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1.
A mesogenic Schiff base, N,N′-di-(4-hexadecyloxysalicylidene)diaminoethane, H2dhdsde (abbreviated as H2L1) that exhibit smectic-C (SmC) mesophase, was synthesized and its structure studied by elemental analyses, mass, NMR & IR spectra and single crystal XRD (triclinic space group with Z = 1) techniques. Bi-dentate bonding of the Schiff base in the mesogenic LaIII complex was implied on the basis of IR & NMR spectral data. As per the spectral studies of the complexes, the Zwitterionic species of the ligand (H2L1) coordinates to LnIII ion through two phenolate oxygens rendering the overall geometry around the metal ion to distorted square antiprism (Ln = La, Pr, Nd, Sm, Eu) and monocapped octahedron (Ln = Gd, Tb, Dy, Ho).  相似文献   

2.
Reactions of H2L [H2L = N,N′-bis(3-methoxysalicylidene)propane-1,2-diamine] and Ln(NO3)3 · 6H2O give rise to two different mononuclear 4f complexes, namely, {[(H2L)La(NO3)3(MeOH)] · H2O}n (1) and [(H2L)Nd(NO3)3] (2). Further additions of Cu(Ac)2 · H2O to the mononuclear 4f complexes yield expected heterodinuclear Cu-4f complexes [LCu(Me2CO)Ln(NO3)3] (3, Ln = Nd; 4, Ln = Eu; 5, Ln = Dy). Complex 1 is a unique 1D polymeric chain structure, and 2 is one of the few structurally characterized discrete hexadentate salen-type mononuclear 4f complexes. Complexes 3-5 are similar to their analogues. However, they are prepared by a reversed synthetic route in contrast to their isomorphic complexes. Electrochemical behavior of heterodinuclear Cu-4f complexes 3-5 has been examined by cyclic voltammetry in acetonitrile. The redox potential of heterodinuclear Cu-4f complexes 3-5 shows significant anodic shift comparing to that of mononuclear copper complex (LCu). A tendency of anodic shift was observed in a sequence of 3 < 4 < 5. This results from the modulating effect of coordination geometry around Cu(II) ion on redox potential.  相似文献   

3.
The syntheses and X-ray crystal structures of the Eu, Gd, Dy, Ho, and Er nitrate complexes of the pentadentate ligand 2,6-diacetylpyridine bis acetic acid hydrazone, or H2dapaah, are reported. The complexes can be divided into 3 groups depending on the number of water molecules per metal ion. The Ln · 4H2O complexes with Eu, Gd and Dy are isomorphous, with the Ln ion being 10 coordinate. The Ln · 6H2O group includes Ho and Er, where the cation is 9 coordinate. The final complex Gd · 5H2O is 10 coordinate like the Eu, Gd and Dy complexes, but the additional water molecule has stabilized an ordered crystal. The bond valence sum method has been used to analyze the bonding in the complexes and has suggested that bond valence equalization in three dimensions may be an important concept.  相似文献   

4.
Chemical implantation of Group 4 cations [Ti(III), Ti(IV), Zr(IV), Hf(IV)] has been carried out under mild conditions by the reaction of polycyclopentadienyl- (MCpn; M = Ti, n = 3, 4; M = Zr, Hf, n = 4), mixed cyclopentadienyl/N,N-dialkylcarbamato (MLx(O2CNEt2)y; M = Ti, L = Cp, C5Me5 (Cp*), x = 2, y = 1; M = Hf, L = Cp, x = 1, y = 3), and N,N-dialkylcarbamato (M(O2CNR2)n, M = Ti, n = 3, R = iPr; M = Ti, Hf, n = 4, R = Et; M = Zr, n = 4, R = iPr) derivatives, with the silanol groups of amorphous silica. Cyclopentadiene/pentamethylcyclopentadiene and/or carbon dioxide and the secondary amine are released in the process. The amount of implanted cations depends on the metal and on the ligands, the pentamethylcyclopentadienyl complex being less reactive than the unsubstituted congener. The starting complexes and the final products have been characterized by EPR or by 13C CP-MAS NMR spectroscopy.  相似文献   

5.
Some new dimethoxyethane (DME) adducts of lanthanide trichlorides of formula [LnCl3(DME)2]n, n=1 or 2; (n=2, Ln=La, Ce, Pr, Nd; n=1, Ln=Eu, Tb, Ho, Tm, Lu) have been prepared by treating Ln2O3, or LnCl3 · nH2O, or Ln2(CO3)3, in DME as medium, with thionyl chloride at room temperature, eventually in the presence of water in the case of Ln2O3 and Ln2(CO3)3. The complexes from lanthanum to praseodymium included are chloro-bridged dimers. In the case of neodymium, the new results complement the literature data, showing that both the mononuclear and dinuclear species exist: neodymium can therefore be regarded as the turning element from dinuclear to mononuclear structures along the series. Only mononuclear complexes were isolated in the Eu-Lu sequence. The lanthanide contraction has been evaluated on the basis of the Ln-O and Ln-Cl bond distances on the isotypical series of the mononuclear complexes LnCl3(DME)2 covering a range of 12 atomic numbers.  相似文献   

6.
The solution structures of the lanthanide complexes, [Ln(L)(NO3)3] and [Ln(L)2(NO3)3], where L = bis(diphenylphosphorylmethyl)mesitylene and Ln = La, Ce, Nd, Er, were investigated by 31P NMR and IR spectroscopy, conductivity and sedimentation analysis. Variable-temperature 31P{1H} NMR spectroscopy was used to identify species present in solution and to monitor their interconversions. The results indicate that equilibrium between molecular complexes [Ln(L)n(NO3)3]0 and cationic species (as ion pairs [Ln(L)n(NO3)2]+ · (NO3) and as free ions [Ln(L)n(NO3)2]+, throughout n = 1, 2) in solutions can be observed by 31P{1H} NMR spectroscopy due to separate detection of the molecular complexes and cationic species. The chelate coordination of the ligand and nitrate ions is retained in all complex species at ambient temperature except for [Er(L)2(NO3)3]. The crystal structure of [Nd(L)(NO3)3(MeCN)]MeCN was determined by X-ray diffraction.  相似文献   

7.
In order to explore the electronic effects of Ru(II) complexes binding to DNA, a series of Ru(II) complexes [Ru(phen)2 (p-MOPIP)]2+ (1), [Ru(phen)2 (p-HPIP)]2+ (2), and [Ru(phen)2(p-NPIP)]2+ (3) were synthesized and characterized by elementary, 1H NMR, and ES-MS analysis. The binding properties of these complexes to CT-DNA were investigated with spectroscopic methods and viscosity experiments. Furthermore, the computations for these complexes applying the density functional theory (DFT) method have also been performed. The results show that all of these complexes can well bind to DNA in intercalation mode and DNA-binding affinity of these complexes is greatly influenced by electronic effects of intercalating ligands. The intrinsic binding constants for 1, 2, and 3 are 0.20, 0.69, and 1.56 × 105 M−1, respectively. This order is in accordance with that of the electron-withdrawing ability of substituent [-OR < -OH < -NO2]. Such a trend in electronic effects of Ru(II) complexes binding to DNA can be reasonably explained by the DFT calculations.  相似文献   

8.
Potentiometric titrations of N,N-bis(2-hydroxyethyl)glycine (bicine) in the presence of Ln(III) cations (Ln=La, Pr, Nd and Eu) in the pH range extended to ca. 9.5 reveal formation of two types of binuclear hydroxo complexes Ln2(bic)2(OH)4 and Ln2(bic)(OH)4 + (bicH=bicine) in addition to previously reported mononuclear mono- and bis-complexes Ln(bic)2+ and Ln(bic)2 +, which predominate at pH below 8. 1H NMR titrations of La(III)-bicine mixtures in D2O show that the complex formation with bicine is slow in the NMR time scale and confirm formation of hydroxide rather than alkoxide complexes in basic solutions. Formation of a different type of hydroxide species under conditions of an excess of metal over ligand is confirmed by studying the absorption spectra of the Nd(III)-bicine system in the hypersensitive region. The binuclear hydroxide complexes are predominant species at pH above 9 and their stabilities increase in the order La < Pr ≈ Nd < Eu. They show fairly high catalytic activity in the hydrolysis of bis(4-nitrophenyl) phosphate (BNPP) at room temperature. Comparison of concentration and pH-dependences of the reaction rates with the species distribution diagrams shows that the catalytic hydrolysis of BNPP proceeds via a Michaelis-Menten type mechanism, which involves the Ln2(bic)(OH)4 + complex as the reactive species. The values of the catalytic rate constants and the Michaelis constants are in the range 0.002-0.004 s−1 and 0.35-1.5 mM, respectively, for all lanthanides studied. The half-life for the hydrolysis of BNPP is reduced from 2000 years to ca. 10 min at 25 °C and pH 9.2 in the presence of 5 mM La(III) and 2.5 mM bicine.  相似文献   

9.
The synthesis and characterization of rare-earth (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) thiocyanate adducts with tripiperidinophosphine oxide (tpppO) with general formula (RE)(SCN)3(tpppO)3 are reported. Conductance measurements in acetonitrile indicate the non-electrolytic nature of the complexes. Infrared absorption spectra evidence that the SCN ion coordinates through the nitrogen atom (isothiocyanate form) and that tpppO coordinates through the phosphoryl oxygen. X-ray powder patterns suggest the existence of three different crystal forms: (1) La; (2) an isomorphous series including Ce, Nd and Pr; and (3) another isomorphous series, including Sm, Gd, Eu, Ho, Er, Tb, Lu and Y. The visible spectra of the Nd adduct and the calculated parameters β = 0.98, b1/2 = 0.072 and δ = 1.06 indicate that the metal-ligand bonds are essentially electrostactic. The emission spectra of the Eu compound showed 5D0 → 7FJ bands (J = 0, 1, 2), suggesting a C3v symmetry for the coordination polyhedron. The lifetime of the 5D0 state is 1.28 ms. The emission spectra of the Tb complex presented 5D4 → 7FJ bands (J = 4, 5, 6) and the Dy complex showed the 4F9/2 → 6H13/2 band. The structure of the Pr complex showed that the coordination polyhedron is a trigonal antiprism, with the isothiocyanate anions in one base and three tpppO ligands in the other. Thermal analyses (TG-DTG) were carried out for the Ce, Nd and Gd adducts. Mass losses start between 250 and 334 °C. The final residues at 1300 °C are the corresponding phosphates.  相似文献   

10.
Synthesis and spectroscopic characterization of new lanthanide complexes [Ln(QAD)3(EtOH)(H2O)], (Ln = Tb, Eu; HQAD = 1-phenyl-3-methyl-4-adamantylcarbonyl-pyrazol-5-one), [H3O][Tb(QAD)4], [Ln(QAD)3(N-N)] (Ln = Tb, Eu; N-N = 1,10-phenanthroline (Phen), 2,2′-bipyridyl (Bipy), 4,4′-dimethyl-2,2′-bipyridyl (4,4′-Me2Bipy)) are reported. The crystal structures of the proligand HQAD and of complexes [H3O][Tb(QAD)4] and [Tb(QAD)3(4,4′-Me2Bipy)] have been determined. In both complexes the lanthanide ions are in a square antiprismatic environment, the H3O+ cation in the former acid complex being stabilized by H-bonding. Luminescence studies have been performed on selected derivatives.  相似文献   

11.
New solid complex compounds of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III) and Gd(III) ions with morin were synthesized. The molecular formula of the complexes is Ln(C15H9O7)3 · nH2O, where Ln is the cation of lanthanide and n = 6 for La(III), Sm(III), Gd(III) or n = 8 for Ce(III), Pr(III), Nd(III) and Eu(III). Thermogravimetric studies and the values of dehydration enthalpy indicate that water occurring in the compounds is not present in the inner coordination sphere of the complex. The structure of the complexes was determined on the basis of UV-visible, IR, MS, 1H NMR and 13C NMR analyses. It was found that in binding the lanthanide ions the following groups of morin take part: 3OH and 4CO in the case of complexes of La, Pr, Nd, Sm and Eu, or 5OH and 4CO in the case of complexes of Ce and Gd. The complexes are five- and six-membered chelate compounds.  相似文献   

12.
Five new supramolecular lanthanide coordination polymers with three different structures, {[La2(IA)3(phen)2] · 2H2O}n (1), {[Ln(IA)1.5(phen)] · xH2O}n [x = 1, Ln = Eu (2); x = 0.25, Ln = Dy (3)], and [Ln(IA)1.5(phen)]n [Ln = Er (4); Yb (5)], were prepared by hydro- and solvothermal reactions of lanthanide chlorides with itaconic acid (H2IA) and 1,10-phenanthroline (phen), and structurally characterized by single crystal X-ray diffraction. 1 Comprises 1-D double-chains that are further assembled to a 3-D supramolecular structure via hydrogen bonds and π-π stacks between phen molecules. 2 and 3 have 2-D infinite networks which are further constructed to form 3-D supramolecular architectures with 1-D channels by π-π aromatic interactions. 4 and 5 have 2-D layer structures consisting of three types of rings which are further architectured to form 3-D supramolecular structures by C-H?O hydrogen bonds. The H2IA ligands are all completely deprotonated and exhibit tetra-, penta-, and hexadentate coordination modes in the titled complexes. The high-resolution emission spectrum of 2 shows only one Eu3+ ion site in 2, which is in agreement with the result of X-ray diffraction. And the magnetic property and the thermal stability of 2 were also investigated.  相似文献   

13.
Six lanthanide two-dimensional network coordination polymers with the general formula of [Ln(pmida)(NO3)(H2O)]n, where Ln = La (1), Nd (2), Sm (3), Gd (4), Dy (5), Er (6) and pmida2− = N-(2-pyridylmethyl)iminodiacetate, have been synthesized by hydrothermal process and characterized by elemental analysis, Infrared spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. All crystals are isostructural and crystallize in the monoclinic space group P21/a. The lanthanide(III) ion is nine-coordinated in a geometry of distorted tricapped trigonal prism by two N atoms and two O atoms from one pmida2− ligand, two bridging carboxylate O atoms from other two pmida2− ligands, two O atoms of a bidentate chelating nitrate and a O atom of a coordinated water molecule. The luminescent properties of [Sm(pmida)(NO3)(H2O)]n (3) and [Dy(pmida)(NO3)(H2O)]n (5) were investigated.  相似文献   

14.
The reaction of halflanthanidocene aryloxides CpR′Ln(OArtBu,R)2 (Ln = Y, La, Lu; CpR′ = C5Me5, C4Me4H; R = H, Me) and halflanthanidocene alkoxides [(C5Me5)Ln(OCH2CMe3)2]2 (Ln = Y, Lu) with trimethylaluminum (TMA) was investigated. Monomeric CpR′Ln(OArtBu,R)2, derived from the ortho-tBu-substituted OC6H2tBu2-2,6-R-4 (R = H, Me) ligands, form mono(tetramethylaluminate) complexes CpR′Ln(OArtBu,R)(AlMe4) for the smaller lanthanide metal centers yttrium and lutetium. Such an [aryloxide] → [aluminate] ligand exchange was not observed at the larger lanthanum metal center. The mobility of the tetramethylaluminate ligands of complexes CpR′Ln(OArtBu,R)(AlMe4) (Ln = Y, Lu) was examined by variable-temperature (VT) 1H NMR spectroscopy, revealing two signals for bridging and terminal methyl groups at lower temperatures. The treatment of complexes CpR′Ln(OArtBu,R)(AlMe4) with donor solvent d8-THF gave CpR′Ln(OArtBu,R)(Me)(d8-THF)2 (Ln = Y, Lu) with terminal methyl groups, according to a donor-induced aluminate cleavage reaction. Dimeric [(C5Me5)Ln(OCH2CMe3)2]2 (Ln = Y, Lu) was synthesized from (C5Me5)Ln(NiPr2)2(THF) and reacted with two equivalents of TMA per Ln center to yield monomeric bis(TMA) adduct complexes (C5Me5)Ln(OCH2CMe3)2(AlMe3)2(Ln = Y, Lu). VT NMR spectroscopic studies confirmed a high mobility of the Ln(μ-OCH2CMe3)(μ-Me)AlMe2 moieties at an ambient temperature. Both bis(TMA) adduct complexes were characterized by X-ray structure analysis.  相似文献   

15.
Five new lanthanide complexes [Ln2(DTDN)4(phen)4]·7H2O·2H3O+ (Ln = Nd (1), Sm (2), Eu (3), Tb (4), Dy (5), H2DTDN = 2,2′-dithiodinicotinic acid, phen = 1,10-phenanthroline) have been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, and TG analyses. By in situ oxidation of 2-mercaptonanicotinic acid (2-H2MN), the expected ligand H2DTDN was generated. All crystals are isostructural and crystallize in monoclinic system with space group C2/c. The metal center is eight-coordinated completely by four carboxylic oxygen atoms from four different DTDN2− ligands, and four nitrogen atoms from two phen molecules with a distorted square-antiprismatic geometry. The structures can be considered as two-dimensional (2D) structures and further linked by hydrogen bonds into the final trinodal 4-connected network. Photoluminescence studies revealed that complexes 2-5 exhibit strong fluorescent emission bands in the solid state at room temperature.  相似文献   

16.
A series of new ternary lanthanide complexes Ln(TFNB)3L (where Ln = Eu, Sm, Nd, Er, Yb, TFNB = 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionate, L = 1-(4-carbazolylphenyl)-2-pyridinyl benzimidazole) have been synthesised. The photoluminescence properties and TGA of them are described in detail. The trifluorinated ligand TFNB displays excellent antenna effect to sensitize the Ln(III) ions to emit characteristic spectra. The carbazole-containing ligand L is testified to be an outstanding synergistic ligand. The luminescence properties investigated and the quantum efficiency measured in dichloromethane solution of Eu(TFNB)3L and Sm(TFNB)3L show that the carbazole moiety is good at absorbing energy to sensitize the metal-centered emitting states and can make the complexes more rigid, provide efficient shielding of the Ln(III) core towards external quenching compared with the reference complexes of Eu(TFNB)3(Pybm) and Sm(TFNB)3(Pybm) (Pybm = 2-(2-pyridine)-benzimidazole) which have no carbazole unit. The quantum efficiency of Eu(TFNB)3L in air-equilibrated CH2Cl2 solution is calculated to be 14.8% by using air-equilibrated aqueous [Ru(bpy)3]2+·2Cl solution as reference sample (Φstd = 2.8%).  相似文献   

17.
Jun Li 《Inorganica chimica acta》2007,360(11):3504-3510
Three lanthanide complexes of 4-acyl pyrazolone derivatives: Ln(PMPP-SHZ)2(CH3OH)2 (Ln = Sm (1), Eu (2), Gd (3); PMPP-SHZ = N-(1-phenyl-3-methyl-4-propionyl-5-pyrazolone)-salicylidene hydrazide) have been synthesized and structurally characterized by X-ray crystallography. And all of them were carefully investigated by elemental analysis, thermal analysis and spectral characterization. The fluorescence of these three complexes 1-3 in solid state was investigated at room temperature. All complexes emit a blue emission band, and there are three characteristic emission peaks of Sm3+ evidently and one characteristic emission peak of Eu3+.  相似文献   

18.
The reactions of Ln(NO3)3 · xH2O, CoSO4 · 7H2O or ZnSO4 · 6H2O and 2-pyridylphosphonic acid under hydrothermal conditions result in heterometallic phosphonate compounds with formula [Ln2M3(C5H4NPO3)6] · 4H2O (Ln2M3; M = CoII or ZnII; Ln = LaIII, CeIII, PrIII, NdIII, SmIII, EuIII, GdIII, TbIII, DyIII). These compounds are isostructural and crystallize in a chiral cubic space group I213. Each structure contains the {LnO9} polyhedra and {MN2O4} octahedra which are connected by edge-sharing to form an inorganic open-framework structure with a 3-connected 10-gon (10, 3) topology. The nature of LnIII-CoII magnetic interactions in Ln2Co3 is investigated by a comparison with their LnIII-ZnII analogues. It is found that the LnIII-CoII interaction is weak antiferromagnetic for Ln = Ce and ferromagnetic for Ln = Sm, Gd, Tb and Dy. In the cases of Ln = Pr, Nd and Eu, no significant magnetic interaction is observed.  相似文献   

19.
A family of neutral and solvent-free bis(amidinate) rare earth metal amide complexes with a general formula [RC(N-2,6-Me2C6H3)2]2LnN(SiMe3)2 (R = phenyl (Ph), Ln = Y (1), Nd (2); R = cyclohexyl (Cy), Ln = Y (3), Nd (4)) were synthesized in high yields by one-pot salt metathesis reaction of anhydrous LnCl3, amidinate lithium salt [RC(N-2,6-Me2C6H3)2]Li, and NaN(SiMe3)2 in THF at room temperature. Single crystal structural determination of complexes 1, 2 and 4 revealed that the central metal adopts distorted pyramidal geometry. In the presence of 1 equivalent of iPr-OH, all these complexes were active for l-lactide polymerization in toluene at 70 °C to give high molecular weight (Mn > 104) polymers.  相似文献   

20.
Three new ligands and their palladium(II) complexes of general formula [PdCl2(R2-S,S-eddp)] (R = n-propyl, n-butyl and n-pentyl) have been synthesized and characterized by microanalysis, infrared and 1H and 13C NMR spectroscopy. Antimicrobial activity of these ligands and complexes was tested by microdilution method and both minimal inhibitory and microbicidal concentration were determined. These tested complexes demonstrated the significant antifungal activity against pathogenic fungi Aspergillus flavus and Aspergillus fumigatus. On the other hand, these complexes demonstrated moderate antibacterial activity.  相似文献   

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