非线性光学新材料K_2Ln(NO_3)_5.2H_2O(Ln=La,Ce,Pr,Nd,Sm)的晶体生长、结构和表征

非线性光学新材料Ｋ２Ｌｎ（ＮＯ３）５·２Ｈ２Ｏ（Ｌｎ＝Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ）的晶体生长、结构和表征董文庭张洪杰苏锵（中国科学院长春应用化学研究所稀土化学与物理开放实验室，长春１３００２２）Ｇｒｏｗｔｈ，ＳｔｒｕｃｔｕｒｅａｎｄＣｈａｒａｃｔ...

Relationship between the dissolution behaviours and current efficiencies of La, Ce, Pr and Nd in their chloride molten salts

The dissolution behaviours of La and Nd in their chloride molten salts were studied by means of the see-through cell, electrochemical weak polarization and quantum chemistry (extended Huckel molecular orbital). The reasons for the low current efficiencies of rare earth metals and the difference between La and Nd in their own chloride electrolytes on the basis of the solubility, rate of dissolution, and existing state of the metals dissolved as well as the structure of the melts, are discussed.

STUDIES ON ORGANOLANTHANIDE COMPLEXES .56. FORMATION OF ION-PAIR COMPLEXES [NA.3PHEN]+[LN(C5H5)3CL]-.PHEN (LN=LA, PR OR ND, PHEN = 1,10-PHENANTHROLINE) AND CRYSTAL-STRUCTURE FOR LN=PR

In the presence of 1,10-phenanthroline (phen), lanthanide chlorides LnCl3 reacted with cyclopentadienylsodium to give the novel complexes [Na.3phen]+[Ln(C5H5)3Cl]-.phen (Ln = La, Pr or Nd). In the praseodymium case, crystal structure analysis showed that

稀土（Nd，Pr）（Ⅲ）双酞菁衍生物的合成、表征和气敏特性

合成了八－４－（四氢糠氧基）酞菁钕（Ⅲ）（Ａ）、八－４－（β－萘氧基）酞菁钕（Ⅲ）（Ｂ）、八－４－（２，４－二叔戊基苯氧基）酞菁钕（Ⅲ）（Ｃ）和八－４－（２，４－二叔戊基苯氧基）酞菁镨（Ⅲ）（Ｄ）４种新的稀土（Ｎｄ、Ｐｒ）（Ⅲ）双酞菁衍生物，经元素分析、红外光谱、核磁共振谱表征．紫外可见光谱表明，它们在氯仿（１０￣（－６）ｍｏｌ／Ｌ）溶液中以单分子形式存在．热重分析证明配合物的热稳定性：Ｂ＞Ｃ～Ｄ＞Ａ．４种配合物成膜性好，Ｚ型沉积形成的单层ＬＢ膜材料对氨气有响应，特别是八－４－（四氢糠氧基）酞菁钕（Ⅲ）的膜材料对氨气很敏感，可与铜酞菁ＬＢ膜气敏性相比．

轻稀土配合物[Li·(DME)_3ⅡCH_3C_5H_4Ln(NPh_2)_3l(Ln=La、Pr、Nd)的合成和镧配合物的晶体结构

CH_3C_5H_4LnCl_2·2LiCl·nTHF与2mol的LiNPh_2在THF、已烷和甲苯混合液中反应,经DME萃取,得到[Li·(DME)_3][(η~5-CH_3C_5H_4)Ln(NPh_2)_3](Ln=La,Pr,Nd)。对其进行了元素分析、IR和NMR表征。镧配合物单晶结构测定表明,属单斜晶系,P2_1/a空间群,晶胞参数为α=1.7461(6)nm,b=1.6576(5)nm,c=1.8335(6)nm,β=96.04°,V=5.277um~3,Z=4,D_c=1.26g/cm_3,R=0.057,R_w=0.048。该配合物是一个离子对,La-N和La-C(环)键的平均距离分别为0.2459(8)和 0.2843(11)nm。稀土离子形成一个六配位的扭曲四面体。

YVO_4∶RE~(3+)(RE∶Pr、Sm、Tb、Es、Dy)晶体的研究

本文探讨了助熔剂法生长 YVO_4:RE~(3+)(RE:Pr,Sm,Tb,Er,Dy)晶体的工艺。讨论了助熔剂 V_2O_5,Pb_2P_2O_7和温度对晶体生长习性和缺陷的影响。测定了晶体的结构参数和光谱。Y_(0.9)Sm_(0.1)VO_4和 Y_(0.95)Dy_(0.05)VO_4晶体具有很好的光谱特性。

LnGa_(1-x)Fe_xO_3(Ln=La,Pr,Nd)的磁化率研究

钙钛矿型含镓的稀土复合氧化物的发光及光谱性质已有研究和报道.进一步在稀土镓复合氧化物体系中掺进过渡元素Fe~(3+)离子,用XRD,XPS和IR方法研究了LaGa_(1-x)Fe_xO_3体系中磁性铁离子的自旋态及其对化合物结构,红外光谱等性质的影响.在此基础上,本文首次对LnGa_(1-x)Fe_xO_3(Ln=La,Pr,Nd)体系化合物的磁化率等磁性质进行初步探讨,以揭

SYNTHESES AND X-RAY STRUCTURES OF BIS(T-BUTYLCYCLOPENTADIENYL)LANTHANIDE CHLORIDE COMPLEXES [(BU(T)CP)2LNCL]2 (LN = PR, GD, ER)

Reaction of lanthanide trichlorides with two equivalents of sodium t-butylcyclopentadienide in THF gave rise to the bis(t-butylcyclopentadienyl)lanthanide chloride complexes [(Bu(t)Cp)2LnCl]2 (Ln = Pr, Gd, Er), which were characterized by elemental analysis, IR and H-1 NMR spectroscopy. In addition, the crystal structures of [(ButCp)2PrCl]2 (1) and [(ButCp)2GdCl]2 (2) were determined by single crystal X-ray diffraction at room temperature. The coordination number for Pr3+ and Gd3+ is 8 and the bond lengths Pr-Cl and Gd-Cl are 2.864(2) and 2.771(3) angstrom, respectively. The structural studies showed the complexes to have C2h symmetry.

(η~5-C_5H_5)Ln(η~8-C_8H_8)(THF)_n(Ln=Pr,Nd,Gd)的合成及(η~5-C_5H_5)Pr(η~8-C_8H_8)(THF)_2的晶体结构

自1969年首次报道稀土环辛四烯基化合物Eu(C_8H_8)和Yb(C_8H_8)的合成以来,相继合成K[Ln(C_8H_8)_2],[Ln(C_8H_8)Cl·2THF]_2和[Ln(C_8H_8)·2THF]等,还报

LnBa_2C_3O_(7-δ)(Ln=Pr、Y)体系的XPS研究

该文研究了YBa_2Cu_3O_(7-δ)和PrBa_2Cu_3O_(7-δ)两体系的XPS谱图,结果表明从XPS图中难以判断三价铜的存在,与YBa_2Cu_3O_(7-δ)体系相比,PrBa_2Cu_3O_(7-δ)体系中Ba的结合能低,O_(18)的两个状态变得模糊不清。讨论了空穴浓度对高T_c超导电性的影响。

SYNTHESIS AND CRYSTAL-STRUCTURE OF HETEROPOLY MOLYBDOSILICIC LANTHANIDE K10H3[PR(SIMO11O39)2].18H2O

The intensity data of the title complex were collected at a low temperature of -90-degrees-C. The compound crystallizes in the monoclinic space group P2(1)/n, a = 17.504(2), b = 27.323 (5), c = 21.616(4) angstrom, beta = 104.49 (2)degrees, Z = 4. The structure was solved by Patterson and Fourier techniques and refined by least-squares to an R = 0.088 for 8320 independent reflections. The central Pr ion is bonded to eight oxygen atoms from two molybdosilicic heteropoly ligands to form a square antiprism. The Pr-O average distance is 2.44 (2) angstrom. Both molybdosilicic heteropoly ligands are of a defective alpha-Keggin structure.

THE SYNTHESES OF THE COMPLEXES (ETA-5-C5H5)LN(ETA-8-C8H8).NTHF AND (ETA-5-C9H7)LN(ETA-8-C8H8).2THF AND THE CRYSTAL-STRUCTURE DETERMINATION OF (ETA-5-C5H5)PR(ETA-8-C8H8).2THF AND (ETA-5-C9H7)PR(ETA-8-C8H8).2THF

LnCL3 reacts with NaC5H5 and K2C8H8 to yield the complexes (eta-5-C5H5)Ln(eta-8-C8H8).nTHF (Ln = Pr, Nd, n = 2; Ln = Gd, n = 1) and LnCl3 reacts with KC9H7 and K2C8H8 to yield the complexes (eta-5-C9H7)Ln(eta-8-C8H8).2THF (Ln = Pr, Nd; eta-5-C9H7 = indenyl); crystallography reveals (eta-5-C5H5)Pr(eta-8-C8H8).2THF and (eta-5-C9H7)Pr(eta-8-C8H8).2THF not to possess the parallel ring sandwich structure.

钙钛矿型LnGaO_3(Ln=La、Pr、Nd)晶体的光谱性质

本文报导了室温下钙钛矿型LnGaO_3(Ln=La、Pr、Nb)晶体的紫外、可见和红外吸收光谱的测定,对主要谱带进行了归属。从理论上计算出点阵振动数目和对称类型,并与实验结果进行了对比。晶体的色心及退火对吸收光谱的影响也做了研究。首次得到LaGaO_3和PrGaO_3晶体室温下的激发光谱和荧光光谱,观察到由于晶场环境不同引起荧光谱线窄化的现象。发现LaGaO_3晶体能够产主峰值为540nm的可见荧光,有成为色心发光晶体的可能性。

稀土钼硅杂多酸根配合物K_(10)H_3[Pr(SiMo_(11)·O_(39))_2]·18H_2O的合成及晶体结构

本文采用低温技术,在—90℃的干燥氮气保护下,收集标题化合物晶体的衍射数据,用重原子法解出结构。P2_1/n空间群,a=17.504(2),b=27.323(5),c=21.616(4),β=104.49(2)°,z=4.8320个衍射参与精修,最后的R值为0.088。中心离子Pr(Ⅲ)同2个钼硅杂多酸根中的8个氧原子键合,形成正方反棱柱配位多面体。Pr—O的平均键长为2.44(2)。钼硅杂多酸根配体具有缺位的α型Keggin结构。

NaLn(WO_4)_2晶体的研究(Ln=La,Pr,Nd)

用助熔剂缓冷法从Na_2WO_4—LiCl熔体中生长出NaLn(WO_4)_2(Ln=La,Pr,Nd)晶体。化学组成分析证明了所得晶体是NaLa(WO_4)_2、NaPr(WO_4)_2和NaNd(WO_4)_2。测定表明该类晶体属白钨矿型结构,四方晶系,空间群I4_1/a。计算了它们的晶胞参数,发现随着稀土元素(La、Pr、Nd)原子序数的增加,Ln~(3+)离子半径减小,Ln—O键长呈规律地递减,NaLn(WO_4)_2晶体的晶胞体积减小。测定了晶体的红外光谱和NaPr(WO_4)_2的激发光谱和荧光光谱。