Ionic liquid as plasticizer for europium(III)-doped luminescent poly(methyl methacrylate) films

Flexible luminescent polymer films were obtained by doping europium(III) complexes in blends of poly(methyl methacrylate) (PMMA) and the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(6)mim][Tf2N]. Different europium(III) complexes have been incorporated in the polymer/ionic liquid matrix: [C(6)mim][Eu(nta)(4)], [C(6)mim][Eu(tta)(4)], [Eu(tta)(3)(phen)] and [choline](3)[Eu(dpa)(3)], where nta is 2-naphthoyltrifluoroacetonate, tta is 2-thenoyltrifluoroacetonate, phen is 1,10-phenanthroline, dpa is 2,6-pyridinedicarboxylate ( dipicolinate) and choline is the 2-hydroxyethyltrimethyl ammonium cation. Bright red photoluminescence was observed for all the films upon irradiation with ultraviolet radiation. The luminescent films have been investigated by high-resolution steady-state luminescence spectroscopy and by time-resolved measurements. The polymer films doped with beta-diketonate complexes are characterized by a very intense D-5(0) -> F-7(2) transition ( up to 15 times more intense than the D-5(0) -> F-7(1)) transition, whereas a marked feature of the PMMA films doped with [choline](3)[Eu(dpa)(3)] is the long lifetime of the D-5(0) excited state (1.8 ms).

Rare-earth complexes of ferrocene-containing ligands: Visible-light excitable luminescent materials

The ferrocene-derivatives bis(ferrocenyl-ethynyl)-1,10-phenanthroline (Fc(2)phen) and ferrocenoyltrifluoroacetone (Hfta) have been used to synthesize ferrocene-containing rare-earth beta-diketonate complexes. The complexes [Ln(tta)(3)(Fc(2)phen)] and [Ln(fta)(3)(phen)] (where Ln = La, Nd, Eu, Yb) show structural similarities to the tris(2-thenoyltrifluoroacetonate)(1,10-phenanthroline)lanthanide(III) complexes, [Ln(tta)(3)(phen)]. The coordination number of the lanthanide ion is 8, and the coordination sphere can be described as a distorted dodecahedron. However, the presence of the ferrocene moieties shifts the ligand absorption bands of the rare-earth complexes to longer wavelengths so that the complexes can be excited not only by ultraviolet radiation but also by visible light of wavelengths up to 420 nm. Red photoluminescence is observed for the europium(III) complexes and near-infrared photoluminescence for the neodymium(III) and ytterbium(III) complexes. The presence of the ferrocene groups makes the rare-earth complexes hydrophobic and well-soluble in apolar organic solvents.

稀土元素的时间分辨光谱法研究

稀土离子的敏化发光早在1942年就被Weissiman发现了，后来，人们对这一现象作了大量的研究工作，并且，开始用于稀土离子的测试。高灵敏度和好的选择性一直是分析工作者追求的真正目的。为此，很长时间以来，人们从化学体系上入手，不断地在配体种类；配体条件；溶剂作用；第二配体影响；胶束；表面活性剂等方面入手，来寻找可获得高的灵敏度和好的选择性的测试体系，并取得了一定的成绩，但还远远满足不了分析工作者的要求。近年来，随着仪器设备的不断改进，人们想到，能否通过新的仪器的出现来改善分析测试的灵敏度和选择性。时间分辨光谱法就是在这种条件下产生的，并且，初步的实验就得到了令人十分满意的结果。时间分辨光谱法顾名思义是以时间做为分辨量的一种方法，是一种多维萤光技术，它采用脉冲激光做为光源和门控检测系统相结合，因此，不但获得了高子常规法的灵敏度，而且还解决了光谱峰有干扰的发光组分的测定，提高了选择性。为了有效地应用时间分辨光谱法即获得更高的灵敏度和更好的选择性，时间分辨光支要求：①待测定的物质必须有较强的发光，这是提高灵敏度的前提：②待测定的物质的寿命必须合适（如测单组分时是通过延迟消除噪声，则被测组分的寿命至少要比噪音信号长；若是二组分的分辨光谱法测定，就要求二组分间寿命差要尽可能大），这样才可能效分辨；③适合彼此间有光谱干扰的多组分中单一组分的测定，这是时间分辨光谱法优于常远见二维光法的最为突出的一点。Eu-TTA_3和SmTTA_3是较合适时间分辨测定体系。Eu_TTA_3和S_m-TTA_3 二元络合物不但有较强的萤光，而且寿命差较大，EuTTA_39寿命400微秒）。SmTTA_3（寿命21微秒），并且Eu和Sm间有光谱干扰，因此在混合体系下，时间分辨光谱法测定Eu和Sm才充分显示了伏越性。为此，为了研究稀土元素的时间分辨光谱测定，本论文分三部分完成。第一部分：几种稀土离子萤光络合物体系的选择通过对Eu~(3+)、Tb~(3+)、Dy~(3+)络合体系最强发光的条件实验，期望找到一系列既有较强的发光，元素间又存在着光谱干扰。而常规法又难以测试的络合物体系。为此，在现有条件下，做了TTA、DBM、Phen、AAE、Sal五种配体Eu~(3+)、Sm~(3+)、Tb~(3+)、Py~(3+)四种稀土离子所有可能的络合物组成的发光条件试验，主要为配体浓度和PH值的影响。确定了不同络合物的最佳组成条件。并且考虑到苯的毒性和萃取的繁琐性。选用乙醇做为溶剂。最后得到TTA、DBM是Eu、Sm较好的络合剂，而且它们与Phen的三元络合物也具有强的发光。Sml:是Tb和Dy的较好络合剂，并且它们与Phen形成三元络合物也具有较强的萤光，AAE、Phen是选择性最差的络合剂，它们与Tb、Eu、Sm、Dy都能形成有一定发光强度的络合剂Eu和Sm以及Tb和Dy之间是无论配体息样变化都有光谱干扰的两对元素。第二部分；发光络合物的萤光寿命的测试：除了要求从化学体系入手，得到具有较强的发光络合物之外，时间分辨光谱法还要求；待分辩的物质间有较大的寿命差异。寿命τ是进行时间分辨光谱法的理论基础。为此，在本室和11室自己安装的仪器上做了已讨论的最佳条件下合成的络合物萤光寿命的测试，并给出了许多络合物的寿命数据。同时还讨论了配体种类，稀土离子浓度，对寿命大小的影响，得出不同的稀土离子络合物寿命差异很大，即使是相同的稀土离子，配体不同，寿命也是不同的，一般而言，Eu,Tb寿命较长，达几百微秒，Dy、Sm寿命较短，一般仅为几微秒或几十微秒，并总有寿命Tb > Eu > Sm > Dy。为了讨论稀土离子浓度对寿命的影响。选Eu. Sm-TTA和Tb. Dy-Sal-乙醇溶液为例，进行了浓度影响实验，得到浓度粹灭的同时，不仅萤光强度减弱，而且寿命缩短，最后总结出: Eu. Sm-TTA(Phen)二元（或三元）络合物和Tb. Dy-Sal(Phen)二元（或三元）络合物彼此间寿命差最大。第三部分：时间分辨光谱法研究在前二部分准备工作完成后，基本上就确定了可供时间分辩的最佳体系，即Eu. Sm-TTA二元络合物（或它与Phen形成的三元络合物）和Tb、Dy-Sal二元络合物（或与Phen形成的三元络合物）－乙醇体系。关于Eu.Sm-TTA体系的时间分辨光谱法测定，已有过研究并得到了十分满意的结果，因此，本论文选不曾有过报导的Tb、Dy-Sal 乙醇体系为时间分辨光谱法研究的对象。首先在本室和11室自建的时间分辨光谱仪上进行了仪器测量参数的选择，然后，对Tb、Dy-sal的时间分辨光谱法给以原理性的讨论，得到在延迟大于30微秒后，可消除Dy对Tb测定的干扰的结果，之后，又作了当延迟大于100微秒的条件下的时间分辩光谱法在Dy存在下测定Rb[Sal]_3的检测限的探索，并与MPF－4型萤光分光光度计的测试结果做了比较，得到了可高于常规法三个数量级的灵敏度的初步结果。本论文建立了寿命测量和激光时间分辨的实验装置，并且完成了原理性实验，在选择体系测定寿命和利用时间分辨排除稀土离子干扰方面得到了较好的初步结果，积累了大量数据完成了本论文目的要求。

Near-infrared luminescent xerogel materials covalently bonded with ternary lanthanide [Er(III), Nd(III), Yb(III), Sm(III)] complexes

A beta-diketone ligand 4,4,5,5,5-pentafluoro-1-(2-naphthyl)-1,3-butanedione (Hpfnp), which contains a pentafluoroalkyl chain, was synthesized as the main sensitizer for synthesizing new near-infrared (NIR) luminescent Ln(pfnp)(3)phen (phen = 1,10-phenanthroline) (Ln = Er, Nd, Yb, Sm) complexes. At the same time, a series of lanthanide complexes covalently bonded to xerogels by the ligand 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline (phen-Si) were synthesized in situ via a sol-gel process. [The obtained materials are denoted as xerogel-bonded Ln complexes (Ln = Er, Nd, Yb, Sm).] The single crystal structures of the Ln(pfnp) 3phen complexes were determined.

Near-infrared luminescent mesoporous materials covalently bonded with ternary lanthanide [Er(III), Nd(III), Yb(III), Sm(III), Pr(III)] complexes

New near-infrared-luminescent mesoporous materials were prepared by linking ternary lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) complexes to the ordered mesoporous MCM-41 through a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline. The resulting materials (denoted as Ln(hfth)(3)phen-M41 and Pr(tfnb)(3)phen-M41; Ln=Er, Yb, Nd, Sm; hfth = 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate; tfnb = 4,4,4-trifluoro-1-(2-naphthyl)- 1, 3-butanedionate) were characterized by powder X-ray diffraction, N-2 adsorption/desorption, and elemental analysis. Luminescence spectra of these lanthanide-complex functionalized materials were recorded, and the luminescence decay times were measured. Upon excitation at the absorption of the organic ligands, all these materials show the characteristic NIR luminescence of the corresponding lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) ions by sensitization from the organic ligands moiety. The good luminescent performances enable these NIR-luminescent mesoporous materials to have possible applications in optical amplification (operating at 1300 or 1500 nm), laser systems, or medical diagnostics.

The optical properties and the natural lifetime calculation of a Sm(III) complex

The photophysical properties of the complex Sm(PM)(3)(TP)(2) [PM = 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone, TP = triphenyl phosphine oxide] are determined in crystal state, and energy transfer process is modeled for ligands to center Sm(III) ion. The characteristic luminescence of Sm(III) is sensitized by PM and TP, and most of transitions from excited state (4)G(5/2) of Sm3+ are detected.

Syntheses, crystal structures, visible and near-IR luminescent properties of ternary lanthanide (Dy3+, Tm3+) complexes containing 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 1,10-phenanthroline

The ligands 4,4,4-trifluoro-1-phenyl-1.3-butanedione (Hbfa) and 1,10-phenanthroline (phen) were used to prepare ternary lanthanide (Ln) complexes [Dy(bfa)(3)phen and Tm(bfa)(3)phen]. Crystal data: Dy(bfa)(3)phen C(42)H(26)FqN(2)O(6)Dy, triclinic, P (1) over bar, a= 9.9450(6) angstrom, b = 14.0944(9) angstrom, c = 14.6043(9) angstrom, alpha = 82.104(1)degrees, beta = 87.006(1)degrees, gamma = 76.490(1)degrees, V = 1971.1(2)angstrom(3), Z = 2; Tm(bfa)(3)phen C42H26F9N2O6Tm, triclinic, P (1) over bar, a = 9.898(5)angstrom, b = 13.918(5)angstrom, c = 14.753(5)angstrom, a = 83.517(5)degrees, alpha = 86.899(5)degrees, gamma = 76.818(5)degrees, V = 1965.3(14)angstrom(3), Z = 2. The coordination number of the central Ln(3+) (Ln = Dy, Tm) ion is eight, with six oxygen atoms from three Hbfa ligands and two nitrogen atoms from the phen ligand.

Ternary lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) complex-functionalized mesoporous SBA-15 materials that emit in the near-infrared range

The tertiary lanthanide complexes [Ln(hfth)(3)phen] (Ln=Er, Nd, Yb, Sm) and [Pr(tfnb)(3)phen] have been Successfully covalently attached in the ordered SBA-15 mesoporous materials via a functionalized 1,10-phenanthroline group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline (Phen-Si). The derivative materials [denoted as Ln(hfth)(3)phen-S15 and Pr(tfnb)(3)phen-S15; Ln=Er, Yb, Nd, Sm; hfth=4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate; tfnb=4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionate] were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and N-2 adsorption/desorption.

Effect of secondary ligands' size on energy transfer and electroluminescent efficiencies for a series of europium(III) complexes, a density functional theory study

In this paper, a quantum chemistry method was used to investigate the effect of different sizes of substituted phenanthrolines on absorption, energy transfer, and the electroluminescent performance of a series of Eu(TTA)(3)L (L = [1,10] phenanthroline (Phen), Pyrazino[2,3-f][1,10]phenanthroline (PyPhen), 2-methylprrazino[2,3-f][1,10] phenanthroline(MPP), dipyrido[3,2-a:2',3'-c]phenazine(DPPz), 11-methyldipyrido[3,2-a:2',3'c]phenazine(MDPz), 11.12-dimethyldipyrido[3,2-a:2',3'-c]phenazine(DDPz), and benzo[i]dipyrido[3,2-a:2',3'-c]phenazine (BDPz)) complexes. Absorption spectra calculations show that different sizes of secondary ligands have different effects on transition characters, intensities, and absorption peak positions.

Near-infrared luminescent mesoporous MCM-41 materials covalently bonded with ternary thulium complexes

Two beta-diketones 4,4,4-trifluoro-1-2-thenoyl-1,3-butanedione (Htta) and 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione (Htfnb), which contain trifluoroalkyl chain, were selected as the main sensitizer for synthesizing Tm(L)(3)phen (L = tta, tfnb) complexes. The two near-infrared (NIR) luminescent thulium complexes have been covalently bonded to the ordered mesoporous material MCM-41 via a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline (phen-Si) [The resultant mesoporous materials are denoted as Tm(L)(3)phen-MCM-41 (L = tta, tfnb)]. The Tm(L)(3)phen-MCM-41 (L = tta, tfnb) mesoporous materials were characterized by small-angle Xray diffraction (XRD) and N-2 adsorption/desorption, and they show characteristic mesoporous structure of MCM-41.

Syntheses, structures and near-IR luminescent studies on ternary lanthanide (Er-III, Ho-III, Yb-III, Nd-III) complexes containing 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate

The ligand Hhfth [4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dione], which contains a heptafluoropropyl group, has been used to synthesize several new ternary lanthanide complexes (Ln = Er, Ho, Yb, Nd) in which the synergistic ligand is 1,10-phenanthroline (phen) or 2,2'-bipyridine (bipy). The two series of complexes are [Ln(hfth)(3)phen] [abbreviated as (Ln)1, where Ln = Er, Ho, Yb] and [Ln(hfth)(3)bipy] [abbreviated as (Ln)2, where Ln = Er, Ho, Yb, Nd]. Members of the two series have been structurally characterized. The growth morphology, diffuse reflectance (DR) spectra, thermogravimetric analyses, and photophysical studies of these complexes are described in detail. After ligand-mediated excitation of the complexes, they all show the characteristic near-infrared (NIR) luminescence of the corresponding Ln(3+) ions (Ln = Er, Ho, Yb, Nd). This is attributed to efficient energy transfer from the ligands to the central Ln(3+) ions, i.e. an antenna effect. The heptafluorinated substituent in the main hfth sensitizer serves to reduce the degree of vibrational quenching. With these NIR-luminescent lanthanide complexes, the luminescent spectral region from 1300 to 1600 nm, which is of particular interest for telecommunication applications, can be covered completely.

Local structure and valences of samariurn in SrB4O7 : Sm and SrB6O10 : Sm prepared in-air

The coordination numbers for the samarium atoms and the Sm-O bond distances in SrB4O7:Sm and SrB6O10:Sm prepared in air were determined by means of Sm-L-3 edge EXAFS. The coordination. was found to be nine-folded for both these hosts and the bond distance was 2.40-2.42 Angstrom in SrB4O7:Sm and 2.42-2.44 Angstrom in SrB6O10:Sm. For SrB4O7:Sm the coordination number is coincident with that of the strontium. atoms suggesting the substitution of the samarium atoms at the strontium sites. The coordination number of the strontium atoms in SrB6O10 was also suggested to be nine assuming the same type of substitution. The valences of samarium were determined from the luminescent spectra. Both divalent and trivalent ions were present in both SrB4O7:Sm and SrB6O10:Sm, while the fraction of Sm2+ was higher in the former than in the latter. This difference has been assigned to the difference in rigidity between the B-O networks in these structures.

UV-VUV excited luminescence of SrBPO5 : Sm phosphor prepared in air

The high-resolution luminescent spectrum of divalent samarium excited by 355 nm UV light at 77 K, the VUV excitation spectra, the VUV excited emission spectra and EXAFS at Sm-L-3 edge were reported for samarium doped strontium borophosphate, SrBPO5:Sm prepared by solid state reaction in air at high temperature. The high-resolution luminescent spectrum showed that the divalent samarium ions occupied the C-2upsilon lattice sites. The VUV excitation spectra indicated that the sample exhibited absorption bands with the maxima at 129 and 148 nm, respectively. The performance of EXAFS at Sm-L3 absorption edge suggested that the samarium ions were nine-coordinated and the mean distances of bond Sm-O were 2.38 Angstrom.

Eu(TTA)_3/MCM-41介孔复合体的溶胶凝胶法组装

利用溶胶 凝胶法将稀土配合物Eu(TTA) 3 组装到MCM 41介孔分子筛的孔道中 ,并初步认定客体分子Eu(TTA) 3 是以加合物形式包裹于表面活性剂胶束中。该法制得的介孔复合体Eu(TTA) 3/MCM 41,用XRD、HRTEM技术证实具有短程有序的、规整的六方介孔结构和大小分布均匀的纳米晶粒。对其光致发光和荧光寿命的研究发现 :与乙醇溶液中相比 ,Eu3 +的荧光寿命没有发生改变 ,但Stokes位移却明显增大 ;复合体中 ,能量是从主体MCM 41传递到客体Eu(TTA) 3 上。

矿物中REE扩散作用的理论研究——兼论白钨矿Sm-Nd定年方法的可靠性

元素在矿物中的扩散作用，对其在地质体中的配布有着重要影响，被越来越多的用来解决地球化学动力学方面的问题。稀土元素（REE）能反映重要的地球化学信息，作为地球化学的示踪剂被广泛应用于探讨各类岩石成因和矿床成因。因此，查明REE在矿物中的扩散行为对于地学研究具有重要意义。 前人对元素（如O、Ar等）在不同矿物中扩散行为的理论研究，大多采用的是矿物晶格单独制约扩散速率的模型，由于稀土元素的离子半径各不相同，用此类模型来探讨其在不同矿物中的扩散行为是不合适的。为了寻求获取矿物中稀土元素扩散参数的简捷途径，本博士论文通过对前人关于矿物中REE扩散作用研究的实验结果进行分析归纳，探讨了扩散体系不同因素对扩散行为的控制规律。在此基础上，使用多元统计分析方法建立了预测REE在不同矿物中扩散参数的多变量模型，由此模型计算的1atm、无水环境下REE的扩散参数与实验测定结果在实验误差范围内相当吻合。与前人的模型相比，多变量模型能更全面地反映扩散体系各因素对扩散速率的制约。 此外，为了检验白钨矿Sm-Nd同位素定年方法的可靠性，本论文从不同角度进行了研究： （一） 理论验证 矿物内部的微量元素信息能否有效保存，在很大程度上取决于其扩散速率，因此本文从扩散动力学角度对白钨矿Sm-Nd同位素体系的封闭性进行了探讨。通过理论计算并结合实验模拟验证的方式获得了白钨矿中Sm、Nd的扩散参数，得出在1atm、无水环境下Sm和Nd的扩散方程为： Nd：D＝4.00exp（－438kJmol-1/RT）cm2/s Sm：D＝1.85exp（－427kJmol-1/RT）cm2/s 借助这些扩散数据，对白钨矿中Sm-Nd信息受扩散作用的影响程度做了分析。结果表明，在大多数地质环境下，Sm、Nd在白钨矿晶体中的扩散速率很低，同位素体系容易保持封闭不受热力学作用的影响。 （二） 地质验证 以湘西沃溪Au-Sb-W矿床为研究对象，通过对不同矿体的白钨矿进行Sm-Nd同位素年龄测定，将其结果与其它同位素方法得到的年龄数据以及野外地质关系、区域构造演化等进行了对比。结果表明，沃溪Au-Sb-W矿床的白钨矿Sm-Nd年龄结果与Ar-Ar年龄是一致的，与野外地质关系及区域构造演化特征等也相当吻合。 通过本论文的工作，得出以下主要成果和认识： （1）首次建立了适合于计算REE在不同矿物中扩散参数的理论模型，为研究矿物中REE的扩散行为提供了可靠的理论方法。 （2）首次获得了白钨矿中Sm-Nd的扩散参数，探讨了白钨矿中REE的扩散性质，并建立了1atm、无水环境下Sm和Nd在此矿物中的扩散方程。 （3）通过扩散动力学研究，得出白钨矿中Sm-Nd同位素体系的封闭性较为理想，为评价Sm-Nd同位素方法是否适合于制约白钨矿的成矿年龄提供了理论依据。 （4）通过不同同位素定年结果的比较以及与野外地质关系、区域构造演化等的对比，得出白钨矿Sm-Nd同位素年龄结果是真实有效的，从矿床学角度为评价该同位素定年方法的可靠性提供了实践证据。