties, but is in the Z isomeric form with intramolecular hydrogen bonding from both thiosemicarbazone moieties to pyridine nitrogen atoms. The nickel(II) complexes possess square‐planar N2S2 (i. e., imine nitrogen and thiolato sulfur atoms) centers and the two pyridine ring nitrogen atoms are not coordinated.  相似文献   

3.
Two aliphatic ether Schiff base lanthanide complexes (Ln = Eu, Ce) with bis(3‐methoxysalicylidene)‐3‐oxapentane‐1,5‐diamine (Bod), were synthesized and characterized by physicochemical and spectroscopic methods. [Eu(Bod)(NO3)3] ( 1 ) is a discrete mononuclear species and [Ce(Bod)(NO3)3DMF] ( 2 ) exhibits an inorganic coordination polymer. In the two complexes, the metal ions both are ten‐coordinated and the geometric structure around the LnIII atom can be described as distorted hexadecahedron. Under excitation at room temperature, the red shift in the fluorescence band of the ligand in the complexes compared with that of the free ligand can be attributed to coordination of the rare earth ions to the ligand. Moreover, the antioxidant activities of the two complexes were investigated. The results demonstrated that the complexes have better scavenging activity than both the ligand and the usual antioxidants on the hydroxyl and superoxide radicals.  相似文献   

4.
(PPh4)2[(SN)ReCl3(μ‐N)(μ‐NSN)ReCl3(THF)] – a Nitrido‐Thionitrosyl‐Dinitridosulfato‐Complex of Rhenium The title compound has been prepared from PPh4[ReVIICl4(NSCl)2] with excess N(SiMe3)3 in dichloromethane solution to give red‐brown single crystals after recrystallisation from acetonitrile/THF solutions. As a by‐product PPh4[ReNCl4] is formed. (PPh4)2[(SN)ReCl3(μ‐N)(μ‐NSN)ReCl3(THF)] ( 1 ): Space group P21/n, Z = 4, lattice dimensions at –80 °C: a = 1024.1(1), b = 2350.2(1), c = 2315.4(2) pm, β = 94.09(1)°, R1 = 0.0403. In the complex anion of 1 the rhenium atoms are connected by an asymmetric Re≡N–Re bridge as well as by a (NSN)4–‐bridge to form a planar Re2N(NSN) six‐membered heterocycle. Both rhenium atoms are coordinated by three chlorine atoms, one of them by a thionitrosyl ligand, the other one by the oxygen atom of a thf molecule.  相似文献   

5.
(PPh4)2[Cl2Re(N3S2)(μ‐NSN)(μ‐N≡ReCl3)]2 – a Rhenium(VII) Complex with a Nitrido, a Dinitridosulfato(II), and a Rhena‐3,5‐dithia‐2,4,6‐triazino Function The title compound has been prepared from PPh4[ReVIICl4(NSCl)2] with N(SiMe3)3 in dichloromethane solution to give red‐brown single crystals, which were suitable for a crystal structure determination. As a by‐product PPh4[ReNCl4] is formed. (PPh4)2[Cl2ReVII(N3S2)(μ‐NSN)(μ‐N≡ReVIICl3)]2 ( 1 ): Space group P21/c, Z = 2, lattice dimensions at –80 °C: a = 1280.8(2), b = 1017.5(1), c = 2467.8(3) pm, β = 95.04(1)°, R = 0.049. The complex anion of 1 consists of a planar ReN3S2‐heterocycle which is connected with the second rhenium atom by a μ‐nitrido bridge as well as by a μ‐dinitridosulfato(II) ligand to form a planar Re2(N)(NSN) six‐membered heterocycle. This [Cl2Re(N3S2)(μ‐NSN)(μ‐N≡ReCl3)] unit dimerizes via one of the N‐atoms of the (NSN)4– ligand to give a centrosymmetric Re2N2 four‐membered ring.  相似文献   

6.
Gold(III) π‐complexes have been authenticated recently with alkenes, alkynes, and arenes. The key importance of PdII π‐allyl complexes in organometallic chemistry (Tsuji–Trost reaction) prompted us to explore gold(III) π‐allyl complexes, which have remained elusive so far. The (P,C)AuIII(allyl) and (methallyl) complexes 3 and 3′ were readily prepared and isolated as thermally and air‐stable solids. Spectroscopic and crystallographic analyses combined with detailed DFT calculations support tight quasi‐symmetric η3‐coordination of the allyl moiety. The π‐allyl gold(III) complexes are activated towards nucleophilic additions, as substantiated with β‐diketo enolates.  相似文献   

7.
Four new complexes of [Cu(bpm)(ox)(H2O)] ( 1 ), [Cu(tpd)(dca)(H2O)] ( 2 ), [Cu(bppz)(N3)2] ( 3 ), and [Cu(bpm)21,3‐N3)(N3)] ( 4 ) (bpm = 2,2′‐bipyrimidine, bppz = 2,3‐bis(2‐pyridyl)pyrazine, tpd = 4‐terpyridone, dca = dicyanamide, ox = oxalate) have been prepared and characterized by X‐ray single‐crystal analysis and variable‐temperature magnetic measurements. Compounds 1–4 are essentially mononuclear Cu(II) complexes. However, in complex 1 , Cu(II) it was found that intermolecular hydrogen bonding through between H2O and ox formed 1‐D chain structure. In complex 2 it was found that the hydrogen bonding between H2O and tpd of the next molecule led to for a binuclear Cu(II) complex. In complex 3 , two nitrogen atoms, one of the pyridyl group of bppz and one of N3? ligands, are weakly coordinated to neighbor Cu(II) ion thus leading to formation of a 1‐D chain structure. In complex 4 , one nitrogen atom of terminated N3? is weakly coordinated to the neighbor Cu(II) site to form a 1‐D polymeric structure. The magnetic susceptibility measurements indicate that complex 1 and 4 exhibit a weak antiferromagnetic interaction whereas a ferromagnetic coupling has been established for complexes 2 and 3 .  相似文献   

8.
The platina‐β‐diketones [Pt2{(COR)2H}2(μ‐Cl)2] ( 1 , R = Me a , Et b ) react with phosphines L in a molar ratio of 1 : 4 through cleavage of acetaldehyde to give acylplatinum(II) complexes trans‐[Pt(COR)Cl(L)2] ( 2 ) (R/L = Me/P(p‐FC6H4)3 a , Me/P(p‐CH2=CHC6H4)Ph2 b , Me/P(n‐Bu)3 c , Et/P(p‐MeOC6H4)3 d ). 1 a reacts with Ph2As(CH2)2PPh2 (dadpe) in a molar ratio of 1 : 2 through cleavage of acetaldehyde yielding [Pt(COMe)Cl(dadpe)] ( 3 a ) (configuration index: SP‐4‐4) and [Pt(COMe)Cl(dadpe)] (configuration index: SP‐4‐2) ( 3 b ) in a ratio of about 9 : 1. All acyl complexes were characterized by 1H, 13C and 31P NMR spectroscopy. The molecular structures of 2 a and 3 a were determined by single‐crystal X‐ray diffraction. The geometries at the platinum centers are close to square planar. In both complexes the plane of the acyl ligand is nearly perpendicular to the plane of the complex (88(2)° 2 a , 81.2(5)° 3 a ).  相似文献   

9.
《Electroanalysis》2003,15(18):1476-1480
Three nickel(II)‐hexaazacyclotetradecane complexes were studied to characterize their abilities as perchlorate ion carrier in PVC membrane electrodes. The electrodes based on these complexes exhibit Nernstian responses for ClO over very wide concentration ranges (1.0×10?1 ?5.0×10?7 M) with detection limits of 2.0×10?7 ?5.0×10?7 M (20–50 ng/mL). The sensors show very good selectivity for ClO ion in comparison with the most common organic and inorganic anions. The responses of the proposed electrodes are independent of pH in the range of 3.5–11.0. The perchlorate selective membranes show fast response time (<10 s) and can be used for 4–12 weeks without any major deviation. The sensors were successfully used to determine the perchlorate ion in water, wastewater and human urine samples.  相似文献   

10.
From the reaction of K3[Cr(CN)6] and [NiL](CIO4)2 (L= 1,8‐di(hydroxyethyl)‐l, 3, 6, 8, 10, 13‐hexaazacyclotetradecane), an infinite stair‐like layered assembly [NiL]3 [Cr‐(CN)6]2‐6.5H2O is obtained, in which each hexacyanochromate(III) ion connects three nickel(II) ions using three cis Of groups and the bridging cyanide ligands coordinate to the nickel ion in a trans fashion forming trans‐NiL(N°C)2 moieties.  相似文献   

11.
Pyridil bis(N(4)‐substituted thiosemicarbazones) have been prepared in which the substituents in place of the NH2 group in the thiosemicarbazone moieties are piperidinyl (H2Plpip), hexamethyleneiminyl (H2Plhexim), diethylaminyl (H2Pl4DE), and dipropylaminyl (H2Pl4DP). IR, electronic, mass, and ESR spectra of their copper(II) complexes are reported. Crystal structure determinations of H2Pl4DE and three of the copper(II) complexes of formula [Cu(Plpip)], [Cu(Plhexim)] and [Cu(Pl4DE)]2 · 2[Cu(Pl4DE)], are included. H2Pl4DE lacks hydrogen bonding between the thiosemicarbazone moieties, but each moiety is in the Z configuration form with hydrogen bonding from the thiosemicarbazone moieties to the pyridyl nitrogen atoms. The crystal used for the structure determination of [Cu(Plhexim)] was isolated from an electrochemical preparation. In all the new compounds the deprotonated ligands are N,N,S,S‐tetradentate, coordinating to the copper(II) centre through their azomethine nitrogen atoms and their thiocarbonyl sulfur atoms.  相似文献   

12.
A two‐dimensional π‐conjugated metal‐organic framework (MOF) with long‐range delocalized electrons has been prepared and applied as modified electrode material without further post‐modification. The MOF (Cu3(HHTP)2) is composed of Cu(II) centers and a redox‐active linker (2,3,6,7,10,11‐hexahydroxytriphenylene, HHTP). Compared to most MOFs, Cu3(HHTP)2 displays higher electrical conductivity and charge storage capacity owing to the collective effect of metal ions and aromatic ligands with π–π conjugation. In order to confirm the superior properties of this material, the electrochemical detection of dopamine (DA) was conducted and the satisfactory results were obtained. The currents increase linearly with the concentration of DA in the range 5.0 × 10?8 to 2.0 × 10?4 M with a detection limit of 5.1 nM. Furthermore, Cu3(HHTP)2 presents high selectivity and applicability in serum samples for electrochemical DA sensing. Overall, this material has excellent potential as a promising platform for establishing an MOF‐based electrochemical sensor.  相似文献   

13.
Coordination polymers constructed from metal ions and organic ligands have attracted considerable attention owing to their diverse structural topologies and potential applications. Ligands containing carboxylate groups are among the most extensively studied because of their versatile coordination modes. Reactions of benzene‐1,4‐dicarboxylic acid (H2BDC) and pyridine (py) with ZnII or CoII yielded two new coordination polymers, namely, poly[(μ4‐benzene‐1,4‐dicarboxylato‐κ4O:O′:O′′:O′′′)(pyridine‐κN)zinc(II)], [Zn(C8H4O2)(C5H5N)]n, (I), and catena‐poly[aqua(μ3‐benzene‐1,4‐dicarboxylato‐κ3O:O′:O′′)bis(pyridine‐κN)cobalt(II)], [Co(C8H4O2)(C5H5N)2(H2O)]n, (II). In compound (I), the ZnII cation is five‐coordinated by four carboxylate O atoms from four BDC2− ligands and one pyridine N atom in a distorted square‐pyramidal coordination geometry. Four carboxylate groups bridge two ZnII ions to form centrosymmetric paddle‐wheel‐like Zn22‐COO)4 units, which are linked by the benzene rings of the BDC2− ligands to generate a two‐dimensional layered structure. The two‐dimensional layer is extended into a three‐dimensional supramolecular structure with the help of π–π stacking interactions between the aromatic rings. Compound (II) has a one‐dimensional double‐chain structure based on Co22‐COO)2 units. The CoII cations are bridged by BDC2− ligands and are octahedrally coordinated by three carboxylate O atoms from three BDC2− ligands, one water O atom and two pyridine N atoms. Interchain O—H…O hydrogen‐bonding interactions link these chains to form a three‐dimensional supramolecular architecture.  相似文献   

14.
15.
Two one‐dimensional (1D) coordination polymers (CPs), namely catena‐poly[[[aqua(2,2′‐bipyridine‐κ2N,N′)(nitrato‐κO)copper(II)]‐μ‐1,3‐bis(pyridin‐4‐yl)propane‐κ2N:N′] nitrate], {[Cu(NO3)(C10H8N2)(C13H14N2)(H2O)]·NO3}n ( 1 ), and catena‐poly[[[aqua(nitrato‐κO)(1,10‐phenanthroline‐κ2N,N′)copper(II)]‐μ‐1,3‐bis(pyridin‐4‐yl)propane‐κ2N:N′] nitrate], {[Cu(NO3)(C12H8N2)(C13H14N2)(H2O)]·NO3}n ( 2 ), have been synthesized using [Cu(NO3)(NN)(H2O)2]NO3, where NN = 2,2′‐bipyridine (bpy) or 1,10‐phenanthroline (phen), as a linker in a 1:1 molar ratio. The CPs were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray structure determination. The 1,3‐bis(pyridin‐4‐yl)propane (dpp) ligand acts as a bridging ligand, leading to the formation of a 1D polymer. The octahedral coordination sphere around copper consists of two N atoms from bpy for 1 or phen for 2 , two N atoms from dpp, one O atom from water and one O atom from a coordinated nitrate anion. Each structure contains two crystallographically independent chains in the asymmetric unit and the chains are linked via hydrogen bonds into a three‐dimensional network.  相似文献   

16.
To investigate the influence of the non‐covalent interactions, such as hydrogen‐bonding, π–π packing and d10–d10 interactions in the supramolecular motifs, three cyanido‐bridged heterobimetallic discrete complexes {Mn(bipy)2(H2O)[Ag(CN)2]}[Ag(CN)2] ( 1 ), {Mn(phen)2(H2O)[Au(CN)2]}2[Au(CN)2]2 · 4H2O ( 2 ), and {Cd(bipy)2(H2O)[Au(CN)2]}[Au(CN)2] ( 3 ) (bipy = 2,2′‐bipyridine, and phen = 1,10‐phenanthroline), which are based on dicyanidometallate(I) groups with 1:2 stoichiometry of metal ions and 2,2′‐bipyridyl‐like co‐ligands were synthesized and structurally characterized. In compound 1 , hydrogen bonding and π–π interactions governed the supramolecular contacts. In compound 2 , the incorporation of aurophilic, hydrogen bonding and π–π interactions result in a 3D supramolecular network. In compound 3 , hydrogen bonding and π–π stacking interactions result in a 2D supramolecular layer. In the three complexes, hydrogen‐bonding, π–π packing and/or d10–d10 interactions can play important roles in increasing the dimensionality of supramolecular assemblies.  相似文献   

17.
[Cu(C12H8N2)(C4H4O4)(H2O)]2 · C4H6O4 was prepared by the reaction of succinic acid, CuCl2 · 2 H2O, 1,10‐phenanthroline (phen = C12H8N2), and Na2CO3 in a CH3OH–H2O solution. The crystal structure (triclinic, P 1 (no. 2), a = 7.493(1), b = 9.758(1), c = 13.517(1) Å; α = 68.89(1)°, β = 88.89(1)°, γ = 73.32(1)°, Z = 1, R = 0.0308, wR2 = 0.0799 for 3530 observed reflections (F ≥ 2σ(F ) out of 3946 unique reflections) consists of hydrogen bonded succinic acid molecules and succinato bridged 1 D zipperlike supramolecular [Cu(phen)(C4H4O4)2/2(H2O)]2 double chains based on 1 D π‐π stacking interactions between the chelating phen systems at distances of 3.71 Å and 3.79 Å. The Cu atoms are fivefold trigonal bipyramidally coordinated by two N atoms of the bidentate chelating phen ligand and three O atoms of one water molecule and two bidentate bridging succinate ligands. The water O atom and one phen N atom are at the apical positions (equatorial: d(Cu–O) = 1.945, 2.254(2) Å, d(Cu–N) = 2.034(2) Å; axial: d(Cu–O) = 1.971(2) Å, d(Cu–N) = 1.995 Å).  相似文献   

18.
Fluorescence detection is the most effective tool for tracking gene delivery in living cells. To reduce photodamage and autofluorescence and to increase deep penetration into cells, choosing appropriate fluorophores that are capable of two‐photon activation under irradiation in the NIR or IR regions is an effective approach. In this work, we have developed six tetranuclear ruthenium(II) complexes, GV1–6 , and have studied their one‐ and two‐photon luminescence properties. DNA interaction studies have demonstrated that GV2–6 , bearing hydrophobic alkyl ether chains, show more efficient DNA condensing ability but lower DNA binding constants than GV1 . However, the hydrophobic alkyl ether chains also enhance the DNA delivery ability of GV2–6 compared with that of GV1 . More importantly, we have applied GV1–6 as non‐viral gene vectors for tracking DNA delivery in living cells by one‐ and two‐photon fluorescence microscopies. In two‐photon microscopy, a high signal‐to‐noise contrast was achieved by irradiation with an 830 nm laser. This is the first example of the use of transition‐metal complexes for two‐photon luminescent tracking of the cellular pathways of gene delivery and as DNA carriers. Our work provides new insights into improving real‐time tracking during gene delivery and transfection as well as important information for the design of multifunctional non‐viral vectors.  相似文献   

19.
A bioactive Schiff base HL i.e. 2‐hydroxy‐benzoic acid(3,4‐dihydro‐2H ‐naphthalen‐1‐ylidene)‐hydrazide was synthesized by reacting equimolar amount of salicylic acid hydrazide and 1‐tetralone. Co(II), Ni(II) and Zn(II) complexes of ligand HL was synthesized in 1:1 and 1:2 molar ratio of metal to ligand. The structure of the synthesized ligand and metal complexes was established by elemental analysis, molar conductance, magnetic susceptibility measurements, electronic, IR and EPR spectral techniques. For determining the thermal stability the TGA has been done. In DFT studies the geometries of Schiff bases and metal complexes were fully optimized with respect to the energy using the 6–31 + g(d,p) basis set. Spectral data reveal that ligand behave uninegative tridentate in ML complexes and uninegative bidentate in ML2 complexes. On the basis of characterization octahedral geometry has been assigned for Co(II) and Ni(II) complexes, while tetrahedral for Zn(II) complexes. Antibacterial activity of the synthesized compounds were evaluated against Staphylococcus aureus , Bacillus subtilis, Escherichia coli , Xanthomonas campestris and Pseudomonas aeruginosa and the results revealed that metal complexes show enhanced activity in comparison to free ligand.  相似文献   

20.
A pair of novel azide‐bridged polynuclear copper(II) complexes, [CuL(μ1,1‐N3)]n ( 1 ) and [Cu4L2(CH3COO)21,1‐N3)4] ( 2 ) (L = 4‐chloro‐2‐[(2‐dimethylaminoethylimino)methyl]phenolate), have been obtained from the same Schiff base ligand and an identical synthetic procedure using anions of the metal salts as the only independent variable. Complex 1 was synthesized using copper(II) nitrate, while complex 2 was synthesized using the copper(II) acetate as the salt. Both of the complexes show novel supramolecular structures in their crystals as elucidated by X‐ray analyses. The polynuclear complex 1 contains [CuL(μ1,1‐N3)]n units as the building blocks, crystallizes in the Pbca space group. The tetra‐nuclear complex 2 contains [Cu4L2(CH3COO)21,1‐N3)4] units as the building blocks, crystallizes in the space group.  相似文献   

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