Cs4[Sc6C]Cl13 und Cs4[Pr6(C2)]I13 — zwei Beispiele für das fehlende Bindeglied bei der Verknüpfung der Baueinheiten [M6Z]XX

Cs₄[Sc₆C]Cl₁₃ and Cs₄[Pr₆(C₂)]I₁₃ — Two Examples for the Missing Link in the Connectivity of [M₆Z]X X Building Units Cs₄[Sc₆C]Cl₁₃ (tetragonal, I4₁/amd, a = 1 540.5(4), c = 1 017.9(7) pm, c/a = 0.661, Z = 4, R = 0.038, R_w = 0.026) and Cs₄[Pr₆(C₂)]I₁₃ (a = 1 804.9(3), c = 1 259.5(3) pm, c/a = 0.698, R = 0.106, R_w = 0.068) are obtained as green-black and blue-black single crystals with brass-like metallic lustre through metallothermic reduction of ScCl₃ and PrI₃, respectively, with cesium in the presence of carbon in sealed tantalum containers. The, overall, isotypic compounds contain isolated [Sc₆C] and [Pr₆(C₂)] clusters, respectively, that are surrounded by 18 halide (X) ligands (12 Xⁱ and 6 X^a; X = Cl or I). The connection is carried out via the motif [M₆Z]XXXX (M = Sc and Pr; Z = C and C₂, respectively) and is thereby the missing link of the motifs of connection for the composition A_x[M₆Z]X₁₃. Analogous interconnection of [TiO₆] octahedra is found in the anatase-type of structure of TiO₂.     

TiO2/SiO2/CeO2复合纳米薄膜超亲水性能的研究

采用溶胶凝胶法在载玻片表面制备了均匀透明的TiO2-SiO2-CeO2超亲水性薄膜，并用X射线衍射、傅立叶红外光谱、紫外-可见分光光度计研究了SiO2及稀土铈添加对TiO2薄膜表面特征及超亲水性能的影响。结果表明，Ti02-SiO2-CeO2薄膜亲水性能及亲水持续效应显著提高。实验中掺杂的铈是以三价离子态引入的，由于Ce^3 在高温下很容易氧化，故在薄膜中铈主要以四价态形式存在。Ce^4 在光激发下很容易捕获光生电子生成Ce^3 离子，光生空穴则与表面氧离子反应形成氧空位，而氧空位对亲水性的提高具有关键作用。添加SiO2后，薄膜表面的羟基含量增加，这主要是由于TiO2与SiO2复合在表面形成Lewis酸所致。表面稳定的羟基可使亲水性在暗中保持较长时间，因而亲水持续效应提高。添加SiO2及稀土铈后，薄膜中TiO2晶粒尺寸变小，量子效应增强，这也导致亲水性提高。因此添加稀土铈及SiO2后，薄膜表面的氧空穴增多，薄膜的超亲水性及亲水持续效应提高。     

1,5-二苯基-1,3,5-戊三酮(H2DBA)及邻菲咯啉(phen)、羟基离子([OH]-)希土混配配合物的合成及性质研究

本文在乙醇-水溶液中合成了H₂DBA及phen、[OH]^-与希土离子的混配配合物Ln(HDBA)₂(OH)(phen)·H₂O(Ln=La、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Y)十三个.通过化学分析,元素分析及电导分析确定了配合物的组成;研究了配合物的紫外、红外光谱及热行为,并对可能的配合物结构进行了推测.     

稀土类尖晶石SnY2O4的软化学合成与表征

尖晶石化合物主要是以化学式AB_2O_4表示的化合物(A和B分别代表二价和三价的金属阳离子)。随A,B离子的改变,化合物的电和磁性也随之改变。因此,可以通过改变A或B来得到我们所希望的材料。稀土元素具有f电子,使得它有着丰富的光     

稀土—色氨酸配合物的pH电位法研究

稀土－色氨酸配合物的ｐＨ电位法研究朱元成（甘肃省天水师范高等专科学校化学系天水７４１００１）邓汝温（兰州大学化学系兰州７３００００）朱春吉倪嘉缵（长春应用化学研究所稀土化学与物理开放实验室长春１３００２２）关键词稀土色氨酸配合物ｐＨ电位法中图分类号Ｏ...     

芳氧基钇配合物催化合成以杯芳烃为核的星形聚己内酯

合成了两种杯芳烃的衍生物(2a,2b),并作为大分子引发剂在三(2,6-二叔丁基-4-甲基-苯氧基)钇[Y(DBMP)3]的催化下,引发己内酯的可控开环聚合,制备了一系列以杯芳烃为核的星形聚己内酯.1H-NMR和SEC研究表明,在一定分子量范围内,以对叔丁基杯[4]芳烃衍生物(2a)为核的星形聚己内酯是四臂且分子量可控的较窄分布星形聚合物,而以对叔丁基杯[6]芳烃衍生物(2b)为核的星形聚己内酯为结构不够明确的星形聚合物.DSC分析表明星形聚己内酯的熔点、结晶温度和结晶度随分子量的增加而增加,且低于相近分子量的线形聚己内酯.POM观察聚己内酯的等温结晶形态,发现星形聚己内酯和相近分子量的线形聚己内酯相比,前者具有不规则的球晶形态和较慢的结晶速度,而后者表现出较快的结晶速度和规则的球晶形态.     

稀土-HEDTA-丝氨酸三元体系的pH电位法和荧光光谱研究

氨基多羧酸是镧、锕系元素促排剂,氨基酸是重要的生物配体。稀土-氨基多羧酸-氨基酸三元体系的研究对探索稀土在人体内代谢及其生物效应具有重要意义,其次,多元配位体系荧光研究亦是令人感兴趣的课题。有关稀土-氨基多羧酸-氨基酸三元体系研究不多,稀土-N-羟乙基乙二胺三乙酸(HEDTA)-丝氨酸(Ser)三元体系研究尚未见报导。本文用pH电位法和荧光光谱研究了稀土(除钷外镧系元素及钇)-HEDTA-Ser三元体系的配位作用,考察了铽配合物配体敏化荧光光谱特点。     

Complexes of rare-earth metals with meconic acid

Two series of complexes of meconic acid (H₃ Mec) with rare-earths have been prepared by varying the preparative procedure. The compounds have the general formulae, [Ln(Mec) (H₂O)₂]·3 H₂O (whereLn=La, Ce, Pr, Nd, Sm, Ho and Y) and [Ln(HMec) (H₂ Mec) (H₂O)₂]·4 H₂O (whereLn=La, Pr, Nd and Sm). The infrared spectral data indicate that the carboxylate groups are bound to the rare-earth metal in a bidentate fashion. Thermal studies indicate that two water molecules are coordinated in each case. The complexes are probably polymeric.

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Komplexe von Seltenerd-Metallen mit Meconsäure

Zusammenfassung Es wurden zwei Reihen von Komplexen der Meconsäure (H₃ Mec) mit Seltenerd-Metallen mit den allgemeinen Formeln [Ln(Mec)(H₂O)₂]·3 H₂O (Ln=La, Ce, Pr, Nd, Sm, Ho, Y) und [Ln(HMec)₂(H₂ Mec) (H₂O)₂]·4 H₂O (Ln=La, Pr, Nd, Sm) hergestellt. Die IR-Spektren zeigen, daß die Carboxylat-Gruppen in zweizähniger Weise mit den Metallionen koordinieren; thermische Untersuchungen ergeben, daß in beiden Reihen jeweils zwei Wassermoleküle zusätzlich koordiniert sind. Die Komplexe weisen wahrscheinlich eine Polymerstruktur auf.

     

Synthesis and Crystal Structure of a Novel 1D Chain-like Organic Inorganic Hybrid Rare Earth Derivative of Polyoxometalate: H_(0.5)[Sm(H_2O)_6]_(0.25)[Sm(H_2O)_5]_(0.25){[Sm(H_2O)_7][Sm(H_2O)_2-(DMSO)][SiW_(11)O_(39)]}·4.5H_2O

Polyoxometalates may be versatile inorganic building blocks for the construction of molecular-based materials. By means of their multiple coordination requirements and oxophilicity, lanthanide cations are suitable to link polyoxometalate building blocks to form new classes of materials with potentially useful magnetic and luminescent properties1-4. Peacock and Weakley studied the interactions between the [α-SiW11 O39]8? isomer and lanthanide cations5, and they reported that the [α-SiW11O39…     

Synthesis,Structure, and Magnetic Properties of the Silicides <Emphasis Type="BoldItalic">RE</Emphasis>IrSi (<Emphasis Type="Italic">RE</Emphasis> = Ce,Pr, Er,Tm, Lu) and SmIr<Subscript>0.266(8)</Subscript>Si<Subscript>1.734(8)</Subscript>

Summary. The equiatomic rare earth metal–iridium–silicides REIrSi (RE=Ce, Pr, Er, Tm, Lu) were prepared by arc-melting of the elements and subsequent annealing. All silicides were characterized through their X-ray powder patterns. The structures of CeIrSi, ErIrSi, and LuIrSi were refined from X-ray single crystal diffractometer data: LaIrSi type, P2₁3, a=629.15(2)pm, wR2=0.1232, 280F² values, and 11 variable parameters for CeIrSi; TiNiSi type, Pnma, a=673.4(1), b=416.07(5), c=744.88(9)pm, wR2=0.0705, 339F² values, and 20 variable parameters for ErIrSi, and a=664.0(3), b=412.9(1), c=742.6(1)pm, wR2=0.0398, 496F² values, and 20 variable parameters for LuIrSi. The iridium and silicon atoms in CeIrSi, ErIrSi, and LuIrSi build three-dimensional [IrSi] networks where the iridium atoms have three (CeIrSi, Ir–Si 229pm) and four (ErIrSi, Ir–Si 247–258pm; LuIrSi, Ir–Si 245–256pm) silicon neighbors. The [IrSi] networks leave larger channels in which the cerium, erbium, and lutetium atoms are located. Temperature dependent susceptibility data for LuIrSi indicate Pauli paramagnetism. CeIrSi shows Curie-Weiss paramagnetism above 100K with an experimental magnetic moment of 2.56(2)_B/Ce atom. With samarium as rare earth metal component the silicide SmIr_0.266(8)Si_1.734(8) with -ThSi₂ type structure was obtained: I4₁/amd, a=409.3(1), c=1397.2(5)pm, wR2=0.0575, 161F² values, and 9 variable parameters. Within the three-dimensional [Ir_0.266Si_1.734] network the Ir/Si–Ir/Si distances range from 230 to 237pm.