On the reported mesomorphism of lanthanide complexes containing the hemicyanine structural unit

Close examination of the thermal behaviour of the (E)-N-hexadecyl-4-N', N'-dimethylaminostilbazolium tetrakis(1-phenyl-3-methyl-4-benzoyl-5-pyrazolonato)lanthanide(III) complexes has revealed that these compounds are not mesomorphic, in contradiction to an earlier report in the literature (K. Z. Wang et al., 1995, Solid State Commun. 95, 223). By replacing the bromide of the hemicyanine precursor (see the scheme) by a tetrakis(beta-diketonato)lanthanide(III) anion, new complexes were synthesized, but none shows a mesophase. Reasons for the absence of mesomorphism are discussed. Transition temperatures for the mesomorphic hemicyanine bromides are reported.     

Yb-邻非啰啉-曙红三元配合物近红外发光测定Yb3+

介绍了Yb-邻菲啰啉-曙红三元配合物的发光性质,并应用这一特性建立了一种新的Yb3+的分析方法.研究结果表明这一三元配合物具有良好的发光特性,曙红对Yb3+发光具敏化作用.测定Yb3+的检出限可达8.0×10-7 moL/L,线性范围为8.0×10-7～2.6×10-5 moL/L, 回收率为102%.     

Sensitized Luminescence of Rare Earths

IntroductionAsearlyas1967,inthestudyofthefluorescentcharacteristicsoftheion..associationcomplexEu' -TTA-pyridine,Melentavaetal.[1Jpointedoutthatthef1uorescenceintensityofthesystemwasgreatlyincreasedbytheadditionofGds orTbf' ,andmoreoveronlyinthesuspensiontheenhancementofthefIuo-rescencewasobserved.However,thisphenomenonwasregardedasinterferenceinthepresenceofotherrareearthionsandwaseliminatedbyanextractionpro-cedure.Thisphenomenonwassystemacticallyinvestigatedandcalledcolumines-cence[2j,co…     

Synthesis and structure of lanthanide complexes with large-bite diphosphine dioxide ligands

Three large-bite diphosphine dioxide ligands were reacted with lanthanide salts to yield either molecular or polymeric complexes. The two flexible ligands gave bischelate complexes of general formulae [Ln(dppfO₂)₂Cl_x(NO₃)_2−x][FeCl₄] and [Ln(dppdO₂)₂(NO₃)₂]NO₃, where dppfO₂ and dppdO₂ are bis(diphenylphosphoryl)ferrocene and bis(diphenylphosphoryl)diphenyl ether, respectively. Reactions of the rigid bis(diphenylphosphoryl)benzene (dppbO₂) with lanthanide salts yielded linear coordination polymers of a 1:1.5 metal-to-ligand stoichiometry. The compounds were studied by single crystal X-ray diffraction, IR spectroscopy, mass spectrometry, and TG/DSC techniques.     

Relationship between the ligand structure and the luminescent properties of water-soluble lanthanide complexes containing bis(bipyridine) anionic arms

A series of six new ligands (L(1)-L(6)) suitable for the formation of luminescent lanthanide complexes in water is described. Ligands L(1)-L(4) are constructed from two 6'-carboxy-6-methylene-2,2'-bipyridine chromophoric arms bonded to the amino function of a 2-aminomethylene-6-carboxy-pyridine (L(1)), an N,N-diacetate-ethylene diamine (L(2)), a serine (L(3)), or an aminomalonic acid (L(4)). For ligands L(5) and L(6), the linking amino function is provided by a glutamic acid, and the anionic functions at the 6'-position of the bipyridyl arms are made of the sodium salts of monoethylphosphonic ester (L(5)) and phosphonic acid (L(6)). The synthesis and characterisation of the ligands are described, together with the study of the formation of lanthanide complexes with europium and terbium. In the case of L(3), the europium complex obtained in acidic conditions was crystallised and the X-ray crystal structure is depicted. Photophysical properties of the complexes were studied by means of UV-visible absorption, and steady-state and time-resolved luminescence spectroscopy. Excited-state luminescence lifetimes of the complexes were determined in water and deuterated water to gain insight into the number of water molecules directly coordinated in the first coordination sphere of the complexes. The coordination behaviour of the series of ligands is questioned in the light of the spectroscopic data and discussed in terms of protection of the cation towards water molecules and their impact on the luminescence efficiency.     

Lanthanide(III) nitrobenzenesulfonates and p-toluenesulfonate complexes of lanthanide(III), iron(III), and copper(II) as novel catalysts for the formation of calix[4]resorcinarene

Lanthanide(III) salts of p-toluenesulfonic acid [lanthanide(III) tosylates, Ln(TOS)₃] and nitrobenzenesulfonic acid [Ln(NBSA)₃], and p-toluenesulfonate complexes of iron(III) and copper(II) were prepared, characterized, and examined as catalysts for the synthesis of resorcinol-derived calix[4]resorcinarenes. The reaction of resorcinol with benzaldehyde yields two isomers, the all-cis isomer (rccc) and the cis-trans-trans isomer (rctt) with the relative isomer ratios depending on the reaction conditions. However, in the reaction of resorcinol with octanal only one isomer, the all-cis isomer, is formed in high yields with less than 0.1 mol % of Yb(TOS)₃. Examination of lanthanide(III) tosylates and lanthanide(III) nitrobenzenesulfonates revealed that ytterbium(III) 4-nitrobenzenesulfonate [ytterbium(III) nosylate, Yb(4-NBSA)₃] and ytterbium(III) 2,4-dinitrobenzenesulfonate [Yb(2,4-NBSA)₃] are the most active catalysts. The catalysts could be easily recovered and reused several times for resorcinarene formation without loss of efficiency. Surprisingly good results were also obtained with iron(III) and copper(II) p-toluenesulfonates. Besides optimizing the reaction conditions, new insights into the reaction mechanism were also obtained.     

Energy transfer in solution of lanthanide complexes

The lanthanides with their well-defined energy levels provide an excellent basis to study different Ln(III)-specific energy transfer processes in a variety of chemical environments. The studies concerning intramolecular and intermolecular energy transfer processes with participation of Ln(III) ions and a variety of ligand groups in solution are reviewed. Phenomena of energy transfer from ligands to Ln(III) ions, resulting consequently in a great enhancement of the Ln(III) ion luminescence (ligand sensitized luminescence), as well as from Ln(III) to other species and between Ln(III) ions are presented.     

Synthesis and nonlinear optical properties of hyperbranched polytriazole containing second‐order nonlinear optical chromophore

The hyperbranched polytriazole (hb‐PTA) containing second‐order nonlinear optical chromophore was synthesized through “A₂ + B₃” approach based on “click reaction.” Its corresponding linear analogue (l‐PTA) was prepared for comparison. The hb‐PTA has better solubility in common organic solvents than the l‐PTA. Both the polymers exhibit good thermal stability with 5% weight loss temperatures over 260 °C. The poled film of hb‐PTA exhibits much higher second‐harmonic coefficient (96.8 pm/V) than that of l‐PTA (23.5 pm/V). The three‐dimensional spatial isolation effect resulting from the highly branched structure and the crosslinking of the terminal acetylene groups at moderate temperature play important roles in the enhancement of optical nonlinearity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1140–1148, 2008     

Remarkable luminescence properties of lanthanide complexes with asymmetric dodecahedron structures

The distorted coordination structures and luminescence properties of novel lanthanide complexes with oxo‐linked bidentate phosphane oxide ligands—4,5‐bis(diphenylphosphoryl)‐9,9‐dimethylxanthene (xantpo), 4,5‐bis(di‐tert‐butylphosphoryl)‐9,9‐dimethylxanthene (tBu‐xantpo), and bis[(2‐diphenylphosphoryl)phenyl] ether (dpepo)—and low‐vibrational frequency hexafluoroacetylacetonato (hfa) ligands are reported. The lanthanide complexes exhibit characteristic square antiprism and trigonal dodecahedron structures with eight‐coordinated oxygen atoms. The luminescence properties of these complexes are characterized by their emission quantum yields, emission lifetimes, and their radiative and nonradiative rate constants. Lanthanide complexes with dodecahedron structures offer markedly high emission quantum yields (Eu: 55–72 %, Sm: 2.4–5.0 % in [D₆]acetone) due to enhancement of the electric dipole transition and suppression of vibrational relaxation. These remarkable luminescence properties are elucidated in terms of their distorted coordination structures.     

Bichromophoric hemicyanine dyes as fluorescence probes applied for monitoring of the photochemically initiated polymerization

The spectroscopic properties of series homodimmeric hemicyanine dyes based on (p-N,N-dimethylaminostyryl)benzothiazolium, (p-N,N-dimethylaminostyryl)benzoxazolium, (p-N,N-dimethylaminostyryl)-2,3,3-trimethyl-3H-indolium residues were determined. The absorption and fluorescence spectra of the dyes under study were measured in different polarity solvents at room temperature. On the basis of the solvatochromic behavior the ground state (μ_g) and excited state (μ_e) dipole moments of bis-(N,N-dimethylaminostyryl) derivatives were evaluated. The dipole moments (μ_g and μ_e) were estimated from solvatochromic shifts of absorption and fluorescence spectra as function of dielectric constant (ε) and refractive index (n) of applied solvents. The absorption and fluorescence spectra are only slightly affected by the solvent polarity. The analysis of solvatochromic behavior of the fluorescence spectra as a function of Δf (ε, n) revealed that the emission occurs from a high polarity excited state. The large dipole moment changes along with the red-shifted fluorescence, as the solvent polarity is increased, demonstrates the formation of an intramolecular charge transfer state (ICT). Six bichromophoric hemicyanine dyes, possessing benzothiazole, benzoxazole or indolinium group linked by 5 or 10 methylene groups were evaluated as fluorescence probes applied for monitoring of the polymerization process. The study on the changes in fluorescence intensity and spectroscopic shift of studied compounds were carried out during photochemically initiated polymerization of 2-ethyl-2-(hydroxymethyl)-propane-1,3-diol triacrylate (TMPTA).     

Towards libraries of luminescent lanthanide complexes and labels from generic synthons

A synthetic approach is developed to obtain families of luminescent lanthanide complexes and markers from a generic family of precursors built from nonadentate coordination sites. The syntheses of the precursors, based on a directed regioselective nucleophilic aromatic substitution on polyfluoropyridines, are described. Functionalisation of the synthons on the aromatic moieties allowed the introduction of labelling functions and/or the extension of the electronic delocalisation, with concomitant changes in the spectroscopic properties. The synthesis of two such families of ligands and of some of their complexes of Eu(III) and Tb(III) are described, and the photo-physical properties of the complexes were measured, revealing excellent luminescence quantum yields reaching unity in some cases. For some of these complexes, the emphasis was further put on the preparation of an N-hydroxylsuccinimide (NHS) ester as activated function for labelling. The Tb and La complexes in the NHS activated form were synthesized and fully characterized. The labelling was first demonstrated on amino functionalized polymer beads and characterized by time-resolved luminescence microscopy. In a second step, the activated Tb complex was used for the labelling of GFR44 monoclonal antibody, and was applied to the detection of carcinoembryonic antigene (CEA) within the frame of a time-resolved fluoroimmunoassay. Comparison with a commercially available kit based on a europium cryptate as energy donor confirms the efficiency of Tb to act as an energy donor with an unoptimised 35% increase of the detection efficiency.     

Mesoporous hybrids containing Eu complexes covalently bonded to SBA-15 functionalized: Assembly, characterization and photoluminescence

A novel series of luminescent mesoporous organic-inorganic hybrid materials has been prepared by linking Eu³⁺ complexes to the functionalized ordered mesoporous SBA-15 which was synthesis by a co-condensation process of 1,3-diphenyl-1,3-propanepione (DBM) modified by the coupling agent 3-(triethoxysilyl)-propyl isocyanate (TEPIC), tetraethoxysilane (TEOS), Pluronic P123 surfactant as a template. It was demonstrated that the efficient intramolecular energy transfer in the mesoporous material Eu(DBMSi-SBA-15)₃phen mainly occurred between the modified DBM (named as DBM-Si) and the central Eu³⁺ ion. So the Eu(DBMSi-SBA-15)₃phen showed characteristic emission of Eu³⁺ ion under UV irradiation with higher luminescence quantum efficiency. Moreover, the mesoporous hybrid materials exhibited excellent thermal stability as the lanthanide complex was covalently bonded to the mesoporous matrix.     

Recent Developments in the Field of Inorganic Phosphors

Energy efficiency is in! New inorganic luminescent materials can help to increase energy efficiency when used in plasma display panels and white‐light‐emitting diodes (see color diagram; mixing the three emissions A–C produces any given point within the triangle). In mercury‐free fluorescent lamps these phosphors might contribute to environmental protection, and they provide better scintillation materials for medical diagnostics.

     

SrS∶Ce薄膜电致发光机制

在分析Ｃｅ３＋ 激发态能级与导带之间杂化相互作用的基础上， 讨论了电场强度与场致电离之间的关系。实验测得的ＳｒＳ∶Ｃｅ ＴＦＥＬ发光波形表明， 在正弦电压驱动下的半周期内， 一种样品在上升沿有发光， 而另一种样品在上升和下降沿有两个发光峰。这种不同的产生与样品中硫空位对ＳｒＳ∶Ｃｅ 激发和发射过程的影响有关。上升沿的发光主要是由直接碰撞激发引起的分立中心的发光， 而下降沿的发光及上升沿的部分发光属于因电离而引起的复合发光。     

Ce3+和Tb3+掺杂的稀土硼酸盐玻璃的发光性质

报道Ｃｅ＾３＋和Ｔｂ＾３＋掺杂的硼酸盐玻璃的合成及该系列玻璃的激发和发射光谱性质。在紫外光激发下,玻璃中的Ｃｅ＾３＋发射蓝紫光,Ｔｂ＾３＋发射有特征的绿光,在Ｃｅ＾３＋和Ｔｂ＾３＋共掺杂的体系中,可观察到Ｃｅ＾３＋强烈敏化Ｔｂ＾３＋发光的现象。分析表明,Ｃｅ＾３＋和Ｔｂ＾３＋之间存在辐射能量传递稿铲无辐射能量传递。     

Synthesis,characterization and thermogravimetric study of Dy and Sm 12-crown-4 bipy,terpy and phen complexes

The synthesis, characterization and thermogravimetric study of [Sm(12C4)(H₂O)₄]Cl₃, [Dy(12C4)(H₂O)₄]Cl₃, [Sm(12C4)(bipy)(H₂O)₂]Cl₃, [Dy(12C4)(bipy)(H₂O)₂]Cl₃, [Sm(12C4)(bipy)(phen)]Cl₃, [Dy(12C4)(bipy)(phen)]Cl₃, [Sm(12C4)(phen)₂]Cl₃, [Dy(12C4)(phen)₂]Cl₃, [Sm(12C4)(terpy)(H₂O)]Cl₃ and [Dy(12C4)(terpy)(H₂O)]Cl₃ (12C4?=?12-crown-4; bipy?=?bipyridine; phen?=?1,10-phanathroline; terpy?=?terpyridine) are reported. All compounds exhibit CN?=?8 and four oxygen–lanthanide bonds of the crown ether provide a very stable (from the thermal point of view) chemical environment, since the crown ether molecules are the last organic moiety to be released under heating.     

Two-photon-excited fluorescence of zinc(Ⅱ),cadmium(Ⅱ) complexes containing phenothiazine ligand

Two new ligands, S-benzyl-β-N-[10-ethylphenothiazine-3-methylene] dithiocarbazate (HL1), S-methyl-β-N-[10-ethylphenothiazine-3-methylene] dithiocarbazate (HL2), and their complexes which exhibit intensive two-photon excited (TPE) fluorescence at 800 nm laser pulses in the femtosecond regime, are synthesized and fully characterized. The measured power dependence of the fluorescence signals provides a direct evidence for TPE. All of them exhibit a large two-photon absorptive crosssection. The two-photon-excited fluorescence spectra of them are compared and contrasted with the corresponding results obtained from the one-photon excitation. Emission peaks of the ligands and their complexes are observed mostly at the region 550-595 nm in the TPE fluorescence spectra.