新型β-二酮铕配合物的合成和性能研究

以肉桂酸和苯乙酮为原料合成了1,5-二苯基-4-烯-1,3-戊二酮（DPPD）配体,以DPPD为第一配体,1,10-邻菲罗啉为第二配体,合成了稀土铕配合物并通过红外光谱进行了表征,同时,研究了配合物的发光性能。     

Complexes of Rare Earths and Dipicolinato Ions Encapsulated in X- and Y-zeolites: Luminescence Properties

The complexes {Ln(DP)}Z where Ln³⁺ = La³⁺ or Eu³⁺, DP is the dipicolinate ion (2,6)-pyridine dicarboxylate: C₅H₃N(COO^-)₂ and Z = one of the faujasite-type X or Y zeolites have been synthesized and investigated by XRD, Raman and IR spectroscopy, and Eu³⁺ luminescence spectroscopy. The rare earth complexes are synthesized inside the super-cages of the zeolites; the degree of complexation never exceeds1DP/1Ln. Only the Ln ions, which are in the super-cages, may be complexed. Luminescent europium complexes encapsulated in zeolite matrices were obtained. The ⁵D₀ F_J luminescence observed under excitation into the lowest-energy ligand-centered absorption band (275 nm)indicates that a DP to Eu energy transfer occurs in these systems. The complex versus the zeolite framework conformations influence the europium emission characteristics: the transfer is more efficient when the complexed europium [Eu(DP)]⁺ is directly bonded to the framework oxygen atoms rather than to a residual water molecule.     

Synthesis and luminescence properties of the europium quaternary complexes nanoparticles

In this paper,the nanometer-sized(200 nm)quaternary rare-earth complex Eu(BA)(TTA)2phen was successfully prepared by using the method of optimizing chemical precipitation.The characterizations of these nanoparticles were performed by using elemental analysis,thermogravimetric analysis,infrared spectroscopy,fluorescence spectroscopy,transmission electron microscopy and luminescence quantum-yield.The results indicate that they are better than common ternary complexes at light-emitting performance,luminescence properties,thermal stability,uniformity and particle size;they can also be further mixed with a suitable polymer to form functional rare earth polymers.Compared to the common solid materials,the quaternary complex has better and unique characteristics such as nanoparticle size effect and surface effect.A foundation had been laid for the further expansion of its application in the field of light-emitting and magnetic materials.     

稀土络合催化合成橡胶

中国是稀土资源最丰富的国家,60年代起为充分利用我国的稀土资源,中国科学院长春应用化学研究所开展了稀土催化剂催化双烯烃聚合的研究,我国在世界上是最早开展这项研究的国家之一．自1964年,我们先后发表了稀土化合物在定向聚合中的催化活性的论文．从1971年开始我国率先进行稀土顺丁橡胶和异戊橡胶产业化开发工作．至今已发表了大量论文和多部专著．本文综述了关于稀土络合催化合成橡胶历年来的研究成果．     

稀土铕三元配合物-甲基丙烯酸甲酯共聚物的合成和荧光性能研究

在较温和的条件下,利用二苯甲酰甲烷为第一配体,甲基丙烯酸为第二配体与氯化铕在乙醇中反应,合成了一个新的稀土三元配合物Eu(DBM)2MA.2H2O[DBM:C6H5COCHCOC6H5,MA:CH2C(CH3)COO-]。然后将铕三元配合物与甲基丙烯酸甲酯(MMA)进行共聚反应,制备了一个新的键合型稀土高分子共聚物。通过元素分析、EDTA配位滴定分析、红外、紫外、荧光光谱分析测定了配合物及共聚物的组成、结构和发光性能;利用差热-热重分析测定了共聚物的热稳定性,用差示扫描量热法和凝胶色谱法测定了共聚物的玻璃化温度和平均分子量。研究结果表明,稀土三元配合物和相应的共聚物在612.94 nm处均能发出强的Eu3+特征荧光。     

Synthetic rubbers prepared by lanthanide coordination catalysts

China is rich in rare earth resources. Rare earth elements, also named lanthanides, are number 58 to number 81 elements in the elemental periodic table. They have unique electronic structures and may form various coordination compounds. In the early 1960s, researchers at the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences (CIAC) found the catalytic activities of lanthanide compounds in stereospecific polymerization of conjugated dienes, and published the first paper on this topic in 19...     

Preparation and properties of yttrium,lanthanum, and lanthanide 3,5-dinitrobenzoates

Summary The condition of the formation of rare earth 3,5-dinitrobenzoates were studied and their quantitative composition and solubilities in water at 298 K determined (their solubilities are of the order of 10^–4 mol dm^–3). From the values of solubilities in water the solubility products were established (in the order of 10^–12 mol⁴ dm^–12). The IR and X-ray spectra for the hydrated and dehydrated complexes were recorded and studied. All complexes are crystalline compounds. The condition of thermal decomposition of the complexes was also investigated. On heating above 573 K the 3,5-dinitrobenzoates decompose explosively and undergo a melting process at the same time. Accordingly, the thermal decomposition for the complexes was studied in the temperature range 273–573 K. The thermal stability data reveal them to dehydrate in two steps. From the obtained results it appears that during the dehydration process no izomerization of the nitro group to the nitrito group occurs.

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Herstellung und Eigneschaften von Y-, La- und Lanthaniden-3,5-Dinitrobenzoaten

Zusammenfassung Die Bedingungen zur Darstellung von Y-, La- und Lanthaniden-3,5-Dinitrobenzoaten wurden untersucht. Ihre quantitative Zusammensetzung und ihre Wasserlöslichkeit bei 298 K wurden bestimmt (die Löslichkeit ist in der Größenordnung 10^–4 mol dm^–3). Die Infrarot- und Röntgenspektren der erhaltenen Komplexe sowie der 3,5-Dinitrobenzoate der seltenen Erden nach der Dehydratisierung wurden gemessen. Es wurde festgestellt, daß es sich stets um kristalline Verbindungen handelt. Das thermische Verhalten der erhaltenen Komplexe wurde untersucht: sie zerfallen über 573 K explosiv und schmelzen zugleich. Der thermische Zerfall der erhaltenen 3,5-Dinitrobenzoate der seltenen Erden wurde im Temperaturbereich von 273–523 K untersucht. Es wurde festgestellt, daß die Y-, La-, und Lanthaniden — 3,5-Dinitrobenzoate bei Temperaturerhöhung oder im Dehydratisierungsprozeß keine Umgruppierung in die entsprechenden Nitritoverbindungen erleiden.

     

A series of two‐dimensional lanthanide coordination polymers: synthesis,structures, magnetism and selective luminescence detection for heavy metal ions and toxic solvents

A series of two‐dimensional (2D) coordination polymers (CPs), namely poly[[bis(μ‐acetato)diaqua(μ₆‐biphenyl‐3,3′,5,5′‐tetracarboxylato)bis(N,N‐dimethylacetamide)digadolinium(III)] N,N‐dimethylacetamide monosolvate], {[Gd₂(C₁₆H₆O₈)(C₂H₃O₂)₂(C₄H₉NO)₂(H₂O)₂]·C₄H₉NO}_n ( CP1 ), poly[[bis(μ‐acetato)diaqua(μ₆‐biphenyl‐3,3′,5,5′‐tetracarboxylato)bis(N,N‐dimethylacetamide)didysprosium(III)] N,N‐dimethylacetamide monosolvate], {[Dy₂(C₁₆H₆O₈)(C₂H₃O₂)₂(C₄H₉NO)₂(H₂O)₂]·C₄H₉NO}_n ( CP2 ), poly[bis(μ‐acetato)diaqua(μ₆‐biphenyl‐3,3′,5,5′‐tetracarboxylato)bis(N,N‐dimethylacetamide)dineodymium(III)], [Nd₂(C₁₆H₆O₈)(C₂H₃O₂)₂(C₄H₉NO)₂(H₂O)₂]_n ( CP3 ), poly[bis(μ‐acetato)diaqua(μ₆‐biphenyl‐3,3′,5,5′‐tetracarboxylato)bis(N,N‐dimethylacetamide)disamarium(III)], [Sm₂(C₁₆H₆O₈)(C₂H₃O₂)₂(C₄H₉NO)₂(H₂O)₂]_n ( CP4 ), has been synthesized from rigid biphenyl‐3,3′,5,5′‐tetracarboxylic acid under solvothermal conditions. Their structures have been determined by single‐crystal X‐ray diffraction analyses, elemental analyses, IR spectra, powder X‐ray diffraction and thermogravimetric analyses, and CP1 – CP4 crystallize in the monoclinic space group P2₁/n. CP1 – CP4 are isomorphous and feature similar 2D double layers, which are further extended via interlayer hydrogen‐bonding interactions into a three‐dimensional (3D) supramolecular structure. Hydrogen‐bonding interactions between N,N‐dimethylacetamide molecules and carboxylate O atoms strengthen the packing of the layers. The organic ligands interconnect with metal ions to generate 2D layered structures with a (4,4)‐connected net having {4⁴.6²} topology. CP1 has been investigated for its magnetic properties and magnetic susceptibility measurements were carried out in the range 2.0–300 K. The results of the magnetic measurements show weak antiferromagnetic coupling between the Gd^III ions in CP1 . Moreover, the strong luminescence of CP2 and CP4 can be selectively quenched by the Fe³⁺ ion and toxic solvents (e.g. acetone).     

脂肪酸铕配合物聚合物材料的合成及发光性质

以一定比例正辛酸和月桂酸为第一配体,通过皂化法合成了脂肪酸铕配合物,并溶于甲基丙烯酸甲酯（MMA）单体通过本体聚合得到了含脂肪酸铕的PMMA光致发光聚合物材料AxByEu/PMMA（其中A=正辛酸根,B=月桂酸根,x、y分别表示正辛酸和月桂酸的比例）。考察了不同的第二配体（咔唑、二甲基-联吡啶、邻菲罗啉、噻吩甲酰三氟丙酮HTTA）对脂肪酸铕聚合物发光性能的影响,选择出合适的第二配体HTTA,进而合成了A3Eu/HTTA/PMMA聚合物。通过红外光谱、紫外光谱及荧光光谱对脂肪酸铕配合物及聚合物的结构和荧光性能进行表征。结果表明：合成的脂肪酸铕配合物及其聚合物均具有很好的光致发光性能,紫外激发能发射Eu3+离子的特征红光。当HTTA的质量分数减小至0.02%时,仍能很好地促进体系的发光,且不影响聚合物本身的透明性。     

Pyridine-based lanthanide complexes combining MRI and NIR luminescence activities

A series of novel triazole derivative pyridine-based polyamino-polycarboxylate ligands has been synthesized for lanthanide complexation. This versatile platform of chelating agents combines advantageous properties for both magnetic resonance (MR) and optical imaging applications of the corresponding Gd(3+) and near-infrared luminescent lanthanide complexes. The thermodynamic stability constants of the Ln(3+) complexes, as assessed by pH potentiometric measurements, are in the range log K(LnL)=17-19, with a high selectivity for lanthanides over Ca(2+), Cu(2+), and Zn(2+). The complexes are bishydrated, an important advantage to obtain high relaxivities for the Gd(3+) chelates. The water exchange of the Gd(3+) complexes (k(ex)(298)=7.7-9.3×10(6) s(-1)) is faster than that of clinically used magnetic resonance imaging (MRI) contrast agents and proceeds through a dissociatively activated mechanism, as evidenced by the positive activation volumes (ΔV(≠)=7.2-8.8 cm(3) mol(-1)). The new triazole ligands allow a considerable shift towards lower excitation energies of the luminescent lanthanide complexes as compared to the parent pyridinic complex, which is a significant advantage in the perspective of biological applications. In addition, they provide increased epsilon values resulting in a larger number of emitted photons and better detection sensitivity. The most conjugated system PheTPy, bearing a phenyl-triazole pendant on the pyridine ring, is particularly promising as it displays the lowest excitation and triplet-state energies associated with good quantum yields for both Nd(3+) and Yb(3+) complexes. Cellular and in vivo toxicity studies in mice evidenced the non-toxicity and the safe use of such bishydrated complexes in animal experiments. Overall, these pyridinic ligands constitute a highly versatile platform for the simultaneous optimization of both MRI and optical properties of the Gd(3+) and the luminescent lanthanide complexes, respectively.     

Crystal structure and luminescence of europium(III) acrylate

The atomic structure of europium acrylate crystals [Eu₂(Acr)₅OH·3H₂O]·2(0.5H₂O) was studied by X-ray analysis (a = 24.360(3) Å, b = 18.466(2) Å, c = 8.5818(9) Å, β = 96.087(2)°, space group C2/c, Z = 6, ρ_calc = 2.036 g/cm³). The crystal structure involves chains of binuclear [Eu₂(C₃H₃O₂)₅OH·3H₂O] molecules, running infinitely in the [101] direction and having pairs of C₉H₉EuO₇H₂O molecules alternating with C₆H₆EuO₄OH·2H₂O molecules that link the pairs. The infinite chains are linked by hydrogen bonds and van der Waals interactions. The thermal behavior of luminescence of the europium(III) complex is discussed.     

Optically hybrid lanthanide ions (Eu3+, Tb3+)‐centered materials with novel functional di‐urea linkages

The synthesis of 3‐(triethoxysilyl)‐propyl isocyanate (TEPIC) modified by (3‐aminopropyl)triethoxysilane (APS) and the preparation of the corresponding organic–inorganic molecular‐based hybrid material with the two components equipped with covalent bonds is described. The coupling agent moiety is a convolution of TEPIC and APS through ? NHC(?O)NH? groups, which is applied to coordinate to RE³⁺ and further formed Si? O backbones after hydrolysis and polycondensation processes. For comparison and luminescence efficiency purposes, we added 2,2‐bipyridyl to the above hybrids in order to increase the conjugating effects and sensitize rare earth ions emissions. Luminescence spectra were utilized to characterize the photophysical properties of the hybrid material obtained, and the above spectroscopic data reveal that the triplet energy of 2,2‐dipyridyl in this favorable hybrid system matches with the emissive energy level of RE³⁺. In this way, the intramolecular energy transfer process took place within these molecular‐based hybrids and strong green and red emissions of RE³⁺ have been achieved. Copyright © 2005 John Wiley & Sons, Ltd.     

Potentiometric, luminescence and NMR study of the interaction of Eu with glyceryl phosphates

Complexation of europium(III) with glyceryl-1- and -2-phosphates has been studied by metal ion luminescence, ¹H and ¹³C NMR spectroscopy and potentiometry. From the luminescence and NMR studies, the formation of a 1:1 inner-sphere complex, in which the glyceryl phosphate is directly bound to the metal, is confirmed. Similar apparent binding constants at pH 2 were obtained by the three methods. Values obtained by NMR at pH 2 are 53 M⁻¹ and 12 M⁻¹ for glyceryl-1- and -2-phosphate, respectively. By comparison with literature data on related systems it is suggested that the ligands bind through the phosphate group. To obtain structural information from the NMR data, complexation has also been studied with the lanthanide ions Dy(III), Er(III) and Gd(III) using both chemical shift and relaxation data. From this, metal-proton distance ratios have been calculated. Comparison of ¹H and ¹³C NMR spectral data in the presence of paramagnetic lanthanides suggests conformational equilibria in the solutions. From the potentiometric studies, global formation constants have been determined, and speciation diagrams obtained over the pH range 1.5pH7.0 for ligand/metal ratios of 1 and 30. Implications of these results on lanthanide induced fusion of phospholipid membranes are discussed.     

Magnetic moments of lanthanide 3-, 4-nitrobenzoates and 3,4-dinitrobenzoates

Summary The magnetic moments for lanthanide 3-nitro and 4-nitrobenzoates were determined at 298 K and those for 3,4-dinitrobenzoates of rare earth elements over the temperature range 77 – 296 K. The complexes of 3,4-dinitrobenzoates of rare earths were found to obey the Curie-Weiss law. The values of calculated for all complexes (except that for europium 3,4-dinitrobenzoates) are close to those obtained for Ln³⁺ ions by Hund and Van Vleck. The results reveal that irrespective of the kind of ligands (3-nitro, 4-nitro or 3,4-dinitrobenzoates) no influence of their field on lanthanide ions occurs.

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Magnetische Momente von Lanthaniden-3-nitro-, -4-nitro- und-3,4-dinitrobenzoaten

Zusammenfassung Die magnetischen Momente von Lanthaniden-3-nitro und -4-nitrobenzoaten wurden bei 298 K untersucht, die von -3,4-dinitrobenzoaten im Temperaturbereich von 77 – 296 K. Die Komplexe entsprechen der Curie-Weiss-Regel. Die für alle Komplexe gefundenen -Werte (ausgenommen das 3,4-Dinitrobenzoat von Eu) sind sehr nahe den von Hund und Van Vleck erhaltenen. Es wurde also kein Einfluß des Ligandenfeldes auf die Lanthanid-Ionen festgestellt.

     

Two novel lanthanide(III) organic frameworks based on a biphenyltetracarboxylate ligand: synthesis,structure and magnetic and luminescence properties

Two new two‐dimensional lanthanide coordination polymers, namely poly[[tetra‐μ₂‐acetato‐tetraaquabis(μ₄‐biphenyl‐3,3′,5,5′‐tetracarboxylato)tetrakis(dimethylacetamide)tetraterbium(III)] pentahydrate], {[Tb₄(C₁₆H₆O₈)₂(C₂H₃O₂)₄(C₄H₉NO)₄(H₂O)₄]·5H₂O}_n, (1), and poly[[tetra‐μ₂‐acetato‐tetraaquabis(μ₅‐biphenyl‐3,3′,5,5′‐tetracarboxylato)tetrakis(dimethylacetamide)tetraeuropium(III)] tetrahydrate], {[Eu₄(C₁₆H₆O₈)₂(C₂H₃O₂)₄(C₄H₉NO)₄(H₂O)₄]·4H₂O}_n, (2), have been synthesized from biphenyl‐3,3′,5,5′‐tetracarboxylic acid (H₄bpt) and Ln(NO₃)₃·6H₂O (Ln = Tb and Eu) under solvothermal conditions. Single‐crystal X‐ray structure analysis shows that the two compounds are isostructural and crystallize in the monoclinic P2₁/n space group. The crystal structures are constructed from bpt⁴⁻ ligands (as linkers) and {Ln₂(μ₂‐CH₃COO)₂} building units (as nodes), which topological analysis shows to be a (4,6)‐connected network with sql topology. Compounds (1) and (2) have been characterized by elemental analysis, IR spectroscopy, powder X‐ray diffraction (PXRD), thermogravimetric analysis (TGA) and fluorescence analysis in the solid state. In addition, a magnetic investigation shows the presence of antiferromagnetic interactions in compound (1).     

聚酰胺与稀土离子相互作用的研究

用热分析和傅里叶变换红外光谱法研究了尼龙6与稀土离子之间的相互作用。实验结果表明,当将稀土离子引入尼龙6体系后,可观察到以下几种效应：1)尼龙6的熔点显著降低。2)红外光谱结果表明,尼龙6-稀土体系熔化过程中,代表N－H伸缩振动的酰胺A带发生红移。3)尼龙6的酰胺Ⅰ和Ⅱ带区段,可观察到代表与稀土配位的酰胺基团的知,随着温度升高,尼龙6的酰胺Ⅰ,Ⅱ带吸光度降低而在1600cm^-^1附近的新峰的吸光度增加。     

Synthesis, structure and X-ray excited luminescence of Ce-doped AREP2O7-type alkali rare earth diphosphates (A=Na, K, Rb, Cs; RE=Y, Lu)

The crystal structures of five new alkali rare earth diphosphates were obtained by Rietveld refinement of powder X-ray diffraction (XRD) profiles, including four alkali lutetium diphosphates ALuP₂O₇ (A=Na, K, Rb, Cs) and the low temperature phase of KYP₂O₇. The scintillation properties of Ce³⁺-doped AREP₂O₇ (A=Na, K, Rb, Cs; RE=Y, Lu) powder samples were studied under static and pulsed X-ray excitations, and featured outstanding scintillation properties with light yields 1–2 times of that of Bi₄(GeO₄)₃ and relatively short decay time of 20–28 ns. Considering the suitable emission wavelength range, large light yield, short decay time, and non-hygroscopic nature, Ce³⁺-doped AREP₂O₇-type alkali rare earth diphosphates are potential candidates for high-counting-rate scintillation applications.