Cs[Er6C]I12 und Cs2Lu[Lu6C]Cl18: Beispiele für quaternäre reduzierte Halogenide der Lanthanide mit isolierten „Clustern”︁

CS[Er₆C]I₁₂ and cs₂Lu[Lu₆C]CI₁₈: Examples for Quaternary Reduced Halides of the Lanthanides with Isolated “Clusters” Cs[Er₆C]I₁₂ and Cs₂Lu[Lu₆C]Cl₁₈ were obtained as byproducts through metallothermic reductions of ErI₃ and LuCl, with cesium in the presence of carbon in sealed tantalum containers at temperatures ranging from 700 to 940 °C. Cs₂Lu[Lu₆C]Cl₁₈ (isostructural with Cs₂Zr[Zr₆H]Cl₁₈, R 3 , a = 981.7 pm, c = 2723.2 pm, Z = 3, R = 0.082, R, = 0.053) contains octahedral [Lu₆C] clusters which are slightly compressed along the threefold axis and edge-bridged by twelve chloride anions to form [Lu₆C]Cl₁₂ units. Six additional Cl in exo positions of the cluster provide octahedral coordination for the seventh Lu³⁺. Cs⁺ occupies anticuboctahedral interstices within the Cl⁺ layers as a part of the (hexagonal) closest packed arrangement. Cs[Er₆C]I₁₂ (trigonal, R 3, a = 1112.0pm, c = 2063.8pm, Z = 3, R = 0.094, R, = 0.068) exhibits [Er₆C]I₁₂ units as well and shows the structural framework of Sc[Sc₆N]Cl₁₂. Instead of Sc³⁺ in octahedral holes, cesium occupies a regular iodide position within the ccp sheets forming [CsI₃] layers. Both halides are compared with other compounds of the lanthanides containing isolated [M₆X₁₂] clusters. The extreme electron deficiency is discussed.     

Electrospun Polyacrylic Acid Polymer Fibers Functionalized with Metallophthalocyanines for Photosensitizing and Gas Sensing Applications

The photophysical and photochemical properties of tetraaminophthalocyanine complexes of lutetium and zinc covalently linked to polyacrylic acid were studied alongside those of unsubstituted zinc phthalocyanine within the same polymeric fiber matrix. All three phthalocyanines within the solid fiber matrices showed photoactivity by the generation of singlet oxygen as was observed in solution. The fluorescence behaviors of the composite fibers equally parallel those in solution. For the unsubstituted zinc phthalocyanine composite, the fiber showed fluorescence quenching on interaction with gaseous nitrogen dioxide similar to that in DMF and, thus could be a promising nanofabric material in developing optoelectronic devices that are responsive to the gas.     

镥的激光共振电离同位素选择性研究

本文在速率方程基础上通过数值模拟方法 ,对镥的激光共振电离通道 :5d6s2 2 D3 /2 (5 73.6 5 5nm)→5d6s6 p4F3 /2 (6 4 2 .5 18nm)→ 6s6 p2 4P1/2 (6 4 3.5 4 8nm)→Autoionizationstate的激光诱导同位素选择性进行了研究。在实际实验条件下用这一方法计算得到的激光波长对激光诱导同位素选择性的关系与实验结果相符合。探讨了在偏振激光作用的情况下各种激光参数 (波长、带宽和激光强度 )对激光诱导同位素选择性的影响 ,并提出了在一定实验条件下激光共振电离质谱计较为准确地测定同位素比值的方法。这一理论方法 ,同样适用于研究其它元素的激光共振电离同位素选择性和选择激光同位素分离电离通道     

Synthesis and Characterization of GaIII,YIII, and LuIII Complexes with Etifenin and Analogues

Complexes of etifenin ( 1a ), disofenin ( 1b ), and mebrofenin ( 1c ) with Ga^III, Y^III, and Lu^III were synthesized and characterized by NMR spectroscopy and UV/Vis spectroscopy. Stability and protonation constants of the complexes of 1a were determined by potentiometry and distribution diagrams were calculated. It was shown that the Y^III and Lu^III species are most stable as bis chelates at higher pH, whereas the Ga^III complex degrades at pH < 4.5.     

慢电子速度成像法结合低温冷离子阱测量镥的电子亲和势

本文采用低温冷离子阱囚禁的手段累积镥的负离子束流,使得对其电子亲和势的测量变得实际可行.运用慢电子速度成像法获得具有高分辨率的镥负离子的光电子能谱,测得镥的电子亲和势为1926.2(50) cm~(-1)或0.23882(62) eV.此外,还观察到镥负离子的两个激发态.     

Bulky Cations and Four different Polyiodide Anions in [Lu(Db18c6)(H2O)3(thf)6]4(I3)2(I5)6(I8)(I12)

Black single crystals of [Lu(Db18c6)(H₂O)₃(thf)₆]₄(I₃)₂(I₅)₆(I₈)(I₁₂) were obtained from lutetium, I₂ and Db18c6 (dibenzo‐18‐crown‐6) in THF solution. In the bulky cation, Lu³⁺ is surrounded by nine oxygen atoms, six of Db18c6 and three of water molecules to which two THF molecules are attached each. Meanwhile, four polyiodide anions, (I₃)^–, (I₅)^–, (I₈)^2– and (I₁₂)^2–, in a 2:6:1:1 ratio form a three‐dimensional network and leave space for the bulky cations.     

Structural and Optical Characterization of Ytterbium Doped Lutetium Double Phosphates

Powder samples of the ternary phosphates A₃Lu(PO₄)₂:Yb³⁺ (A = Na, Rb) have been synthesised by solid state reactions. The spectroscopic properties of Yb³⁺ in double phosphate host lattices were investigated using absorption, emission and excitation spectra at 4, 10 and 293 K in the VUV to IR range. The results obtained for both types of phosphates are compared. Together with the fundamental ²F_5/2 → ²F_7/2 emission in the IR range, a broad band emission with two peaks in the UV region were observed in Yb³⁺‐activated Na₃Lu(PO₄)₂. The second emission is due to a charge–transfer transition type. The influence of the alkali metal cation site of the host lattice on the luminescence properties was investigated. The tentative energy level scheme of the ground and excited ²F_J (J=7/2, 5/2) levels is described.     

Synthesis and Characterization of donor‐functionalized ansa‐Cyclopentadienyl‐Indenyl and ansa‐Indenyl‐Indenyl Complexes of Yttrium,Samarium, Thulium,and Lutetium

The stepwise reaction of Me₂SiCl₂ with K[C₅H₃ ^tBuMe‐3] or Li[C₉H₇] and then with K[C₉H₆CH₂CH₂‐ NMe₂‐1] followed by double deprotonation with NaH or LiBu, yields the two dimethylsilicon bridged cyclopentadienyl‐indenyl and indenyl‐indenyl donor‐functionalized ligand systems K₂[(C₅H₂ ^tBu‐3‐Me‐5)SiMe₂(1‐C₉H₅CH₂CH₂NMe₂‐3)] ( 1 ), and Li₂[(1‐C₉H₆)SiMe₂(1‐C₉H₅CH₂CH₂NMe₂‐3)] ( 2 ), respectively. Treatment of 1 with YCl₃(THF)₃, SmCl₃(THF)_1.77, TmI₃(DME)₃, and LuCl₃(THF)₃ gives the mixed ansa‐metallocenes [(C₅H₂ ^tBu‐3‐Me‐5)SiMe₂(1‐C₉H₅CH₂CH₂NMe₂‐3)]LnX (X = Cl, Ln = Y ( 3 ), Sm ( 4 ), Lu ( 5 ); X = I, Ln = Tm ( 6 )), respectively. The reaction of 2 with LuCl₃(THF)₃ yields [(1‐C₉H₆)SiMe₂(1‐C₉H₅CH₂CH₂NMe₂‐3)]LuCl ( 7 ). Compound 4 reacts with LiMe to give the corresponding alkyl derivative [(C₅H₂ ^tBu‐3‐Me‐5)SiMe₂(1‐C₉H₅CH₂CH₂NMe₂‐3)]Sm(CH₃) ( 8 ). The new complexes were characterized by elemental analyses, MS spectrometry, and NMR spectroscopy. The molecular structures of 5 and 6 were determined by single crystal X‐ray diffraction.     

Die Deprotonierung silylierter Amido-Komplexe von Seltenerdelementen

Deprotonation Reactions of Silylated Amido Complexes of Rare Earth Elements The deprotonation of the rare earth element-tris(bistrimethylsilyl)amides Ln[N(SiMe₃)₂]₃ of scandium, ytterbium, and lutetium with sodium-bis(trimethylsilyl)amide in THF leads to the complexes [Na(THF)₃LnCH₂SiMe₂NSiMe₃{N(SiMe₃)₂}₂] [Ln = Sc ( 1 ), Yb ( 2 ), and Lu ( 3 )]. According to crystal structure analyses of 1 and 2 the metal atoms Sc and Yb are constituents of planar LnCSiN four-membered rings. At the same time, the C atom of the CH₂ group is coordinated with the sodium ion in a linear axis Ln–C–Na; the sodium ion obtains a distorted tetrahedral arrangement by three THF molecules. The equatorial positions of the methylene-C atom, which is coordinated in a trigonal bipyramidal fashion, are occupied by the two H atoms and the Si atom of the four-membered ring. 2.6-dimethylbenzoisonitrile can be inserted into the Yb–CH₂ bond of 2 and the new five-membered heterocylce YbNCSiN originates, the exocyclic CH₂ group of which enters into a C–C coupling with the centrosymmetric dimer 4 while the ytterbium undergoes reduction. At the same time, sodium-7-methyl indolate is formed, which together with [NaN(SiMe₃)₂(THF)₂] forms the centrosymmetric dimeric molecular aggregate [NaN(SiMe₃)₂(THF)₂Na(C₉H₁₆N)]₂ ( 5 ). 1 : Space group P2₁/n, Z = 8, lattice dimensions at –80 °C: a = 2941.4(2), b = 1205.5(1), c = 2952.4(3) pm; β = 113.455(8)°; R₁ = 0.0625. 2 : Space group P2₁/n, Z = 8, lattice dimensions at –80 °C: a = 2943.9(1), b = 1219.5(1), c = 2944.3(1) pm; β = 113.372(4)°; R₁ = 0.0361. 4 : Space group P 1, Z = 4, lattice dimensions at –80 °C: a = 1117.0(1), b = 1207.5(1), c = 1614.3(2) pm; α = 73.634(10)°, β = 82.091(10)°, γ = 74.391(10)°; R₁ = 0.0525. 5 : Space group P2₁/n, Z = 2, lattice dimensions at –80 °C: a = 1126.7(1), b = 1459.3(1), c = 1741.1(1) pm; β = 96.461(8)°; R₁ = 0.0458. Quantum chemical DFT calculations of the scandium model compound [Na(Me₂O)₃ScCH₂SiMe₂NSiH₃{N(SiH₃)₂}₂] ( 1 M ) give a very large negative charge at the pentacoordinated carbon atom of the four-membered ring that is concentrated in a lone-pair orbital which has mainly p character. The carbon atom interacts with the positively charged scandium atom mainly by Coulombic interactions.     

Gemischte Sandwichkomplexe der 4 f‐Elemente: Enantiomerenreine Cyclooctatetraenyl‐Cyclopentadienyl‐Komplexe des Samariums und Lutetiums mit donorfunktionalisierten Cyclopentadienylliganden

Organometallic Compounds of the Lanthanides. 139 Mixed Sandwich Complexes of the 4 f Elements: Enantiomerically Pure Cyclooctatetraenyl Cyclopentadienyl Complexes of Samarium and Lutetium with Donor‐Functionalized Cyclopentadienyl Ligands The reactions of [K{(S)‐C₅H₄CH₂CH(Me)OMe}], [K{(S)‐C₅H₄CH₂CH(Me)NMe₂}] and [K{(S)‐C₅H₄CH(Ph)CH₂NMe₂}] with the cyclooctatetraenyl lanthanide chlorides [(η⁸‐C₈H₈)Ln(μ‐Cl)(THF)]₂ (Ln = Sm, Lu) yield the mixed cyclooctatetraenyl cyclopentadienyl lanthanide complexes [(η⁸‐C₈H₈)Sm{(S)‐η⁵ : η¹‐C₅H₄CH₂CH(Me)OMe}] ( 1 a ), [(η⁸‐C₈H₈)Ln{(S)‐η⁵ : η¹‐C₅H₄CH₂CH(Me)NMe₂}] (Ln = Sm ( 2 a ), Lu ( 2 b )) and [(η⁸‐C₈H₈)Ln{(S)‐η⁵ : η¹‐C₅H₄CH(Ph)CH₂NMe₂}] (Ln = Sm ( 3 a ), Lu ( 3 b )). For comparison, the achiral compounds [(η⁸‐C₈H₈)Ln{η⁵ : η¹‐C₅H₄CH₂CH₂NMe₂}] (Ln = Sm ( 4 a ), Lu ( 4 b )) are synthesized in an analogous manner. ¹H‐, ¹³C‐NMR‐, and mass spectra of all new compounds as well as the X‐ray crystal structures of 3 b and 4 b are discussed.