Synthesis and structural characterization of organolanthanide complexes with 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate ligands

Reactions of anhydrous LnCl(3) (Ln = Nd, Gd, Dy, Er, Yb) with 2 equiv of LiCp' in THF afford the lanthanocene complexes Of CP'(2)Ln(mu-Cl)(2)Li(THF)(2) (CP' = eta(5)-t-BuC5H4, Ln = Nd (1), Gd (2), Dy (3), Er (4), Yb (5); Cp'= 1,3-eta(5)-t-Bu2C5H3, Ln = Nd (6), Gd (7), Dy (8), Er (9), Yb (10)). The molecular structures of 7 and 8 were characterized by X-ray crystallographic analysis. In these complexes, two Cp' ring centroids and two it-bridging chloride atoms around the lanthanide atoms form a distorted tetrahedron. The insertion of elemental chalcogen E (E = S, Se) into Li-C bonds of dilithium o-carborane in THF solution afforded dimers of dilithium. dichalcogenolate carboranes, [(THF)(3)LiE2C2B10H10Li(THF)](2) (E = S (12a), Se (12b)), which were confirmed by a crystal structure analysis. Reactions Of Cp'(2)Ln(mu-Cl)(2)Li(THF)(2) (1-10) with 12a or 12b gave dinuclear complexes of the formula [Li(THF)(4)](2)[Cp'(2)LnE(2)C(2)B(10)H(10)](2) (Cp'= eta(5)-t-BuC5H4, E = S, Ln = Nd (13a), Gd (14a), Dy (15a), Er (16a), Yb (17a); E = Se, Ln = Nd (13b), Gd (14b), Dy (15b), Er (16b), Yb (17b); Cp'= 1,3-eta(5)-t-Bu2C5H3 E = S, Ln = Nd (18a), Gd (19a), Dy (20a), Er (21a), Yb (22a); E = Se, Ln = Nd (18b), Gd (19b), Dy (20b), Er (21b), Yb (22b)). According to the X-ray structure analyses, the dianions of 13a and 13b contain two o-carborane dichalcogenolate bridges, and each CP'2Ln fragment is attached to one terminal and two bridging chalcogen ligands. The central Ln(2)E(2) four-membered ring is not planar, and the direct metal-metal interaction is absent.

复合氟化物中缺陷对Eu~(2+)光谱的影响

用传统的高温固相法及近几年兴起的温和水热法合成了KMgF3 ∶Eu多晶粉末 ,同时用Bridgman Stockbarger法生长了KMgF3 ∶Eu单晶体。对三种方法合成的样品进行比较发现 :水热和单晶样品中 ,除了Eu2 + 的f→f锐线发射外 ,还观察到了 4 2 0nm处的宽带发射 ;这些发射带主要应归属于晶体中存在的色心和氧中心。而且与高温样品相比 ,Eu2 + 在 36 0nm处的线发射强度明显减小 ,原因是发生了Eu2 + 到色心的能量传递

Synthesis and characterization of polynuclear half-sandwich lanthanoid complexes [Na(THF)(6)](2)[(Cp6Sm6Se13)-Sm-t] and [Li(LHF4](2)[Cp6Nd6Se13]

The half-sandwich tert-butyl cyclopentadienyl lanthanoid complexes {[Cp ' Ln(THF)](2)(mu (2)-Cl)(2)(mu (3)-Cl)(3)Na(THF)}(n) [Cp ' = eta (5)-' BuC5H4; Ln = Nd (1a), Sm (1b), Gd (1c), Yb (1d)] are prepared by the reaction of anhydrous lanthanoid trichloride, LnCl(3), with NaCp ' in THF solution. Complex 1b reacts with Na2Se5 to give hexanuclear samarium polyselenide complexes [Na(THF)(6)](2)[Cp-6' SM6(mu (6)-Se)(mu -Se-2)(6)] (2). An analogous cyclopentadienyl neodymium polyselenide complex [Li(THF)(4)](2)[Cp6Nd6(mu (6)-Se)(mu -Se-2)(6)] (3) is synthesized by the reaction of [CpNdCl2. 2LiCl . 5THF] with Na2Se5 in THF solution. The molecular structures of 1a and 2 were determined by X-ray crystal structure analysis. Complex 2 contains an interstitial selenium atom which is coordinated with six samarium atoms. (C) 2001 Elsevier Science BN. All rights reserved.

Syntheses and crystalline structures of clusters Co-3(CO)(7)(mu(3)-S)(mu, eta(2)-SCNR2)

Through the reaction of Co-2(CO)(8) with four thiuram [R2NC(S)S](2), four new sulfur-capped trinuclear cobalt carbonyl clusters Co-3 (CO)(7) (mu(3)-S) (mu, eta(2)-S* C* NR2) ( I : R = Me; I : R = Et; II : R = i-Pr; IV : NR= -N [GRAPHICS] were prepared and characterized by elementary analysis, IR,H-1 NMR and MS spectroscopy. The crystal structure of the cluster Co-3(CO)(7)(mu(3)-S)[mu, eta(2)-S*C*N (i-Pr)(2)]( III) was determined by X-ray single crystal diffraction method. The crystal of m is monoclinic, belonging to space group P2(1)/n, and the cell parameters are as follows: a = 1, 145 2(2) nm, b = 1. 502 8(3) nm, c = 1, 214 4(2) nmj alpha = 90 degrees, beta = 92, 15(3)degrees, gamma = 90 degrees; V = 2. 088 5(7) nm(3) , Z = 4, F (000) = 1 096, D-c = 1. 747 mg . m(-3), mu = 2. 588 mm(-1), R=0. 040 7, R-w=0. 062 4, The structural analysis shows that cluster II has a pyrimidal Co3S framework and contains a heterocylic bridging bidentate ligand [mu, eta(2)-S* C* N (i-Pr)(2)] linked to the Co2 and Co3 atoms of the cluster by a cobalt-carbon and a cobalt-sulfur bond respectively.

Synthesis, properties and crystal structure of organic-inorganic radical salt (DBTTF)(6)HPMo12O40 center dot 2H(2)O

Organic-inorganic radical salt (DBTTF)(6)PMo12O40 . 2H(2)O was synthesized by electrocrystallization and characterized by IR spectrum, electronic spectrum and ESR technology, Its magnetic property, conductivity and crystal structure were determined. The title compound crystallized in a triclinic system with P1 space group, a = 1.378 7(7), b = 1.420 4 (2), c = 1.570 2(2) nm, alpha = 104.57(1)degrees, beta = 103.41(2)degrees, gamma = 95.80(2)degrees, V = 2.853(2) nm(3) Z = 1 and a final R = 0.072 7.

The reactivity of lanthanide alkyl compounds with phenylacetylene: Synthesis and structure of [(Bu(t)Cp)(2)LnC CPh](2) (Ln=Nd, Gd)

[(Bu(t)Cp)(2)LnCH(3)](2) (Ln = Nd, Gd) react with PhC=CH to form the dimeric alkynide-bridged complexes [(Bu(t)Cp)(2)LnC=CPh](2) [Ln = Nd (I), Gd (II)]. Both compounds crystallized from toluene in the monoclinic space group C2/c. The two complexes are homologous, composed of asymmetric metal-alkynide bridges with Nd-C, Gd-C (alkynide) bond lengths of 2.602(4), 2.641(5) (I) and 2.532(6), 2.601(7) Angstrom (II), respectively. The average Nd-C (ring) and Gd-C (ring) distances are 2.746(13) and 2.703(19)Angstrom.

三-(2-甲基氮丙啶)氧化膦异构体的核磁共振和量子化学研究

三-(2-甲基氮丙啶)氧化膦(MAPO)为黄色油状液体,其化学性质活泼,可用作塑料、橡胶及造纸业中高分子化合物的交联剂等。本文对MAPO进行了~1H、~(13)C、~(15)N、~(31)P和~(17)O的核磁共振研究及量子化学计算。结果表明,该化合物存在4种异构体,其中2种为对映体,并得到了这4种异构体的几何构型。

THE CHARACTERIZATION OF 2 COPPER PHTHALOCYANINE LANGMUIR-BLODGETT-FILMS AND THEIR GAS-SENSITIVE PROPERTIES

The monolayer and deposition behaviour of a symmetrically substituted copper tetra-4-(2, 4-di-t-amylphenoxy) phthalocyanine (tapCuPc) and an asymmetrically substituted copper [tri-4-(2, 4-di-t-amylphenoxy)-mono-4-(-2-methoxyethoxy)]phthalocyanine (AsyCuPc) were investigated. The results on monolayer behaviour and spectroscopic characterization of the LB films show that both CuPc molecules in a monolayer at the air-water interface and the LB films are stacked and inclined. The gas-sensitive properties show that the responding speed of AsyCuPc LB film is faster than that of tapCuPc LB film.

2种大黄叶片色素及紫外吸收物质含量的比较研究

[目的]探讨唐古特大黄与药用大黄对高原强紫外线辐射的生理适应特征。[方法]以栽培于同一生境下的4年生唐古特大黄与药用大黄为研究对象，测定2种大黄叶片中的叶绿素、类胡萝卜素及紫外吸收物质的含量，研究了在高原强紫外线辐射下2种大黄的生理适应性。[结果]同一生境下唐古特大黄叶片中的叶绿素a、叶绿素b、叶绿素总量、类胡萝卜素和紫外吸收物质的含量高于药用大黄。[结论]叶绿素a．b及类胡萝卜素和紫外吸收物质的积累，有利于唐古特大黄对高原强紫外辐射的适应，是长期进化适应高原环境的结果。

钝体尾流的双重小波包分解

根据湍流相干结构和非相干结构不相关的特性，提出了一种钝体尾流双重小波包分解的新算法，将湍流的运动分解成相干分量和非相干分量，该算法以湍流相干分量和非相干分量的相关系数作为迭代的控制指标，减小了过去算法中的随意性，用该算法对大长宽比的钝体尾流三维超声波流速仪测量数据的分析表明：1)钝体间距与宽度之比大于4时，钝体间的相互影响可以忽略不计；2)流线型的钝体尾流紊动强度较小。

Localized Solid-State Amorphization at Grain Boundaries in a Nanocrystalline Al Solid Solution Subjected to Surface Mechanical Attrition

Using high-resolution electron microscopy, localized solid-state amorphization (SSA) was observed in a nanocrystalline (NC) Al solid solution (weight per cent 4.2 Cu, 0.3 Mn, the rest being Al) subjected to a surface mechanical attrition treatment. It was found that the deformation-induced SSA may occur at the grain boundary (GB) where either the high density dislocations or dislocation complexes are present. It is suggested that lattice instability due to elastic distortion within the dislocation core region plays a significant role in the initiation of the localized SSA at defective sites. Meanwhile, the GB of severely deformed NC grains exhibits a continuously varying atomic structure in such a way that while most of the GB is ordered but reveals corrugated configurations, localized amorphization may occur along the same GB.

重力对异向聚集过程影响的探讨

自90年代初,分散体系聚集过程的微重力研究开始受到重视,并有一系列论文发表[1－4].Folkersma[3,4]等人在最近发表的文章中,公布了他们的最新研究结果.在探空火箭实现的微重力条件下,他们发现聚集速率要比地面实验快11倍多.为了解释这一现象,他们把重力的影响分为两部分,即沉降和自然对流.用密度匹配法,检验了在无沉降时的聚集过程.得到的结果是,聚集速率在无重力沉降影响时会比有沉降时快2.7倍.即便如此,微重力实验的聚集速率仍高出4.2倍.他们推断,这一巨大差异是由在地面上无法避免的自然对流造成的.

动态压应力对离体培养骨组织骨折愈合的作用研究

采用鸡胚绒毛尿囊膜上培养经人工骨折的鸡胚胫骨,以自行设计机械加压装置施力于骨折线骨段。经培养后取出标本,行大体、光镜及扫描电镜观察骨折愈合情况,并运用能谱分析仪检测骨折修复组织钙磷元素的含量。结果表明:该模型可有效地排除其他生理因素的干扰.有利于单纯确定压应力对骨折的作用;本模型所提供的压力对骨折愈合有明显的促进作用。

风浪充分发展下海面阻力系数的数值研究

考虑海气界面附近大气边界层内海浪充分发展情况下的海气动量交换. 根据Donelan的观点建立海气界面模型, 采用K-ε模式以计算湍流流场. 所得流场结构包括风速、湍流动能、湍能耗散及湍流粘性系数等都较合理; 计算的海面阻力参数C_D在中等风速时与实测结果符合良好.