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1.
Asymmetric bidentate Schiff base ligand (HL) and its cobalt(III), nickel(II), and copper(II) complexes have been synthesized (where L = 2-[(4-methoxy-2-nitrophenyl)iminomethyl]phenol). The ligand and its metal complexes have been characterized by elemental analyses (CHN) and FTIR spectroscopy. Thermogravimetric analyses of the compounds reveal their thermal stabilities along with their thermal decomposition pattern. In addition, the complexes have been used for the preparation of corresponding metal oxide nanoparticles by controlled aerobic thermal decomposed at 500 °C. The FTIR pattern of the obtained solids receals the formation of the metal oxides nanoparticles.  相似文献   

2.
Four homochiral coordination polymers incorporating two chiral reduced Schiff base ligands, namely, [Cu(L1)(H2O)]·H2O (1), [Zn2(L2)2] (2), [Co(L2)(H2O)] (3), and [Ni(L2)(H2O)] (4) (H2L1 = N-(4-carboxyl)benzyl-l-alanine, H2L2 = N-(4-carboxyl)benzyl-l-leucine) have been obtained by hydrothermal methods and characterized by physico-chemical and spectroscopic methods. X-ray crystallographic analysis reveals that complex 1 exhibits a chain structure with 1D channels. Complexes 24 all are 3D network structures with 1D channels in which the isobutyl group of the ligand points toward to the channel. Complex 2 displays strong photoluminescent emission in the purple region.  相似文献   

3.
The Ni(II) complexes [Ni(L)2](ClO4)2 (1) and [Ni(L)2(NO3)2] (2), where L is the Schiff base ligand of 4,5,9,13,14-pentaaza-benzo[b] triphenylene, were synthesized and characterized by physico-chemical and spectroscopic methods. Nano-sized particles of (1) were prepared both by sonochemistry (3) and solvothermal (4) methods. NiO nanoparticles were obtained by calcination of the nano-structure complexes at 500 °C. The structures of the nano-sized compounds were characterized by X-ray powder diffraction and scanning electron microscopy. The thermal stabilities of the bulk complexes (1–2) and nano-sized particles (3–4) were studied by thermogravimetric and differential scanning calorimetry. The catalytic activities of complexes of (1–4) are reported. The free Schiff base and its Ni(II) complexes have been screened for antibacterial activities against three Gram-positive bacteria. The metal complexes are more active than the free Schiff base. Electrochemical studies show that the Ni complexes undergo irreversible reduction in MeCN solution.  相似文献   

4.
A new Schiff base complex [Ni(H2L1)(NO3)](NO3) (1) (H2L1 = 3-[N,N′-bis-2-(5-bromo-3-(morpholinomethyl) salicylideneamino) ethyl amine]) was synthesized from reaction of the ditopic ligand H2L1 with Ni(NO3)2 in anhydrous MeOH. Complex 1 is stable in the solid state, but prone to hydrolysis. Recrystallization of 1 from wet MeOH led to the isolation of a novel unsymmetrical complex [Ni(HL2)(NO3)](NO3) (2) (HL2 = 2-[(2-(2-aminoethylamino) ethylimino) ethyl)-5-bromo-3-(morpholino methyl) salicylidene amine]). X-ray single-crystal analysis of complex 2 showed that complex 1 had undergone partial decomposition of one imine bond. In contrast, the Schiff base complex [Ni(HL3)](NO3) (3) (H2L3 = N,N′-bis(5-methyl-salicylidene) diethylenetriamine) was stable in wet methanol, and the single-crystal structure of 3 showed that the Ni(II) center was coordinated in an unsymmetrical square planar geometry. Density functional theory calculations were performed in order to obtain a geometry-optimized model of complex 1, in which the Ni(II) center was coordinated in a similar manner as that in complex 3. The thermodynamic parameters were calculated, in order to rationalize the difference in hydrolytic reactivity between complexes 1 and 3.  相似文献   

5.
A new oxidovanadium(IV) Schiff base complex, VOL2 (1), containing furfuryl pendant group was synthesized by the reaction of the related bidentate O, N-type Schiff base ligand and VO(acac)2 in the ratio of 2:1 in methanol in the reflux conditions. The Schiff base ligand and its vanadyl complex were characterized by 1H-NMR and FT-IR spectra and elemental analysis. The crystal structure of 1 was also determined the single-crystal X-ray analysis. It showed that the metal center located in a distorted tetragonal pyramidal (N2O3) geometry in which the two bidentate Schiff base ligands were coordinated to the vanadium(IV) ion in four equatorial positions, and one oxygen atom in its axial position. The catalytic activity of the vanadyl Schiff base complex was elucidated in the epoxidation of cyclooctene as a model substrate. Different reaction parameters were investigated in this reaction and the results showed that it was an effective and selective catalyst in these optimal conditions. Thermogravimetric analysis of 1 showed that it was decomposed in two stages by losing two methoxy groups and other organic residuals, respectively, in the temperature range of 253–532 °C. In addition, the vanadyl Schiff base complex (1) was thermally decomposed in air at 660 °C and the XRD pattern of the obtained solid showed the formation of the V2O5 nano-particles with the average size of 52 nm.  相似文献   

6.
Novel comparison of the structural, electronic and energy aspects of lanthanide complexes of model phosphoramides (PAs) with those of phosphine oxides (POs), phosphate esters (PEs) and phosphoryl trihalides (PHs) has been carried out by ab initio and DFT calculations. Atoms in Molecules (AIM) and Natural Bonding Orbital (NBO) analyses were performed to understand the electronic structure of ligands L and related complexes, L–Ln3+. NBO analysis indicates that the negative charge on phosphoryl oxygen (OP) and the p character of the phosphoryl lone pair, Lp(OP), increase in the order PH < PE < PO < PA. Positive charge of the lanthanide cation in PA complexes is less than those of PH, PE and PO complexes, due to the more intense ligand to metal charge transfer (LMCT). The metal–ligand distance decreases in the order PH > PE > PO > PA, which is confirmed by the results of AIM analysis. Charge density at the bond critical point of L–Ln3+ follows the sequence PH < PE < PO < PA. The results of the Energy Decomposition Analysis (EDA) indicate that the donative interaction and LMCT increases in order PH < PO < PE < PA. The effect of basis set superposition error (BSSE) on the L···Ln3+ interaction energies was also studied in detail at DFT, MP2 and CCSD(T) levels using the counterpoise (CP) method. Trends in the CP-corrected L–Ln3+ bond energies are in good accordance with the optimized OP···Ln3+ distances. The results show that the difference between CP-corrected and uncorrected interaction energies in PA complexes is larger than those in the others, because PAs are more deformable. It is depicted that PAs are comparable with POs in lanthanide complexation.  相似文献   

7.
The Schiff base bis(4-ethylbenzyl) p-phenylenediimine, 4-eb-p-phen (1), and six new dimeric Pd(II) complexes of the type [Pd(μ-X)(4-eb-p-phen)]2 {X = Cl (2), Br (3), I (4), N3 (5), NCO (6), SCN (7)} have been synthesized and characterized by elemental analysis, IR spectroscopy, and 1H and 13C{1H}-NMR experiments. The thermal behavior of the complexes 27 has been investigated by means of thermogravimetry and differential thermal analysis. From the final decomposition temperatures, the thermal stability of the complexes can be ordered in the following sequence: 3 > 4 > 7 > 2 ≈ 5 > 6. The final products of the thermal decompositions were characterized as metallic palladium by X-ray powder diffraction (XRD).  相似文献   

8.
Three new Schiff base complexes, namely [Mn(L)Cl] · H2O (1), [Co(L)Cl]2 · 2CH3COCH3 (2) and [Co(L)NCS]2 (3), where H2L = 2,2′-[propane-1,2-diylbis(nitriloeth-1-yl-1-ylidene)]diphenol, have been prepared and characterized. The syntheses of 1 and 2 have been achieved by reacting equimolar amounts of the respective metal chloride and the tetradentate Schiff base ligand (H2L). While the mononuclear Mn(III) complex 1 was obtained with MnCl2 in acetone medium, the same synthetic system yielded the binuclear Co(III) complex 2 in the presence of CoCl2. Dissolution of 1 and 2 followed by crystallization with ammonium thiocyanate in methanol yielded two isostructural phenoxo-bridged binuclear complexes, namely [Mn(L)NCS]2 (previously reported by us) and a new complex [Co(L)NCS]2 (3), respectively. All the complexes 13 have been characterized by microanalytical, spectroscopic, single crystal X-ray diffraction and other physicochemical studies. Structural studies reveal that 1 adopts a distorted tetragonal pyramidal geometry while 2 and 3 comprise dimeric Co(III) units with bridging phenolate oxygen atoms. All the complex units in 1–3 and the respective solvent molecules are held together by weak intermolecular H-bonding to constitute a supramolecular network in the solid state. The antibacterial activity of the complexes has been tested against some Gram(+) and Gram(?) bacteria.  相似文献   

9.
The combined use of 1,1,1-tris(hydroxymethyl)ethane (thmeH3) and azides in Mn carboxylate chemistry has yielded a new family of decanuclear [Mn6Na4O(N3)(O2CR)5(thme)4(H2O)4] (R = Me (1); Et (2)) complexes consisting of mixed-valence Mn 2 II Mn 4 III units with a very rare [Mn66-O)]14+ octahedral core contained within a tetrahedron of four NaI atoms. The [Mn6Na4] units of 1 and 2 are connected via the Na atoms to neighboring units, giving 3-D supramolecular assemblies with large channel cavities. Variable-temperature, solid-state dc and ac magnetization studies carried out in the 1.8–300 K range reveal that the Mn6 units of 1 and 2 are antiferromagnetically coupled to give S = 0 ground states for both complexes.  相似文献   

10.
Four new mononuclear triazido-cobalt(III) complexes [Co(L 1/2/4 )(N3)3] and [Co(L 3 )(N3)3]·CH3CN where L 1  = [(2-pyridyl)-2-ethyl]-(2-pyridylmethyl)-N-methylamine, L 2  = [(2-pyridyl)-2-ethyl]-[6-methyl-(2-pyridylmethyl)]-N-methylamine, L 3  = [(2-pyridyl)-2-ethyl]-[3,5-dimethyl-4-methoxy-(2-pyridylmethyl)]-N-methylamine, and L 4  = [(2-pyridyl)-2-ethyl]-[3,4-dimethoxy-(2-pyridylmethyl)]-N-methylamine, respectively, were synthesized and structurally characterized. The four complexes were characterized by elemental microanalyses, IR and UV–VIS spectroscopy and X-ray single crystal crystallography. The complexes display two strong IR bands over the frequency region 2,020–2,050 cm?1 assigned for the asymmetric stretching frequency, νa(N3) of the coordinated azides indicating facial geometry. The molecular structure determinations of the complexes were in complete agreement with fac-[Co(L)(N3)3] conformation in distorted octahedral Co(III) environment.  相似文献   

11.
Two Pd(II) complexes involving Schiff base ligands, namely, [Pd(L1)2] (1), [Pd2(L2)Cl2] (2) [HL1 = 2-((2,6-diisopropylphenylimino)methyl)-4,6-dibromophenol, L2 = N-(4-isopropylbenzylidene)-2,6-diisopropylbenzenamine] have been synthesized using solvothermal methods and characterized by elemental analysis, IR-spectroscopy, thermogravimetric analysis, powder X-ray diffraction, UV–vis absorption spectra, and single-crystal X-ray diffraction. Complex 1 is a mononuclear cyclometalated Pd(II) complex, whereas complex 2 is a μ-chloro-bridged dinuclear. Both 1 and 2 display photoluminescence in the solid state at 298 K and possess fluorescence lifetimes (τ 1 = 86.40 ns, τ 2 = 196.21 ns, τ 3 = 1,923.31 ns at 768 nm for 1, τ 1 = 69.92 ns, τ 2 = 136.40 ns, τ 3 = 1,714.26 ns at 570 nm for 2). The Suzuki reactions of 4-bromotoluene with phenylboronic acid by complexes 12 have also been studied.  相似文献   

12.
In this work, we have focused on the synthesis of p-tert-butyl calix[4]crown with amine units (H 3 L) as a class of selective receptors for metal ions. The macrocyclic ligand (H 3 L) with N2O7 donors was synthesized via condensation between 1,3-diaminocalix[4]arene and 2-[3-(2-formylphenoxy)-2-hydroxypropoxy] benzaldehyde, followed by reduction of the Schiff base product in situ with sodium borohydride, then it was characterized by FT-IR, 1H NMR and X-ray crystallography. Two Cu(II) complexes were prepared from the reaction of H 3 L with Cu(II) salts (CuX2, X = ClO4 ? and Cl?). FT-IR, UV–Vis, elemental analysis, molar conductivity and cyclic voltammetry techniques were used for study and characterization of these complexes. On the basis of liquid–liquid extraction experiments, ligand H 3 L indicated good affinity toward Pb2+ and Cu2+.  相似文献   

13.
Two new cobalt(III) complexes of the hexadentate ligand [1,4-bis[o-(pyridine-2-carboxamidophenyl)]-1,4-dithiobutane] (H2bpctb) with N4S2 donor set atoms have been synthesized. A reaction of Co(CH3COO)2·4H2O with (H2bpctb) leads to the formation of [CoIII(bpctb)]PF6 (1) having a CoN2(pyridine)N′2(amide)S2(thioether) coordination by symmetric bpctb2? ligand. A similar reaction under slightly different conditions, however, gives [CoIII(L a )(L b )] (2), resulting from a C–S bond cleavage reaction triggered by an acetate ion as a base, having CoN2(pyridine)N′2(amide)S(thioether)S′(thiolate) coordination. These two Co(III) complexes have been characterized by elemental analyses and spectroscopic methods, and the crystal and molecular structures of [CoIII(bpctb)]PF6 (1) in the form of the solvate (1·MeOH·H2O) and of [CoIII(L a )(L b )] (2) have been determined by X-ray crystallography. The Co atoms of both complexes exhibit distorted octahedral geometry. The electrochemical investigation of [Co(bpctb)]PF6·MeOH·H2O (1·MeOH·H2O) and [CoIII(L a )(L b )] (2) by cyclic voltammetry reveals a reversible CoIII–CoII redox process at E 1/2 = ?0.32 V (ΔE p = 80 mV); for 1, and E 1/2 = ?0. 87 V (ΔE p = 70 mV) for 2.  相似文献   

14.
A new copper(I) coordination polymer, [Cu((3,4-MeO-ba)2bn)I]n (1), using a bridging Schiff base ligand, N,N′-bis(3,4-dimethoxybenzylidene)butane-1,4-diamine, (3,4-MeO-ba)2bn, containing a flexible spacer (=N–CH2–CH2–CH2–CH2–N=) has been synthesized and characterized by elemental analyses (CHN) and FTIR spectroscopy, thermal analysis and powder X-ray structure analysis. In 1, Cu(I) ions are bridged by Schiff base ligands and iodine atoms forming 1D-chain. The thermal stability of 1 was studied by thermal gravimetric and differential thermal analyses. 1 is used to prepare CuO nanoparticles via solid state thermal decomposition in air and nanoparticles thus formed are characterized by scanning electron microscopy, transmission electron microscopy and powder X-ray diffraction techniques.  相似文献   

15.
Three new Pd(II) complexes of Schiff base ligands, namely, [Pd4(L1)4] (1), [Pd2(L2)2Cl2] (2) and [Pd(L3)2Cl2] (3) [HL 1 ?=?N-(benzylidene)-2-aminophenol; L 2 ?=?N-(2,4-dichlorobenzylidene)-2,6-diethylbenzenamine, L 3 ?=?4-(2,4-dichlorobenzylide-neamino)phenol] have been synthesized using solvothermal methods and characterized by elemental analysis, spectroscopy and single crystal X-ray diffraction. The crystal structures of the free ligands were also determined. The ??-oxygen-bridged tetranuclear cyclometallated Pd(II) complex (1) contains four nearly planar units, in which PdII is four-coordinate. Complex 2 is a ??-chloro-bridged dinuclear cyclometallated Pd(II) complex, whereas complex 3 is mononuclear. The Heck reactions of bromobenzene with acrylic acid catalyzed by complexes 1?C3 have also been studied.  相似文献   

16.
The interaction of Cu(II), Fe(III) and Co(III) with 6,6,13-trimethyl-13-amino-1,4,8,11-tetraazacyclotetradecane (L 3 ) incorporating a pendent amine group has led to isolation of the new octahedral complexes [Cu(HL 3 )(ClO4)2]Cl·H2O (1), [Fe(L 3 )Cl](S2O6)·H2O (2), [Co(L 3 )Cl](ClO4)1.5Cl0.5·0.25H2O (3), [Co(HL 3 )Cl2](ClO4)2·H2O (4) and [Co(L 3 )Cl]2(S2O4)(ClO4)2 (5). In (1) the copper ion occupies the macrocyclic cavity of protonated (–NH3 +) L 3 which is present in its trans-III configuration; weakly bound ClO4 ? ligands occupy the axial positions. The X-ray structure of (2) showed that Fe(III) occupies the N4-macrocyclic cavity of L 3 in a trans-III configuration, with the pendent amine group binding in an axial position. The remaining axial position is occupied by a Cl? ligand. Chromatography of the product obtained from the reaction of Na3[Co(CO3)3] with L 3 yielded three fractions. Fraction 1 yielded crystals (3) composed of three crystallographically independent species incorporating cations of type [Co(L 3 )Cl]2+ with very similar structures; in each case the macrocyclic ring nitrogens of L 3 are bound to the Co(III) in an asymmetric cis-fashion. Fraction 2 yielded the trans-III octahedral cationic complex (4) incorporating L 3 in its protonated form. The Co(III) complex (5) from fraction 3 shows a different coordination arrangement to the products from fractions 1 or 2. The macrocyclic ring coordinates in its trans-III form, but the axial sites in this case are occupied by the pendent-NH2 group and a Cl? ligand.  相似文献   

17.
A new open-cubane MnIII, [{(H2O)MnIIIL}{MnIIIL}]2·2(CH3OH).2(CH3CH2OH)·2Cl, 1 where H 2 L=[N-(2-hydroxyethyl)-3-methoxysalicylaldimine] has been synthesized and characterized by element analysis, FT-IR, solid UV–Vis spectroscopy and single crystal X-ray diffraction. The crystal structure determination shows an open-cubane tetranuclear complex. The Mn1 (Mn1i) ions is hexacoordinate by NO5 donor sets while the Mn2 (Mn2i) is pentacoordinate by NO4 donor sets. The solid state photoluminescence properties of complex 1 and its ligand H 2 L have been investigated under UV light at 349 nm in the visible region. H 2 L exhibits blue emission while complex 1 shows orange-red emission at room temperature. Variable-temperature magnetic susceptibility measurements on the complex 1 in the range 2–300 K indicate an antiferromagnetic interaction.  相似文献   

18.
The reactions of a racemic four-coordinate Ni(II) complex [Ni(rac-L)](ClO4)2 with l- and d-alanine in acetonitrile/water gave two six-coordinate enantiomers formulated as [Ni(RR-L)(l-Ala)](ClO4)·2CH3CN (1) and [Ni(SS-L)(d-Ala)](ClO4) (2) (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclo-tetradecane, Ala? = alanine anion), respectively. Evaporation from the remaining solutions gave two four-coordinate enantiomers characterized as [Ni(SS-L)](ClO4)2 (S-3) and [Ni(RR-L)](ClO4)2 (R-3), respectively. Single-crystal X-ray diffraction analyses of complexes 1 and 2 revealed that the Ni(II) atom has a distorted octahedral coordination geometry, being coordinated by four nitrogen atoms of L in a folded configuration, plus one carboxylate oxygen atom and one nitrogen atom of l- or d-Ala? in mutually cis-positions. Complexes 1 and 2 are supramolecular stereoisomers, constructed via hydrogen bonding between [Ni(RR-L)(l-Ala)]+ or [Ni(SS-L)(d-Ala)]+ monomers to form 1D hydrogen-bonded zigzag chains. The homochiral natures of complexes 1 and 2 have been confirmed by CD spectroscopy.  相似文献   

19.
The reaction of Fe(III) with the substituted salicylaldehydes [X-saloH, where X = 3-OCH3 (L 1 ), 5-CH3 (L 2 ), 5-Cl (L 3 ), 5-NO2 (L 4 )] led to the formation of four new iron(III) hetero-heptanuclear complexes (Fe–Na) under the general formula [Fe2(X-salo)8Νa5] · 3OH · zH2Ο. The two different coordination modes of the ligand, as well as the geometry around the metal ions were deduced by X-ray structure analysis of compound 1, [Fe2(3-OCH3-salo)8Νa5] · 3OH · 8H2Ο. The complexes have also been characterized by physicochemical and spectroscopic (IR, UV–Vis, Mössbauer) methods.  相似文献   

20.
Three new coordination complexes of Zn(II) and Mn(II) have been synthesised using two different tridentate N,N,O donor hydrazone ligands, Hpbh and Hacpbh respectively. The complexes [Zn(pbh)2] (1) and [Zn(acpbh)2] (2) have been synthesized by the treatment of ZnSO· 7H2O with Hpbh and Hacpbh hydrazone ligands, respectively. The Mn(II) complex [Mn(acpbh)2] (3) was obtained on reacting Mn(NO3)· 4H2O with the ligand Hacpbh. The ligands Hpbh and Hacpbh were prepared by condensing pyridine-2-carboxaldehyde and 2-acetylpyridine with benzhydrazide respectively. Inspite of varying the carbonyl functionality attached to the pyridine moiety present in the hydrazone ligands in both the Schiff bases, we obtained three mononuclear complexes 1, 2, and 3 which were clearly characterized from single crystal X-ray diffraction studies. Spectroscopic investigations like IR and UV/Vis have been carried out for 1, 2, and 3. Fluorescence studies have been performed for 1 and 2. For 3 cyclic voltammetry, room temperature magnetic study and EPR measurements have been recorded.  相似文献   

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