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.

Lanthanide-doped luminescent ionogels

Ionogels are solid oxide host networks con. ning at a meso-scale ionic liquids, and retaining their liquid nature. Ionogels were obtained by dissolving lanthanide(III) complexes in the ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, [C(6)mim][Tf2N], followed by confinement of the lanthanide-doped ionic liquid mixtures in the pores of a nano-porous silica network. [C(6)mim][Ln(tta)(4)], where tta is 2-thenoyltrifluoroacetonate and Ln = Nd, Sm, Eu, Ho, Er, Yb, and [choline](3)[Tb(dpa)(3)], where dpa = pyridine-2,6-dicarboxylate (dipicolinate), were chosen as the lanthanide complexes. The ionogels are luminescent, ion-conductive inorganic-organic hybrid materials. Depending on the lanthanide(III) ion, emission in the visible or the near-infrared regions of the electromagnetic spectrum was observed. The work presented herein highlights that the confinement did not disturb the first coordination sphere of the lanthanide ions and also showed the excellent luminescence performance of the lanthanide tetrakis beta-diketonate complexes. The crystal structures of the complexes [C(6)mim][Yb(tta)(4)] and [choline](3)[Tb(dpa)(3)] are reported.

Fully fluorinated imidodiphosphinate shells for visible- and NIR-Emitting lanthanides: Hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties

In this paper we demonstrate that the effect of aromatic C-F substitution in ligands does not always abide by conventional wisdom for ligand design to enhance sensitisation for visible lanthanide emission, in contrast with NIR emission for which the same effect coupled with shell formation leads to unprecedented long luminescence lifetimes. We have chosen an imidodiphosphinate ligand, N-{P,P-di-(pentafluorophinoyl)}-P,P-dipentafluoro-phenylphosphinimidic acid (HF(20)tpip), to form ideal fluorinated shells about all visible- and NIR-emitting lanthanides. The shell, formed by three ligands, comprises twelve fully fluorinated aryl sensitiser groups, yet no-high energy X-H vibrations that quench lanthanide emission. The synthesis, full characterisation including X-ray and NMR analysis as well as the photophysical properties of the emissive complexes [Ln(F(20)tpip)(3)], in which Ln=Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Y, Gd, are reported. The photophysical results contrast previous studies, in which fluorination of alkyl chains tends to lead to more emissive lanthanide complexes for both visible and NIR emission. Analysis of the fluorescence properties of the HF(20)tpip and [Gd(F(20)tpip)(3)] reveals that there is a low-lying state at around 715 nm that is responsible for partially quenching of the signal of the visible emitting lanthanides and we attribute it to a pi-sigma* state. However, all visible emitting lanthanides have long lifetimes and unexpectedly the [Dy(F(20)tpip)(3)] complex shows a lifetime of 0.3 ms, indicating that the elimination of high-energy vibrations from the ligand framework is particularly favourable for Dy. The NIR emitting lanthanides show strong emission signals in powder and solution with unprecedented lifetimes. The luminescence lifetimes of [Nd(F(20)tpip)(3)], [Er(F(20)tpip)(3)] and [Yb(F(20)tpip)(3)] in deuteurated acetonitrile are 44, 741 and 1111 mu s. The highest value observed for the [Yb(F(20)tpip)(3)] complex is more than half the value of the Yb ion radiative lifetime.

Cobalt(II) Complexes of Nitrile-Functionalized Ionic Liquids

A series of nitrile-functionalized ionic liquids were found to exhibit temperature-dependent miscibility (thermomorphism) with the lower alcohols. Their coordinating abilities toward cobalt(II) ions were investigated through the dissolution process of cobalt(II) bis(trifluoromethylsulfonyl)imide and were found to depend on the donor abilities of the nitrile group. The crystal structures of the cobalt(II) solvates [Co(C1C1CNPyr)2(Tf2N)4] and [Co(C1C2CNPyr)6][Tf2N]8, which were isolated from ionic-liquid solutions, gave an insight into the coordination chemistry of functionalized ionic liquids. Smooth layers of cobalt metal could be obtained by electrodeposition of the cobalt-containing ionic liquids.

Synthesis, structural characterization, luminescent properties and theoretical study of three novel lanthanide metal-organic frameworks of Ho(III), Gd(III) and Eu(III) with 2,5-thiophenedicarboxylate anion

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Novel europium and gadolinium complexes with methaneseleninate as ligand: Synthesis, characterization and spectroscopic study

The methaneseleninate and 1,10-phenanthroline were used as ligands in the synthesis of new lanthanide complexes. The photostability, emission quantum yield (q) and quantum efficiency (eta) of the D-5(0) emitting level of the Eu3+ ion were determined. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal intramolecular energy transfer process. The nephelauxetic effect was investigated to assess the covalency of the ligand-metal chemical bond. The values of the experimental 4f-4f intensity parameters, suggest that this ion is in a chemical environment less polarisable than in the case of complexes with beta-diketonates as ligands. (C) 2011 Elsevier B.V. All rights reserved.

Synthesis and Characterization of the Europium(III) Pentakis(picrate) Complexes with Imidazolium Countercations: Structural and Photoluminescence Study

Six new lanthanide complexes of stoichiometric formula (C)(2)[Ln(Pic)(5)]-where (C) is a imidazolium cation coming from the ionic liquids 1-butyl-3-methylimidazolium picrate (BMIm-Pic), 1-butyl-3-ethylimidazolium picrate (BEIm-Pic), and 1,3-dibutylimidazolium picrate (BBIm-Pic), and Ln is Eu(III) or Gd(III) ions-have been prepared and characterized. To the best of our knowledge, these are the first cases of Ln(III) pentakis(picrate) complexes. The crystal structures of (BEIm)(2)[Eu(Pic)(5)] and (BBIm)(2)[Eu(Pic)(5)] compounds were determined by single-crystal X-ray diffraction. The [Eu(Pic)(5)](2-) polyhedra have nine oxygen atoms coordinated to the Eu(III) ion, four oxygen atoms from bidentate picrate, and one oxygen atom from monodentate picrate. The structures of the Eu complexes were also calculated using the sparkle model for lanthanide complexes, allowing an analysis of intramolecular energy transfer processes in the coordination compounds. The photoluminescence properties of the Eu(III) complexes were then studied experimentally and theoretically, leading to a rationalization of their emission quantum yields.

Linewidths and line shapes in the vicinity of graphene

It is well known that graphene, by virtue of its pi-cloud delocalization, has a continuum of electronic energy states and thus behaves nearly like a metal. Instances involving quenching of electronic energy excitation in fluorophores placed in the proximity of graphene sheets are well documented. In this paper, we perform theoretical investigations on the broadening of vibrational and electronic transitions in the vicinity of graphene. We find that for CO vibrations in the vicinity of undoped graphene, the broadening at a distance of 5 angstrom is similar to 0.008 cm(-1)((kappa) over tilde = 2, (kappa) over tilde being the effective dielectric constant). In comparison, for electronic transitions, the linewidth is much larger, being of the order of several cm(-1). Also, if the transition dipole were parallel to the graphene sheet, the linewidth would be reduced to half the value for the case where it is perpendicular, an observation which should be easy to check experimentally for electronic transitions. This should be observable for the f - f transitions (which are rather narrow) of Lanthanide complexes placed within a distance of a few nanometers from a graphene sheet. Further the linewidth would have a (distance)(-4) dependence as one varies the distance from graphene. (C) 2014 AIP Publishing LLC.

Mechanistic aspects of the Ziegler-Natta polymerization

The isotope effect on propagation rate was determined for four homogeneous ethylene polymerization systems. The catalytic system Cp_2Ti(Et)Cl + EtA1Cl_2 has a k^H_p/k^D_p = 1.035 ± 0.03. This result strongly supports an insertion mechanism which does not involve a hydrogen migration during the rate determining step of propagation (Cossee mechanism). Three metal-alkyl free systems were also studied. The catalyst I_2 (PMe_3)_3Ta(neopentylidene)(H) has a k^H_p/k^D_p = 1.709. It is interpreted as a primary isotope effect involving a non-linear a-hydrogen migration during the rate determining step of propagation (Green mechanism). The lanthanide complexes Cp*_2LuMe•Et_2O and Cp*_2YbMe•Et_2O have a k^H_p/k^D_p = 1.46 and 1.25, respectively. They are interpreted as primary isotope effects due to a partial hydrogen migration during the rate determining step of propagation.

The presence of a precoordination or other intermediate species during the polymerization of ethylene by the mentioned metal-alkyl free catalysts was sought by low temperature NMR spectroscopy. However, no evidence for such species was found. If they exist, their concentrations are very small or their lifetimes are shorter than the NMR time scale.

Two titanocene (alkenyl)chlorides (hexenyl 1 and heptenyl 2 were prepared from titanocene dichloride and a THF solution of the corresponding alkenylmagnesium chloride. They do not cyclize in solution when alone, but cyclization to their respective titanocene(methyl(cycloalkyl) chlorides occurs readily in the presence of a Lewis acid. It is demonstrated that such cyclization occurs with the alkenyl ligand within the coordination sphere of the titanium atom. Cyclization of 1 with EtAlCl_2 at 0°C occurs in less than 95 msec (ethylene insertion time), as shown by the presence of 97% cyclopentyl-capped oligomers when polymerizing ethylene with this system. Some alkyl exchange occurs (3%). Cyclization of 2 is slower under the same reaction conditions and is not complete in 95 msec as shown by the presence of both cyclohexyl-capped oligomers (35%) and odd number α-olefin oligomers (50%). Alkyl exchange is more extensive as evidenced by the even number n-alkanes (15%).

Cyclization of 2-d_1 (titanocene(hept-6-en-1-yl-1-d_1)chloride) with EtA1Cl_2 demonstrated that for this system there is no α-hydrogen participation during said process. The cyclization is believed to occur by a Cossee-type mechanism. There was no evidence for precoordination of the alkenyl double bond during the cyclization process.

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。