New development of organolanthanide complexes containing chalcogenide ligands

This article is to present and outline new approaches to chalcogen coordination chemistry from the organolanthanides point of view.

Synthesis of the first mono(cyclopentadienyl)lanthanide Schiff base complex bearing C-2-symmetric tetradentate ligand: crystal structure of [(eta(5)-C5H5)Yb(mu-OC20H20N2O)](2)(mu-THF)(THF)

Reaction of YbCl3 with 3 equimolar CpNa (Cp = cyclopentadienide) in THF, followed by treatment with trans-(+/-)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine led to the isolation of first mono(cyclopentadienyl) lanthanide Schiff base complex, [(eta(5)-C5H5)Yb(mu-OC20H20N2O)](2) (mu-THF)(THF) (1). The molecular structure of 1 shows that it is a dimer in which the two [(eta(5)-C5H5)Yb(mu-OC20H20N2O)] units connecting via a bridging THF oxygen and two bridging oxygen atoms from Schiff base ligands. (C) 1998 Elsevier Science S.A.

A novel structure analysis method for lanthanide complex - None paramagnetic shift tri-lanthanide mixture method

A new structure analysis method for lanthanide complexes was proposed, that is, none paramagnetic shift tri-lanthanide mixture method, It was found that the paramagnetic induced shift could be cancelled by mixing three kinds of paramagnetic lanthanide ions in appropriate proportion. As a result, the chelating sites would he seen simplely from the half widths and the relative distances between lanthanide ion and the ligand nucleus could be calculated from the relaxation time (T-1) or the half width. Care should be addressed that the analysis method is suitable for the systems in which intramolecular arrangements and intermolecular ligand exchanges are relatively fasten NMR time scale used.

Preparation and characterization of polymer-supported rare earth complexes

The polymers containing different ligand groups of atoms (mainly O, N, and S) and their rare earth complexes were prepared, characterized and classified based on the type of metal-ligand tending. The catalytic activities of the complexes are briefly discussed. The polymer-supported rare earth complexes showed much greater activities than the corresponding complexes with a low molecular weight.

吡唑酮衍生物的稀土配合物光致和电致发光性能研究

稀土配合物的发光具有发射带窄、色纯度高、峰发光位置不受配体环境变化的影响、发光不受温度影响等特点，而且发射峰覆盖400-1800纳米的可见区和近红外区，因此可以作为有机电致发光器件的发光层材料。现在的研究大多集中于铕、铽配合物的电致发光器件研究，对于近红外稀土配合物的电致发光以及发白光的镝配合物研究相对较少，但是近红外发光的稀土铒、钕、镱在光通讯、激光技术、生物医学、荧光探针等方面具有特殊的应用前景。在本论文中主要阐述了新型稀土配合物的设计与合成、在器件方面的应用以及器件结构机理的研究。 在本论文中，我们主要研究吡唑酮的衍生物配体对于稀土离子的敏化激发作用。通过配体基团的改性，得到发光更有效的新型稀土配合物。首先，合成了配体PM，并选择TP、Phen、Bipy、Bath做第二配体制备镝、铒、钕、镱、钐等的配合物。解析了配合物的晶体结构，测试得到了各种配合物的光致发光性能，系统分析了几种配合物中配体到中心稀土离子的能量传递过程，研究了配体对稀土的敏化机制。其中镝配合物显示近白光的发射，色坐标为x=0.35，y=0.40，以此配合物为发光层的器件显示明亮的白光，最大发光亮度为527cd/m2，是目前已经报道的镝配合物器件中，性能最突出的一个。 设计合成了配体PT、PC、PF，利用TP和Bath做中性配体与镱离子形成配合物YbPT3Bath、YbPT3TP、YbPC3Bath，它们都显示977纳米的近红外发射。经过分析发现，配体对镱离子的敏化过程是通过电子转移的机制来完成的。通过几种镱配合物发光强度对比发现YbPT3Bath、YbPC3Bath的发射最强。首先将YbPT3Bath用于电致发光器件中，发现其具有较好的电子传输特性，而且YbPM3TP2具有较好的空穴传输特性。因此，我们将这两种配合物结合制备了双发光层电致发光器件，得到的器件比单发光层器件的性能提升了若干倍。我们认为，双发光层器件结构改善了载流子的传输和最终的复合，使得激子在发光层内形成，提高激子激发发光层材料的效率。最后，利用这种双发光层器件结构得到了辐照度比较理想的镱配合物近红外器件。 对ErPM3TP2、NdPM3TP2配合物的发光性能做了系统研究。首先，分析了它们的晶体结构，得到了具体的晶体参数和结构组成。二者在紫外区的吸收光谱都显示为配体的吸收，在紫外区之后出现了稀土离子的特征吸收峰，由此我们利用Judd-Ofelt理论分析计算了Er3+、Nd3+离子在这个配位环境中的振子强度参数，最后得到Er3+、Nd3+离子从激发态能级到下能级的电偶极跃迁辐射几率以及相应的自然寿命值。利用这两种配合物做为发光层材料制备了系列近红外电致发光器件，得到理想的辐照度强度，证明它们在制备近红外器件方面具有潜在应用价值。

四氢糠环戊二烯基烯土配合物的合成及表征

本文合成了四氢糠基环戊二烯, 并以其为配体合成了四氢糠基环戊二烯基钠盐及四氢糠基环戊二烯基稀土配合物，用元素分析，红外光谱，质谱，核磁共振谱，光电子能谱进行了表征，用X－射线衍射法测定了四氢糠基环戊二烯基钠和四氢糠基环戊二烯基镝和镱的晶体结构。

Syntheses, structures and reactions of a series of beta-diketiminatoyttrium compounds

This paper describes the synthesis and selected reactions of a series of crystalline mono(beta-diiminato) yttrium chlorides 3a, 3b, 4a, 4b, 5a, 5b, 5c and 9. The X-ray structure of each has been determined, as well as of [YCl(L-4)(2)] (6), [Y(L-1)(2)OBut] (7) and [Y{CH(SiMe3)(2)}(thf)(mu-Cl)(2)Li(OEt2)(2)(mu-Cl)](2) (8).

Holmium porphyrin compound liquid crystals: Synthesis and properties

5,10,15,20-Tetra-[(p-alkoxy-m-ethyloxy)phenyl]porphyrin and [5-(p-alkoxy)phenyl-10,15,20-tri-phenyl]porphyrin and their holmium(III) complexes are reported. They display a hexagonal columnar discotic columnar Col(h)) liquid crystal phase and were studied by cyclic voltammetry, surface photovoltage spectroscopy (SPS), electric-field-induced surface photovoltage spectroscopy (EFISPS) and luminescence spectroscopy. Within the accessible potential window, all these compounds exhibit two one-electron reversible redox reactions. Quantum yields of Q band are in the region 0.0045-0.21 at room temperature. The SPS and EFISPS reveal that all the compounds are p-type semiconductors and exhibit photovoltaic response due to pi-pi* electron transitions.

Near-infrared luminescent properties and natural lifetime calculation of a novel Er3+ complex

in this communication, a novel Er3+ complex Er(PT)(3)TPPO [PT = 1-phenyl-3-methyl-4-tert-butylbenzoyl-5-pyrazolone, TPPO = triphenyl phosphine oxide] is successfully synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. Its optical properties and the energy transfer process from the ligand PT to the Er3+ ion are investigated, the typical near-infrared (NIR) luminescence (centered at around 1530 nm) is attributed to the I-4(13/2) -> I-4(15/2) transition of Er3+ ion which results from the efficient energy transfer from PT to Er3+ ion (an antenna effect). The wider full width at half maximum (78 nm) peaked at 1530 nm in the emission spectrum and the Judd-Ofelt theory calculation on the radiative properties suggest that Er(PT)(3)TPPO should be a promising candidate for tunable lasers and planar optical amplifiers.

Construction and Photoluminescence of Monophase Hybrid Materials Derived from a Urea-Based Bis-Silylated Bipyridine

A urea-based bis-silylated bipyridine ligand derived from 4,4'-diamino-2,2'-bipyridine has been prepared. Organic-inorganic hybrid materials with a high loading of lanthanide 2,2-bipyridine moieties were obtained by using the silylated bipyridine as the only siloxane network precursor in the presence of lanthanide ions (or lanthanide complexes). The in-situ formation of lanthanide complexes from lanthanide ions and the silylated bipyridine during the sol-gel processing was confirmed by the luminescence behavior of the obtained hybrid materials and that of the corresponding pure lanthanide complex [Ln(bpy)(2)Cl-3 center dot 2H(2)O].

Stabilization of Imidosamarium(III) Cubane by Amidinates

An imidosamarium(III) cubane has been prepared from the reductive cleavage of azobenzene by a divalent samarium bis (amidinate) complex, indicating that the "spectratoe" bis(amidinate) and the resulting imido ligands help to stabilize the cubane framework. The cubane-type imido cluster is a novel unit in lanthanide chemistry.

Synthesis, characterization, and near-infrared luminescent properties of the ternary thulium complex covalently bonded to mesoporous MCM-41

The crystal structure of a ternary Tm(DBM)(3)phen complex (DBM - dibenzoylmethane; phen = 1. 10-phenanthroline) and the synthesis of hybrid mesoporous material in which the complex covalently bonded to mesoporous MCM-41 are reported. Crystal data: Tm(DBM)(3)phen C59H47N2O7Tm, monoclinic P21/c, a = 19.3216(12) A, b = 10.6691(7) A, c = 23.0165(15)A, alpha = 90, beta = 91.6330(10), gamma = 90, V = 4742.8(5) A(3), Z = 4. The properties of the Tm(DBM)(3)phen complex and the corresponding hybrid mesoporous material [Tm(DBM)(3)phen-MCM-41] have been studied. The results reveal that the Tm(DBM)(3)phen complex is successfully covalently bonded to MCM-41.

Coordination-Induced Formation of One-Dimensional Nanostructures of Europium Benzene-1,3,5-tricarboxylate and Its Solid-State Thermal Transformation

Novel one-dimensional europium benzene-1,3,5-tricarboxylate compressed nanorods have been synthesized oil it large scale through direct precipitation in solution phase under moderate conditions without the assistance of any surfactant, catalyst, or template. The obtained nanorods have widths of about 50-100 not, thicknesses of 10-20 nm, and lengths ranging from a few hundred nanometers to several micrometers. X-ray powder diffraction. elemental analysis, Fourier transform infrared Studies, and thermogravimetric and differential thermal analysis show that the nanorods have the structural formula of Eu(1,3,5-BTC)center dot 6H(2)O. Upon UV excitation, these nanorods exhibit a highly efficient luminescence. which comes from the Eu3+ ions. Moreover, Eu2O3 nanorods Could also be obtained via a thermal decomposition method using the corresponding complex as a precursor. This synthetic route is promising for the preparation of other one-dimensional crystalline nanomaterials because of its simplicity and the low cost of the starting reagents.

A monometallic tri-spin single-molecule magnet based on rare earth radicals

A mononuclear tri-spin single-molecule magnet based on the rare earth radical [Tb(hfac)(3)(NITPhOEt)(2)] (NITPhOEt = 4'-ethoxy-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized, structurally characterized and the alternating current signals show a slow relaxation of magnetization and frequency-dependent signals.

Synthesis, structure, photoluminescence, and electroluminescence properties of a new dysprosium complex

A new dysprosium complex Dy(PM)(3)(TP)(2) [where PM = 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone and TP = triphenyl phosphine oxide] was synthesized, and its single-crystal structure was also studied. Its photophysical properties were studied by absorption spectra, emission spectra, fluorescence quantum efficiency, and decay time of the f-f transition of the Dy3+ ion. In addition, the antenna effect was introduced to discuss the energy transfer mechanism between the ligand and the central Dy3+ ion. Finally, a series of devices with various structures was fabricated to investigate the electroluminescence (EL) performances of Dy(PM)(3)(TP)(2). The best device with the structure ITO/CuPc 15 nm/Dy complex 70 nm/BCP 20 nm/AlQ 30 nm/LiF 1 nm/Al 100 nm exhibits a maximum brightness of 524 cd/m(2), a current efficiency of 0.73 cd/A, and a power efficiency of 0.16 lm/W, which means that a great improvement in the performances of the device was obtained as compared to the results reported in published literature. Being identical to the PL spectrum, the EL spectrum of the complex also shows characteristic emissions of the Dy3+ ion, which consist of a yellow band at 572 nm and a blue emission band at 480 nm corresponding to the F-4(9/2)-H-6(13/2) and F-4(9/2)-H-6(15/2) transition of the Dy3+ ion, respectively. Consequently, an appropriate tuning of the blue/yellow intensity ratio can be presumed to accomplish a white luminescent emission.