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1.
Solid complexes of rare earth nitrates with a new amide type podand ligand, 2,3-bis{[(2′-benzylaminoformyl)phenoxyl]methyl}quinoxaline (L), were prepared. These complexes were characterized by elemental analysis, conductivity measurements and IR spectroscopy. Spectrographic analyses suggest that the complexes show a similar coordination mode. At the same time, the luminescence properties of the Eu(Ⅲ) and Tb (Ⅲ) complexes were also studied.  相似文献   

2.
Solid complexes [REL(NO3)3]n with novel (10,3)-a type three-dimensional networks structure have been assembled using rare earth nitrates and an amide type semirigid tripodal bridging ligand, 1,3,5-tris {[(2′-benzylaminoformyl)phenoxyl]methyl}benzene (L), as building blocks. The complexes were crys- tallized in the orthorhombic system with chiral space group P212121. The whole structure consists of an infinite array of trigonal RE(III) ions bridged by tridentate ligands, and a novel (10,3)-a net is formed, which is very uncommon in the rare earth complexes. At room temperature, the Sm(III), Eu(III), Tb(III), Dy(III) complexes all exhibited characteristic luminescence emissions of central metal ions under UV light excitation.  相似文献   

3.
Amide-type tripodal ligands have been used as ac-tive materials in ion-selective electrodes, ion recogni-tion and ion-transfer carrier, etc.,1-3 but their lanthanide complexes have not yet attracted much attention in spite of their high tendency to coordinate towards Ln(III) ions. The first three dimensional network of Eu(III) complex, which contains 1,1,1-tris{[(2-benzylaminoformyl)- phenoxy]methyl}propane (the hexadentate ligand) and Eu(NO3)3 as building block, assembled by coordination …  相似文献   

4.
Two new zinc(Ⅱ) complexes, [Zn2L2Ch].2[ZnL(CH3OH)Cl2] 1 and [ZnL2(NO3)2] 2, were synthesized by reacting ZnX2.nH2O (X = Cl^-, NO3^-) and a Schiff base ligand 2-[(4-methylphenylimino)methyl]-6-methoxyphenol (C15HIsNO2, L) which was obtained by the condensation of o-vanillin (2-hydroxy-3-methoxybenzaldehyde) with p-toluidine. Both 1 and 2 were characterized by single-crystal X-ray diffraction technique, elemental analysis, molar conductance, FT-IR, UV-Vis, IH-NMR spectra and thermogravimetrie analysis. The Schiff base ligand and its zinc(Ⅱ) complexes have been tested in vitro to evaluate their antibacterial activity against bacteria, viz., Escherichia Coli, Staphylococcus aureus and Bacillus Subtilis. The results show that these complexes have higher activity than the corresponding free Schiff base ligand against the same bacteria.  相似文献   

5.
The present paper covers the synthesis and the characterization of ligand 2-decyl-3, 6, 9-tris (car-boxymethyl)-3,6,9-triazaundecan-1,11-dioic acid, HsL, and its Gd (Ⅲ) chelate. The protonation constantsfor HsL(IgKi^H= 10. 90, 8.50, 4.55, 2.92., 2.20) and the stability constant for GdL^2- (lgKGdL^2- = 2.2.80)were determined by means of potentiometric titration. They are similar to the corresponding values of DTPAand Gd-DTPA, respectively. The results obtained show that the basicity of the ligand and the stability con-stant of its Gd (Ⅲ) chelate are not obviously altered after the introduction of a linear chain decyl group intothe terminal acetic acid residue of DTPA. The Gd(Ⅲ) chelate may be a potential contrast agent with liver-specificity for magnetic resonance imaging(MRI).  相似文献   

6.
A novel podand ligand using crown ether as skeleton and N-benzylsalicylamide as functional arms, 4,5-bi{2′-methylbenzeneaminoformyl)phenoxyl]methyl}-benzo-12-crown-4 (L), and its rare earth nitrate complexes have been synthesized. These complexes were characterized by elemental analysis, conductivity measurements and IR spectroscopy. Spectrographic analyses suggest that the complexes show a similar coordination mode. At the same time, the luminescent properties of the Eu(Ⅲ) and Tb(Ⅲ) complexes were also studied.  相似文献   

7.
Two zinc(Ⅱ) complexes, namely, [Zn(L_1)Cl_2]_2(1) and {[Zn(L_2)(tbta)]·3H_2O}n(2)(L_1 = 1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2 tbta = tetrabromoterephthalic acid, L2_ = 1,3-bis(2-methylbenzimidazol-1-yl)-2-propanol), have been successfully obtained under hydrothermal conditions. Complex 1 displays a binuclear structure which is further extended into a 1D supramolecular chain through π-π stacking. Complex 2 features a 2D(4,4) network based on a L2/tbta2- double linker. The thermal stability, fluorescence properties and catalytic activities of two complexes for the degradation of methyl orange in a Fenton-like process were discussed.  相似文献   

8.
A new supramolecular compound, {[Cd(L)2]2[PMo12O40NO3]·CH3CN·2H2O}n 1 (L is 1,4-bis(4-imidazolyl)-2,3-diaza-1,3-butadiene), based on Cd(II)-Schiff-base and Keggin- type [PMo12O40]3- was synthesized via self-assembly and structurally characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a = 12.0128(11), b = 13.6196(13), c = 13.9995(13) , α = 103.868(2), β = 95.225(2), γ = 101.024(2)°, V = 2160.0(3) 3, Z = 1, C34H39N26O45Cd2Mo12P, Mr = 2938.96, Dc = 2.259 g/cm3, μ = 2.276 mm-1, F(000) = 1400, the final R = 0.0565 and wR = 0.1613 for 4973 observed reflections with I 2σ(I). The crystal structure can be described by the packing of Keggin anionic and Metal-Schiff-base cationic layers.  相似文献   

9.
Two new metal-organic frameworks, {[Cd2CI(HL)(H20)2"0.5H20]}n (1) and {[Cd2L(H20)2]'H20}n (2), have been hydrothermally synthesized with designed ligand H4L (HaL = 1,3,5-triazine-2-iminodiacetic acid-4,6-biglycine) under the same condition except for different pH values. Single-crystal X-ray determination shows that they are 3-D frameworks. Complex 1 crystallizes in monoclinic, space group P21/n. Complex 2 crystallizes in triclinic, space group Pi. The photoluminescence properties of those two complexes have been investigated in solid state. Complexes 2 exhibited remarkable blue luminescence emissions with high quantum yield of 40.3% On the other hand, complexes 1 featured weak quantum yields of 13.7%.  相似文献   

10.
Two 2D layer complexes {[La(TBTA)1.5(phen)2H2O]·3H2O}n (1) and {[Ce(TBTA)1.5(phen)2H2O]·3H2O}n (2) (H2TBTA = 2,3,5,6-tetrabromoterephthalic acid, phen = 1.10-phenanthroline) have been synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra and thermogravimetric analyses. Both crystals belong to monoclinic, space group P21/n. Crystal data for 1: a = 8.7097(11), b = 34.276(4), c = 13.7281(17) , β = 95.397(2)o, V = 4080.1(9) 3, Z = 4, LaC36H24Br6N4O10, Mr = 1290.96, Dc = 2.102 g/cm3, μ(MoKα) = 6.983 mm-1, F(000) = 2460.0, T = 296(2) K, the final R (I > 2σ(I)) = 0.0478 and wR (all data) = 0.0985 for 10127 independent (Rint = 0.0775) and 7137 observed reflections with I > 2σ(I). Crystal data for 2: a = 8.709(2), b = 34.202(9), c = 13.685(4), β = 95.714(4), V = 4055.9(19)3, Z = 4, CeBr6C36H24O10N4, Mr = 1292.17, Dc = 2.116 g/cm3, μ(MoKα) = 7.094 mm-1, F(000) = 2464.0, T = 296(2) K, the final R (I > 2σ(I)) = 0.0590 and wR (all data) = 0.1453 for 10014 independent (Rint = 0.1253) and 6081 observed reflections with I > 2σ(I). Both complexes are allomerism with the general molecular formula of {[M(TBTA)1.5(phen)2H2O]·3H2O}n. In the structures, the H2TBTA ligands adopt a monodentate coordination mode. Both the 2D layer frameworks are further extended to be 3D layers via H-bonding interactions.  相似文献   

11.
IntroductionLanthanidecomplexeshaveattractedmuchattentionbecauseoftheirimportantapplications .1InparticularEu(III)andTb(III)canbecharacterizedbylong lived(mstimescale)andstrongluminescentelectronicallyex citedstates ,whichmakesthemimportantinanalyticalchem…  相似文献   

12.
New copper(II) complexes of asymmetrical tetradentate Schiff bases containing pyrazine have been prepared and thoroughly characterised by elemental analysis, IR and electronic spectroscopy, mass spectrometry and magnetic measurements. Two alternative methods were used in the isolation of the complexes: template synthesis in the preparation of Cu(SalDpyz)ClO4 (HSalDPyz = derived from the condensation of salicylaldehyde, acetylpyrazine and 1,2‐ethylendiamine, 2‐methyl‐1,2‐propylendiamine, 1,2‐phenylendiamine) and direct interaction between copper perchlorate and the corresponding Schiff base, as in the isolation of Cu(AEPyz)(ClO4) (HAEPyz = (Z)‐4‐[2‐{[2‐{[(E)‐1‐(pyrazinyl)ethylidene]amino} ethyl)amino]‐3‐penten‐2‐one)]. [Cu(SalEn)(py)(OClO3)][Cu(SalEn)(py)]ClO4 ( 1 ) (SalEn = 4‐(2‐hydroxyphenyl)‐3‐aza‐3‐buten‐1‐amino, py = pyridine), metal precursor in the preparation of Cu(SalEnpyz)(ClO4) (HSalEnpyz = 2‐{E(2‐{[(E)‐1‐(2‐pyrazinyl)ethylidene]amino}ethyl)imino]methyl}phenol), was crystallographically characterised. The crystal structure of [Cu(AEpyz)]ClO4 ( 2 ) is also reported.  相似文献   

13.
A simple and effective synthetic route to homo‐ and heteroleptic rare‐earth (Ln = Y, La and Nd) complexes with a tridentate Schiff base anion has been demonstrated using exchange reactions of rare‐earth chlorides with in‐situ‐generated sodium (E)‐2‐{[(2‐methoxyphenyl)imino]methyl}phenoxide in different molar ratios in absolute methanol. Five crystal structures have been determined and studied, namely tris(2‐{[(2‐methoxyphenyl)imino]methyl}phenolato‐κ3O1,N,O2)lanthanum, [La(C14H12NO2)3], ( 1 ), tris(2‐{[(2‐methoxyphenyl)imino]methyl}phenolato‐κ3O1,N,O2)neodymium tetrahydrofuran disolvate, [La(C14H12NO2)3]·2C4H8O, ( 2 )·2THF, tris(2‐{[(2‐methoxyphenyl)imino]methyl}phenolato)‐κ3O1,N,O23O1,N,O22N,O1‐yttrium, [Y(C14H12NO2)3], ( 3 ), dichlorido‐1κCl,2κCl‐μ‐methanolato‐1:2κ2O:O‐methanol‐2κO‐(μ‐2‐{[(2‐methoxyphenyl)imino]methyl}phenolato‐1κ3O1,N,O2:2κO1)bis(2‐{[(2‐methoxyphenyl)imino]methyl}phenolato)‐1κ3O1,N,O2;2κ3O1,N,O2‐diyttrium–tetrahydrofuran–methanol (1/1/1), [Y2(C14H12NO2)3(CH3O)Cl2(CH4O)]·CH4O·C4H8O, ( 4 )·MeOH·THF, and bis(μ‐2‐{[(2‐methoxyphenyl)imino]methyl}phenolato‐1κ3O1,N,O2:2κO1)bis(2‐{[(2‐methoxyphenyl)imino]methyl}phenolato‐2κ3O1,N,O2)sodiumyttrium chloroform disolvate, [NaY(C14H12NO2)4]·2CHCl3, ( 5 )·2CHCl3. Structural peculiarities of homoleptic tris(iminophenoxide)s ( 1 )–( 3 ), binuclear tris(iminophenoxide) ( 4 ) and homoleptic ate tetrakis(iminophenoxide) ( 5 ) are discussed. The nonflat Schiff base ligand displays μ2‐κ3O1,N,O2O1 bridging, and κ3O1,N,O2 and κ2N,O1 terminal coordination modes, depending on steric congestion, which in turn depends on the ionic radii of the rare‐earth metals and the number of coordinated ligands. It has been demonstrated that interligand dihedral angles of the phenoxide ligand are convenient for comparing steric hindrance in complexes. ( 4 )·MeOH has a flat Y2O2 rhomboid core and exhibits both inter‐ and intramolecular MeO—H…Cl hydrogen bonding. Catalytic systems based on complexes ( 1 )–( 3 ) and ( 5 ) have demonstrated medium catalytic performance in acrylonitrile polymerization, providing polyacrylonitrile samples with narrow polydispersity.  相似文献   

14.
A novel family of four 1‐bromo‐2,6‐bis{[(λ5‐phosphanylidene)imino]methyl}benzene ligands has been synthesized and characterized. The phosphiniminomethyl substituents are decorated with either three phenyl groups, two phenyl and one cyclohexyl group, one phenyl and two cyclohexyl groups, or three cyclohexyl groups. Each ligand was metallated using zero‐valent nickel through an oxidative addition to form a family of organonickel(II) complexes, namely (2,6‐bis{[(triphenyl‐λ5‐phosphanylidene)imino]methyl}phenyl‐κ3N,C1,N′)bromidonickel(II) dichloromethane hemisolvate, [NiBr(C44H37N2P2)]·0.5CH2Cl2, (2,6‐bis{[(cyclohexyldiphenyl‐λ5‐phosphanylidene)imino]methyl}phenyl‐κ3N,C1,N′)bromidonickel(II) diethyl ether hemisolvate, [NiBr(C44H49N2P2)]·0.5C4H10O, (2,6‐bis{[(dicyclohexylphenyl‐λ5‐phosphanylidene)imino]methyl}phenyl‐κ3N,C1,N′)bromidonickel(II), [NiBr(C44H61N2P2)], and (2,6‐bis{[(tricyclohexyl‐λ5‐phosphanylidene)imino]methyl}phenyl‐κ3N,C1,N′)bromidonickel(II), [NiBr(C44H73N2P2)]. This family of complexes represents a useful opportunity to investigate the impact of incrementally changing the steric characteristics of a complex on its structure and reactivity.  相似文献   

15.
Oxidovanadium(IV) complexes [VO(L1)(phen)] ? Cl ( 1 ) and [VO(L2)(L3)] ? Cl ( 2 ), in which HL1 is 2‐{[(benzimidazol‐2‐yl)methylimino]‐methyl}phenol (sal‐ambmz), HL2 is 2‐[({1‐[(anthracen‐9‐yl)methyl]‐benzimidazol‐2‐yl}methylimino)‐methyl]phenol (sal‐an‐ambmz), phen is 1,10‐phenanthroline and L3 is dipyrido[3,2‐a:2′,3′‐c]phenazine (dppz) conjugated to a Gly‐Gly‐OMe dipeptide moiety, were prepared, characterized, and their DNA binding, photoinduced DNA‐cleavage, and photocytotoxic properties were studied. Fluorescence microscopy studies were performed by using complex 2 in HeLa and HaCaT cells. Complex 1 , structurally characterized by X‐ray crystallography, has a vanadyl group in VO2N4 core with the VO2+ moiety bonded to N,N‐donor phen and a N,N,Odonor Schiff base. Complex 2 , having an anthracenyl fluorophore, showed fluorescence emission bands at 397, 419, and 443 nm. The complexes are redox‐active exhibiting the V(IV)/V(III) redox couple near ?0.85 V versus SCE in DMF 0.1 M tetrabutylammonium perchlorate (TBAP). Complex 2 , having a dipeptide moiety, showed specific binding towards poly(dAdT)2 sequence. The dppz‐Gly‐Gly‐OMe complex showed significant DNA photocleavage activity in red light of 705 nm through a hydroxyl radical (.OH) pathway. Complex 2 showed photocytotoxicity in HaCaT and HeLa cells in visible light (400–700 nm) and red light (620–700 nm), however, the complex was less toxic in the dark. Fluorescence microscopy revealed the localization of complex 2 primarily in mitochondria. Apoptosis was found to occur inside mitochondria (intrinsic pathway) caused by ROS generation.  相似文献   

16.
Tin(IV) complexes of the series of dianionic terdentate Schiff bases N‐[(2‐pyrroyl)methylidene]‐N′‐tosylbenzene‐1,2‐diamine, (H2L1), N‐[(2‐hydroxyphenyl)methylidene]‐N′‐tosylbenzene‐1,2‐diamine (H2L2) and some R substituted 2‐{[(2‐hydroxyphenyl)imino]methyl}phenols [R = H (H2L3), 4,6‐(OCH3)2 (H2L4), 3‐(OC2H5) (H2L5) and 3,5‐Br2 (H2L6)] have been synthesized. The compounds were obtained by the electrochemical oxidation of a tin anode in a cell containing an acetonitrile solution of the corresponding ligand. The complex [SnL12] was also obtained by reaction of SnCl2·2H2O and H2L1 in methanol in the presence of triethylamine. The crystal structure of the ligand [H2L6] and the complexes [SnL12] (1) , [SnL22] (2) , [SnL32] (3) and [SnL62] (6) were determined by X‐ray diffraction. In the complexes, the tin atom is in an octahedral environment coordinated by two dianionic terdentate ligands. Spectroscopic data for the complexes (IR, 1H and 119Sn NMR and mass spectra) are discussed and related to structural information.  相似文献   

17.
Two two‐dimensional supramolecular copper(II) and cobalt(III) complexes, Cu(L1)2 ( 1 ; HL1 = 2‐hydroxy‐3‐methoxybenzaldehyde oxime) and [Co(L2)2]2⋅2CH3COOCH2CH3 ( 2 ; HL2 = 1‐(2‐{[(E )‐3‐methoxy‐2‐hydroxybenzylidene]amino}phenyl)ethanone oxime), have been synthesized via complexation of Cu(II) nitrate trihydrate and Co(II) acetate tetrahydrate with HL. A plausible reaction mechanism for the formation of HL1 is proposed. HL was synthesized and characterized using infrared, 1H NMR and 13C NMR spectra, as well as elemental analysis. Complexes 1 and 2 were investigated using single‐crystal X‐ray diffraction and have a 2:1 ligand‐to‐metal ratio. Different geometric features of both complexes are observed. In their crystal structures, 1 and 2 form infinite two‐dimensional structures and 2 forms a three‐dimensional supramolecular framework. Electron paramagnetic resonance spectra of 1 and 2 were also investigated. Moreover, thermal and electrochemical properties and antimicrobial activity of 2 were also studied. In addition, the calculated HOMO and LUMO energies show the character of complex 1 .  相似文献   

18.
A series of novel complexes of the type Cu(II)(Ln)2(H2O)2]xH2O [where Ln = L 1–4 , these ligands being described as: L 1 , 2‐({4‐[6,7‐dihydrothieno[3,2‐c]pyridin‐5(4H)‐ylsulfonyl]phenylimino}methyl)phenol, x = 1; L 2 , 2‐({4‐[6,7‐dihydrothieno[3,2‐c] pyridin‐5(4H)‐ylsulfonyl]phenylimino}methyl)‐5‐(methoxy)phenol, x = 2; L 3 , 5‐chloro‐2‐({4‐[6,7‐dihydrothieno[3,2‐c]pyridin‐5(4H)‐ylsulfonyl]phenylimino}methyl)phenol, x = 2; and L 4 , 5‐bromo‐4‐chloro‐2‐({4‐[6,7‐dihydrothieno[3,2‐c]pyridin‐5(4H)‐ylsulfonyl]phenylimino} methyl)phenol, x = 1] was investigated. They were characterized by elemental analysis, IR, 1H‐NMR, 13C‐NMR and electronic spectra, magnetic measurements and thermal studies. The FAB‐mass spectrum of [Cu(II)( L 1 )2(H2O)2]H2O was determined. A magnetic moment and reflectance spectral study revealed that an octahedral geometry could be assigned to all the prepared complexes. Ligands (Ln) and their metal complexes were screened for their in vitro antibacterial activity against Bacillus subtillis, Pseudomonas aeruginosa, Escherichia coli and Serratia marcescens bacterial strains. Kinetic parameters such as order of reaction (n), the energy of activation (Ea), the pre‐exponential factor (A), the activation entropy (ΔS), the activation enthalpy (ΔH) and the free energy of activation (ΔG) are reported. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

19.
Three tripodal ligands H3L1–3 containing imidazole rings were synthesized by the reaction of 1,10‐phenanthroline‐5,6‐dione with 1,3,5‐tris[(3‐formylphenoxy)methyl]benzene, 1,3,5‐tris[(3‐formylphenoxy)methyl]‐2,4,6‐trimethylbenzene, and 2,2′,2"‐tris[(3‐formylphenoxy)ethyl]amine, respectively. Trinuclear RuII polypyridyl complexes [(bpy)6Ru3H3L1–3](PF6)6 were prepared by the condensation of Ru(bpy)2Cl2 · 2H2O with ligands H3L1–3. The pH effects on the UV/Vis absorption and fluorescence spectra of the three complexes were studied, and ground‐ and excited‐state ionization constants of the three complexes were derived. The three complexes act as “off‐on‐off” fluorescence pH switch through protonation and deprotonation of imidazole ring with a maximum on‐off ratio of 5 in buffer solution at room temperature.  相似文献   

20.
Two two‐dimensional supramolecular Nickel(II) and Cobalt(III) complexes, [Ni( L 2 )2]·2CH3OH ( 1 ) and [2Co( L 2 )2] ( 2 ) ( HL 2  = 1‐(2‐{[(E)‐3‐bromo‐5‐chloro‐2‐hydroxybenzylidene]amino}phenyl)ethanone oxime), were synthesized via complexation of salts acetate with HL 1 (2‐(3‐bromo‐5‐chloro‐2‐hydroxyphenyl)‐4‐methyl‐1,2‐dihydroquinazoline 3‐oxide, H is the deprotonatable hydrogen). During the reaction, the C–N bond in HL 1 is converted into the C=N–OH group in HL 2 . The spectroscopic data of both complexes were compared with the ligand HL 1 . HL 1 and both complexes were determined by single‐crystal X‐ray crystallography. The differently geometric features of the obtained complexes 1 and 2 are observed. In the crystal structure, 1 and 2 form an infinite 1‐D chain‐like and 2‐D supramolecular frameworks. EPR spectroscopy of 2 was investigated. Moreover, electrochemical properties and antimicrobial activities of both complexes were also studied. In addition, the calculated HOMO and LUMO energies show the character of HL 1 , complexes 1 and 2 . The electronic transitions and spectral features of HL 1 and both complexes were discussed by TD‐DFT calculations.  相似文献   

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