色氨酸与稀土元素Eu(Ⅲ)配合物的合成及配位位置的研究

氨基酸是生命系统中蛋白质的基本结构单位.本文通过共沉淀法合成了色氨酸与稀土元素Eu(Ⅲ)的固体配合物,并对其进行了光谱及波谱研究,确定了配合物的配位机理及配位点.     

The unusual magnetotransport properties of La0.67Sr0.33MnO3 with Nb2O5 addition

Enhancements of the low-field (LFMR) and high-field magnetoresistance (HFMR) were observed in the manganite system prepared by doping Nb₂O₅ into La_0.67Sr_0.33MnO₃ powders. The maximum MR ratios at 77 K with H=1 T and 1 kOe are 30% and 20% for the 0.07 molar ratio doped sample, which are 1.7 times and 1.6 times as large as that for LSMO, respectively. An MR effect up to 6.5% was also found for the sample with x=0.03 at room temperature (RT). The spin-dependent tunneling and scattering at the interfaces of grain boundaries are responsible for the LFMR while the HFMR originates from a noncollinear spin structure in the surface layer. With increasing x, the Curie temperature (T_C) decreases monotonically from 364 to 154 K while the temperature T_P related to the peak resistivity decreases firstly to a minimum of 204 K (x=0.06) and then rises up to 240 K (x=0.1). There is a maximum resistivity ρ for the sample with x=0.06, which is higher than that for LSMO by five orders of magnitude. It is due to the enhancement of spin-dependent and independent scattering and tunneling effects on the interfaces of grain boundaries and inside the grains.     

稀土元素R4OCl6四面体嵌合物的化学键研究

以SCC-DV-X,方法对Sm_4OCl_6、Eu_4OCl_6、Yb_4OCl_6和Gd_6N_2Cl_(12)等4个体系作了量化计算。结果表明,嵌入原子在四面体簇的合成中起决定性作用。体系6个骨架轨道中,3个是嵌入原子与稀土原子的成键轨道,另3个是稀土原子通过嵌入原子形成的弱键轨道。用Sm、Eu等元素能合成四面体嵌合物,与其价态较低有关,低价态使稀土元素d、f轨道收缩较少、成键能力增大。而富含f电子的Yb体系,4f为主要价轨道。     

ICP-AES法测定高纯氧化铕中稀土杂质元素

研究了锌粉还原 5709萃淋树脂分离富集 ICP AES法测定高纯氧化铕中14个稀土杂质元素的方法,用ICP AES法测定稀土元素工作曲线下限为(以氧化物计)镧为0.05mg·L-1,铈、镨、钇为0.25mg·L-1,钕、钐、铽、镝、钬为0.1mg·L-1,铒、铥、镱、镥、钇为0.05mg·L-1,回收率为90%～106%。方法简便、准确、快速,可用于99.99%氧化铕中14个稀土杂质元素的测定。     

稀土富勒烯与苯的气相加合

内嵌稀土元素的富勒烯化合物一稀土富勒烯Lit＠CZ。是一类新型的化合物．它具有独特的“超分子结构和巨大的潜在用途，将在未来的功能材料开发中起到不可估量的作用［‘］．目前关干稀土富勒烯的研究主要集中于稀土富勒烯的合成、分离、纯化、表征和理论方面．关于稀土富勒烯化     

The first rubidium rare-earth(III) thiophosphates: Rb3M3[PS4]4 (M=Pr, Er)

The two non-isotypical rubidium rare-earth(III) thiophosphates Rb₃M₃[PS₄]₄ of praseodymium and erbium can easily be obtained by the stoichiometric reaction of the respective rare-earth metal, red phosphorus and sulfur with an excess of rubidium bromide (RbBr) as flux and rubidium source at 950°C for 14 days in evacuated silica tubes. The pale green platelet-shaped single crystals of Rb₃Pr₃[PS₄]₄ as well as the pink rods of Rb₃Er₃[PS₄]₄ are moisture sensitive. Rb₃Pr₃[PS₄]₄ crystallizes triclinically in the space group (, , , α=84.329(4)°, β=88.008(4)°, γ=80.704(4)°; Z=2), Rb₃Er₃[PS₄]₄ monoclinically in the space group P2₁/n (, , , β=95.601(6)°; Z=4). In both structures, there are three crystallographically different rare-earth cations present. (M1)³⁺ is eightfold coordinated in the shape of a square antiprism, (M2)³⁺ and (M3)³⁺ are both surrounded by eight sulfur atoms as bicapped trigonal prisms each with a coordination number of eight as well as for the praseodymium, but better described as CN=7+1 in the case of the erbium compound. These [MS₈]¹³⁻ polyhedra form a layer according to by sharing edges with the isolated [PS₄]³⁻ tetrahedra (d(P-S)=200-209 pm, ?(S-P-S)=102-116°). These layers are stacked with a repetition period of three in the case of the praseodymium compound, but of only two for the erbium analog. The rubidium cation (Rb1)⁺ is located in cavities of these layers and tenfold coordinated in the shape of a tetracapped trigonal antiprism. The also tenfold but more irregularly coordinated rubidium cations (Rb2)⁺ and (Rb3)⁺ reside between the layers.     

AB5型贮氢合金电极的性能

在金属氢化物一镍电池（MH／Ni）负极材料中，ABS型贮氢合金是非常具有吸引力的一种，以AB。型贮氢合金作为负极材料的MH／Ni电池目前已大批量进入市场．其中A代表混合稀土RE（主要成分为La，Ce，Pr，Nd）；B代表Ni和Co，Mll，AI等取代元素．B侧取代元素已被广泛研究D，习，A侧混合稀土的成分也已引起人们的广泛重视＊‘，’］，＊血1c等【阿针对儿一N13。5C00．75Mll。。A10．3，详细研究了L31。CI。BS系列合金，得出在。＝0．2处合金具有较好的综合性能．本文针对B侧Ni。。。Coo，。Mno、。Alo二。（记为民）成分，在研…     

Syntheses and structures of CsHo3Te5 and Cs3Tm11Te18 and the electronic structure of CsHo3Te5

Single crystals of CsHo₃Te₅ and Cs₃Tm₁₁Te₁₈ have been grown as byproducts in the synthesis of CsLnZnTe₃ (Ln=Ho or Tm) through the reaction of Ln, Zn, and Te with a CsCl flux at 850 °C. The crystal structures have been determined from single-crystal X-ray diffraction data. CsHo₃Te₅ crystallizes in space group Pnma of the orthorhombic system whereas Cs₃Tm₁₁Te₁₈ crystallizes in the space group C2/m of the monoclinic system. Each of the compounds adopts a three-dimensional structure; each possesses tunnels built from LnTe₆ octahedra that are filled with Cs atoms. The pseudo-rectangular tunnel in CsHo₃Te₅ is large enough in cross-section to accommodate two symmetrically equivalent Cs atoms. In the Cs₃Tm₁₁Te₁₈ structure there are two different sized tunnels: the smaller one is only large enough to host one Cs atom per unit cell whereas the larger one can accommodate two Cs atoms. The electronic structure of CsHo₃Te₅ was calculated. The band gap is estimated to be about 1.2 eV, consistent with the black color of the crystals.     

Metallic behavior of the Zintl phase EuGe2: combined structural studies, property measurements, and electronic structure calculations

The Zintl compound EuGe₂ crystallizes in the trigonal space group (No. 164) with the CeCd₂-structure type. Its structure can be formally derived from the hexagonal AlB₂-structure type by a strong puckering of the hexagonal layers. The chemical bonding in EuGe₂ can be rationalized according to the Zintl concept as (Eu²⁺)(Ge¹⁻)₂, since the europium atoms are divalent and each germanium atom receives one additional valence electron. In that sense, EuGe₂ is expected to be a closed-shell compound with semiconducting behavior. However, temperature dependent resistivity measurements show EuGe₂ to be metallic. Subsequently, detailed crystallographic studies revealed the structure and the composition of EuGe₂ to be free of defects and impurities, which, along with the confirmed divalent oxidation state of the europium atoms by means of magnetic measurements, make EuGe₂ another example of a metallic Zintl phase. These results are in good agreement with the results of electronic structure calculations such as TB-LMTO-ASA (LDA) and FLAPW (GGA), which reveal non-zero DOS at the Fermi level.     

Understanding spin configuration in the geometrically frustrated magnet TbB4: A resonant soft X-ray scattering study

The frustrated magnet has been regarded as a system that could be a promising host material for the quantum spin liquid (QSL). However, it is difficult to determine the spin configuration and the corresponding mechanism in this system, because of its geometrical frustration (i.e., crystal structure and symmetry). Herein, we systematically investigate one of the geometrically frustrated magnets, the TbB₄ compound. Using resonant soft x-ray scattering (RSXS), we explored its spin configuration, as well as Tb's quadrupole. Comprehensive evaluations of the temperature and photon energy/polarization dependences of the RSXS signals reveal the mechanism of spin reorientation upon cooling down, which is the sophisticated interplay between the Tb spin and the crystal symmetry rather than its orbit (quadrupole). Our results and their implications would further shed a light on the search for possible realization of QSL.