Photolysis of light-transforming polymer material

Light-transforming polymer materials activated with the compositions on the basis of the europium carboxylates with different ligands and anthranilic acid exhibiting the intense luminescence in the spectral range 400–700 nm are prepared. It is shown that light stability of polymer materials on the basis of the aboveprepared compositions is higher than of polymer materials activated with the europium salts. The photolysis of luminescent polymers was studied. For the compositions EuL₃C₁₃H₁₃N₃·xH₂O + anthranilic acid gradual increase in the luminescence intensity of the europium ion is marked.     

Photochemical properties of mixed-ligand complexes europium carboxylates

The photochemical behavior of mixed-ligand complexes of europium carboxylates with nitrogen-and phosphorus-containing neutral ligands of island and dimer types, Eu(L)₃ · xD · nH₂O and [Eu(L)₃ · xD]₂ · nH₂O (L is the trifluoroacetate, toluate, or cinnamate anion), was studied. During UV irradiation of the complexes of europium carboxylates with 1,10-phenanthroline and 2,2′-dipyridyl, a luminescence buildup was observed. EPR measurements demonstrated that the observed buildup of luminescence from europium occurs in parallel with the increase of the concentration of radical anions formed from neutral ligands.     

The interaction of 1-oxy-2,6-di[(N,N-biscarboxymethyl)aminomethyl]4-chlorobenzene with lanthanides

This paper reports on some complexes of lanthanum(III) and europium(III) with the title ligand (H₅L) which possesses two similar coordination sites: mononuclear and homo- and hetero-dinuclear species are described. The isolated compounds have the formulas [M(H₂L)·3H₂O], [M₂LNO₃·4H₂O], (M = La, Eu); [MM′LOH·nH₂O] (M = Fe, M′= La, n = 2; M = Eu, M′= La, n = 4). In addition [Li₂LaL·3H₂O] and [CuLaL·3H₂O] have also been obtained. Relevant IR and visible spectral data and magnetic moment values are given and discussed.     

Luminescence and magnetic properties of mixed-ligand europium trifluoroacetates

The luminescence and magnetic properties of mixed-ligand europium trifluoroacetates with nitrogen- and phosphorus-containing neutral ligands [Eu(TFA)₃ · 3H₂O]₂ and Eu(TFA)₃ · 2D · nH₂O were studied (here TFA is the trifluoroacetic acid anion, and D is Phen (1,10-phenanthroline), n = 1; DMF (dimethylformamide), n = 1; or TPPO (triphenylphosphine oxide), n = 3). The molar magnetic susceptibility increased in the series of complex compounds Eu(TFA)₃ · 2Phen · H₂O < [Eu(TFA)₃ · 3H₂O]₂ < Eu(TFA)₃ · 2DMF · H₂O < Eu(TFA)₃ · 2TPPO · 3H₂O. Correlations were found between the luminescent and magnetic characteristics of the complex compounds.     

Preparation,Structure, and Optical Properties of the 1D Chain Red Luminescent Europium Coordination Polymer: {[Eu2L6(DMF)­(H2O)]·2DMF·H2O}n (L = C9H6ClO2–)

The 1D chain red luminescent europium coordination polymer: {[Eu₂L₆(DMF)(H₂O)] · 2DMF · H₂O}_n ( I ) (L = 4‐chloro‐cinnamic acid anion, C₉H₆ClO₂^–, DMF = N, N‐dimethylformamide) was synthesized by the reaction of Eu(OH)₃ and 4‐chloro‐cinnamic acid ligand. The structure of the coordination polymer was determined by single‐crystal X‐ray diffraction analysis. It reveals that there exists two crystallographically nonequivalent europium atoms in each unit of this coordination polymer and Eu³⁺ ions are connected by two alternating bridging modes to form an endless polymer structure. The luminescent properties and energy transfer process in the complex are investigated at room temperature.     

Luminescent and magnetic properties of europium compounds with cinnamic acid

The temperature dependences of the molar magnetic susceptibility of luminescent europium compounds with cinnamic acid [Eu(Cin)₃] _n and Eu(Cin)₃ · 2D · H₂O (where Cin is the cinnamic acid anion and D is phen (1,10-phenanthroline) or dipy (2,2-dipyridyl)) were studied at temperatures from 300 to 2 K. The molar magnetic susceptibility of the compounds increased in the series Eu(Cin)₃ · 2dipy · H₂O < Eu(Cin)₃ · 2phen · H₂O < [Eu(Cin)₃] _n . The energy distances λ_lum between the ⁷ F ₀ ground level and the ⁷ F ₁ state in the luminescence spectra correlated well with λ_magn obtained from magnetochemical data.     

Interaction in the system Bi(NO3)3-K3HCit-(H2O + glycerol)

The interaction in the system Bi(NO₃)₃-K₃HCit-(H₂O + glycerol) was studied by chemical analysis and pH titration over a wide range of ratios between the initial components. Solid phases of the compositions Bi(OH)_3?3x HCit _x · nH₂O and KBiCit · H₂O were isolated and investigated by X-ray powder diffraction and differential thermal analyses and IR spectroscopy. The effect of the chemical nature of the alkali metal on the solubility in the system under consideration was demonstrated.     

Chemiluminescence arising from the decomposition of 1,4-dimethylnaphthalene endoperoxide applied to silica gel in the presence of NdIII,YbIII, and EuIII β-diketonates

Visible and near-IR chemiluminescence was observed upon the decomposition of 1,4-dimethylnaphthalene endoperoxide applied to silica gel in the presence of the β-diketonate complexes Nd(L)3·nH₂O, Yb(L)3·nH₂O, and Eu(L)3·nH₂O (L is 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctane-3,5-dionate, 1,1,1-trifluoro-3-thenoylacetonate, and acetylacetonate). Excited lanthanide ions serve as luminescent emitters with emission maxima at λ = 870 and 1060 nm for Nd^III, 990 nm for Yb^III, and 615 nm for Eu^III. Singlet oxygen generated by decomposing endoperoxide was found to play a key role in the chemiluminescence mechanism.     

Luminescent and triboluminescent properties of europium(III) hexafluoroacetylacetonate and trifluoroacetate complexes with triphenylphosphine oxide

Crystalline and strongly luminescent complexes of europium hexafluoroacetylacetonate and trifluoroacetate with triphenylphosphine oxide of Eu(HFAA)₃ · 2TPPO and [Eu(TFA)₃ · 2TPPO(H₂O)]₂ composition are synthesized that demonstrating triboluminescent properties. It is established that the measured photoluminescence and triboluminescence spectra of these noncentrosymmetric complex compounds are identical, due to the characteristic f-f-luminescence of the europium(III) ion.     

Synthesis and Properties of a Novel 3D Europium Coordination Polymer with Helical Chain and (3,6)‐Connected rtl Net

The first coordination polymer of 2,2′‐((4‐carboxymethyl‐1,3‐phenylene)bis(oxy)) diacetic acid (H₃L) with europium(III) ion, [Eu(L)(H₂O)]·3H₂O ( 1 ), has been hydrothermally synthesized and structurally characterized. Complex 1 exhibits a 3D coordination polymer with helical chain and rtl topology of the point symbol (4·6²)₂(4²·6¹⁰·8³) based on [Eu₂(COO)₄] as secondary building unit (SBU). Furthermore, the luminescent and magnetic properties of complex 1 are studied.     

Nanocomposites with the layered structure of V2O5 · nH2O xerogel

New layered nanocomposites of V₂O₅ · nH₂O xerogels with poly(vinyl alcohol) (PVA), pyrocatechol (PC), and hydroquinone (HQ) were synthesized with the compositions (C₂H₃)_0.32V₂O_4.90 · nH₂O, (C₆H₄)_xV₂O_4.60 · nH₂O, and (C₆H₄)_0.17V₂O_4.94 · nH₂O and the interlayer distances d ₀₀₁ = 11.73, 12.85, and 15.28 ± 0.05 Å, respectively. IR and Raman spectroscopy was used to analyze which structural changes occur in the V-O layers of the xerogel upon composite formation. X-ray photoelectron spectroscopy showed V⁴⁺ and V⁵⁺ ions in the layers with binding energies lower than in V₂O₅ · nH₂O. The electrical conductivity of the nanofilms and the thermal properties of the nanopowders were studied.     

Synthesis, Crystal Structure and Optical Properties of Europium Trifluoroacetate Complexes with 1,10-Phenanthroline and 2,2-Bipyridine

Two europium trifluoroacetate complexes, Eu(CF₃COO)₃·phen ( 1 ) and Eu(CF₃COO)₃·bpy ( 2 ) (where phen=1,10‐phenanthroline, bpy=2,2′‐bipyridine), were synthesized and characterized by elemental analysis, Fourier transform infrared spectroscopy (FT‐IR), photoluminescence (PL) spectroscopy and thermogravimetric analysis (TA). Single‐crystal X‐ray structure has been determined for the complex [Eu₂(CF₃COO)₆·(phen)₃·(H₂O)₂]·EtOH. The crystal structure of [Eu₂(CF₃COO)₆·(phen)₃·(H₂O)₂]·EtOH shows that two different coordination styles with europium ions coexist in the same crystal and have entirely different coordination geometries and numbers. This crystal can be considered as an 1:1 adduct of [Eu(CF₃COO)₃·(Phen)₂·H₂O]·EtOH (9‐coordination part) and Eu(CF₃COO)₃·phen·H₂O (8‐coordination part). The excitation spectra of the two complexes demonstrate that the energy collected by "antenna ligands" is transferred to Eu³⁺ ions efficiently. The room‐temperature PL spectra of the complexes are composed of the typical Eu³⁺ ions red emission, due to transitions between ⁵D₀→⁷F_J(J=0→4). The lifetimes of ⁵D₀ of Eu³⁺ in the complexes were examined using time‐resolved spectroscopic analysis, and the lifetime values of Eu(CF₃COO)₃·phen and Eu(CF₃COO)₃·bpy were fitting with bi‐exponential (2987 and 353 µs) and monoexponential (3191 µs) curves, respectively. In order to elucidate the energy transfer process of the europium complexes, the energy levels of the relevant electronic states had been estimated. The thermal analyses indicate that they are all quite stable to heat.     

Low temperature rehydration of thermally dehydroxylated Bayer–gibbsite,evolution and transformation of phases

The hexahydrate of europium nitrate hexahydrate Eu(NO₃)₃·6H₂O shows no phase transitions in the range of ?40 to 76 °C when it melts in its own water of crystallization. It was shown that the thermal decomposition is a complex step-wise process, which starts with the simultaneous condensation of 6 mol of the initial monomer Eu(NO₃)₃·6H₂O into a cyclic cluster 6[Eu(NO₃)₃·6H₂O]. This hexamer gradually loses water and nitric acid, and a series of intermediate amorphous oxynitrates is formed. The removal of HNO₃ azeotrope is essentially a continuous process occurring in the liquid phase. At higher temperatures, oxynitrates undergo further degradation, lose water, nitrogen dioxide, and oxygen, and finally, after having lost lattice water, are transformed into europium oxide. All mass losses are satisfactorily accounted for under the proposed scheme of thermal decomposition.     

Phase composition,formation parameters,and morphology of precipitates in the LiVO<Subscript>4</Subscript>-VOSO<Subscript>4</Subscript>-H<Subscript>2</Subscript>O system

The phase and chemical compositions of the precipitates formed in the LiVO₃-VOSO₄-H₂O system at initial pH within 1 ≤ pH ≤ 4 and 90°C were studied. The following phases were prepared: an α phase Li_1.4(VO)_1.3[H₂V₁₀O₂₈] · nH₂O and a β phase Li_{0.6 ? x} H_{1.4 + x} [V₁₂O_{31 ? y/2}] · nH₂O (0 ≤ x ≤ 0.5, 1.3 ≤ y ≤ 2.0) with a layered structure. Li_0.4V₂O₅ · H₂O nanorods with the interlayer distance 10.30 ± 0.08 Å were synthesized at 180°C in an autoclave. The morphology, IR spectra, and main formation processes for these polyvanadates were studied.     

Synthesis,structure, and properties of trinuclear pivalate {Zn2Eu} complexes with N-donor ligands

New luminescent heterometallic complexes of Eu³⁺ and Zn²⁺ were synthesized: Zn₂Eu(NO₃)(Piv)₆(L)₂ (Piv is pivalate anion, L = MeCN (1), 2,3-lutidine (2), 2,2′-bpy (3)) and [Zn₂(Piv)₃(2,2′-bpy)₂][ZnEu(NO₃)₃(Piv)₃(2,2′-bpy)] (4). In the case of 2,2′-bpy, the order of mixing of the reagents ([Zn(Piv)₂] _n , Eu(NO₃)₃·6H₂O, and 2,2′-bpy) affects the composition of the final reaction product: the reaction of [Zn(Piv)₂] _n and Eu(NO₃)₃·6H₂O (in the ratio Zn : Eu = 3 : 1) in MeCN affords complex 1 and the subsequent addition of 2,2′-bpy (Zn : L = 1 : 1) affords complex 3. Complex 4 is formed in the reaction of [Zn(Piv)₂] _n and 2,2′-bpy (Zn : L = 1 : 1) in MeCN followed by the addition of Eu(NO₃)₃·6H₂O (Zn : Eu = 3 : 1). The luminescence spectra of compounds 1–4 (Zn : Eu = 3 : 1) exhibit metal-centered luminescence of Eu³⁺. The most efficient ligand-antenna is 2,2′-bpy, which is due to the optimum position of the triplet level of this ligand.     

Synthesis, characterization and thermal analysis of 1:1 and 2:3 lanthanide(III) citrates

The synthesis and characterization of lanthanide(III) citrates with stoichiometries 1:1 and 2:3; [LnL·xH₂O] and [Ln₂(LH)₃·2H₂O], Ln=La, Ce, Pr, Nd, Sm and Eu are reported. L stands for (C₆O₇H₅)^3? and LH for (C₆O₇H₆)^2?. Infrared absorption spectra of both series evidence coordination of carboxylate groups through symmetric bridges or chelation. X-ray powder patterns show the amorphous character of [LnL·xH₂O]. The compounds [Ln₂LH₃·2H₂O] are crystalline and isomorphous. Emission spectra of Eu compounds suggest C _2v symmetry for the coordination polyhedron of [LnL·xH₂O] and C _4v for [Ln₂(LH)₃·2H₂O]. Thermal analyses (TG-DTG-DTA) were carried out for both series. The thermal analysis patterns of the two series are quite different and both fit in a 4-step model of thermal decomposition, with lanthanide oxides as final products.     

多色发光层状稀土氢氧化物/聚甲基丙烯酸甲酯复合荧光薄膜的组装

本文通过水热法合成了含有3种不同稀土离子的层状稀土氢氧化物(Gd0.5Tb0.5-xEux)2(OH)5NO3.nH2O,并选择有机物水杨酸(HSA)作为敏化剂,通过在水热条件下的离子交换反应,成功将其以有机阴离子形式与层状稀土氢氧化物插层组装获得有机-无机杂化荧光材料(SA--LRHs∶xEu)。荧光性质测定表明,SA-通过有效的能量转移增强了Tb3+的特征绿色荧光发射,随着Eu3+含量的增加,Eu3+的特征红色荧光发射随之增强,而Tb3+的特征绿色荧光发射随之减弱。在此基础上,将发光颜色可调的有机-无机荧光材料与聚甲基丙烯酸甲酯(PMMA)复合组装出透明的荧光薄膜。     

A new approach to the preparation of lanthanide catalysts for the synthesis of 2-propyl-3-ethylquinoline based on the reactions of LnCl3 · 6H2O crystalline hydrates with triisobutylaluminum

A new approach to the preparation of lanthanide catalysts for the synthesis of nitrogen heterocycles (exemplified by 2-propyl-3-ethylquinoline) was developed based on the reactions of LnCl₃ · 6H₂O crystalline hydrates with alkylaluminums. It was found that the interaction of LnCl₃ · 6H₂O (Ln = Ce, Pr, Tb, and Eu) with iso-Bu₃Al in aromatic solvents (20°C) resulted in the formation of soluble (isobutane and the alumoxane (iso-Bu₂Al)₂O) and insoluble products (with the empirical formula LnCl₃ · xH₂O · y(iso-Bu₂Al)₂O (x = 0.4–0.7; y = 0.04–0.07)). The physiochemical properties of LnCl₃ · xH₂O · y(iso-Bu₂Al)₂O were studied, and these compounds were found to be highly efficient catalysts for the reaction of aniline condensation with butyraldehyde to form 2-propyl-3-ethylquinoline.     

Coordination polymers of rare-earth elements with 2-aminoterephthalic acid

Coordination polymers of REEs with 2-aminoterephthalic acid [Ln₂(C₈H₅NO₄)₃(H₂O)₅] _n · 2nH₂O (Ln = Eu, Gd, or Tb) and [Y₂(C₈H₅NO₄)₃(H₂O)₄] _n · 4nH₂O were prepared by hydrothermal synthesis. Studies of the thermal behavior of these coordination polymers have shown that the removal of the solvate and the coordinated water molecules occurs at heating to 250°C and dehydratation products are stable up to 400°C. Detailed studies of the magnetic behavior of Eu, Gd, and Tb polymers were performed.     

Syntheses,Molecular Structure and Thermodynamic Properties of 3‐Nitro‐1,2,4‐triazol‐5‐one Europium Complex [Eu(NTO)3(H2O)5]·5H2O

3‐Nitro‐1,2,4‐triazol‐5‐one (NTO) europium complex of [Eu(NTO)₃(H₂O)₅]·5H₂O was synthesized by mixing the aqueous solution of lithium 3‐nitro‐1,2,4‐triazol‐5‐onate and the dilute nitric acid solution of europium oxide. The title complex was characterized by elemental analysis and IR spectra. The single crystal structure was determined by a four‐circle x‐ray diffractometer. The title complex is monoclinic with space group P2₁/n and unit cell parameters of a = 1.8720(2) nm, b = 0.6548(3) nm, c = 1.9323(3) nm and β = 95.33(1)°. The coordination geometry around the europium ion is a distorted dodecahedron and there are five crystalline water molecules to form the stable structure of the crystal. From measurements of the enthalpy of solution in water at 298.15 K, the standard enthalpy of formation, lattice enthalpy and lattice energy have been determined as ‐(3798.6 ± 3.7), ?4488.4 and ?4452.4 kJ·mol^?;1, respectively.