配合基

The UV-Visible absorption spectra and the fluorescence emission spectra of sixteen tetra-substituted metallo-phthalocyanine complexes {R4PcM, where R=2-［4-(2-sulfonic ethyl)piperazin-1-］ ethoxyl, 2-(piperidin-1-yl)ethoxyl; substitution position at α-position and β-position of phthalocyanine ring; M=Zn, Ni, Coand Cu} were measured.

报道了16种含哌嗪或含哌啶四取代酞菁金属配合物{R4PcM， R=2-［4-(2-磺基乙基)哌嗪-1-基］乙氧基、 2-(哌啶-1-基)乙氧基；取代位置分别在α位和β位； M=Zn， Ni， Co， Cu}的UV-Vis吸收光谱和荧光发射光谱的测定，探讨了中心金属离子、取代基种类及其取代位置、溶剂等因素对酞菁金属配合物UV-Vis吸收光谱和荧光发射光谱性质的影响。

In this paper, with 2-oxo-propionic acid salicyloyl hydrazone as a ligand, one calcium complex, three copper complexes and thirteen rare earth(RE=La, Ce, Pr, Nd, Sm, Eu. Gd, Tb, Dy, Er, Tin, Yb and Lu) complexes have been synthesized. The crystals of four complexes were obtained, and the crystal structures were determined by single crystal X ray diffraction. One of the crystals is calcium complex, the other are binary and trinary complexes of copper.

本文选用2-羰基丙酸水杨酰腙作为配体，在水中分别与钙、铜、稀土(RE=La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Er、Tm、Yb和Lu)的盐反应，共制得了17种未见文献报道的配合物，另外还培养了2-羰基丙酸水杨酰腙、咪唑与铜、钙的二元及三元配合物的四种单晶，对La-Gd的稀土的配合物进行了溶解热的测定，并用Gauss-98软件包对铜的配合物进行了有关量化计算。

The Molar conductivity indicates that all the complexes are nonelectrolyte. IR spectra show the ligand is bonded with RE ion through its oxygen atom in hydroxyl group of phenol; NO3 is coordinated as a symmetrical chelating bidentate group; the coordinated atoms of DMF and DMSO are the oxygen atoms in carbonyl and sulfoxyl groups. Fluorescence spectrum suggests that the Tb3+complexes have characteristic luminescence and its fluorescence intensity is enhanced after doping with La3+, Gd3+, Y3+, influence of doping ions and neutral ligands have also been discussed.

摩尔电导率表明，所有配合物均为非电解质；红外光谱及核磁共振氢谱表明，对叔丁基杯[8]芳烃通过酚羟基的氧原子与稀土离子配位；硝酸根为双齿螯合配位；DMF和DMSO则分别通过羰基氧和亚砜基氧与稀土离子配位；配合物的荧光光谱表明，所有Tb的配合物具有较强的特征荧光，掺杂La~(3+)、Gd~(3+)、Y~(3+)离子对Tb~(3+)的荧光有较强的增强作用。

Under the protection of purified water-free, oxygen-free argon, using Schlenk technique, the rare rarth organometallic complexes containing piperonal dimethyl acetal and dicyclopentadienyl and involving silylene-bridged fluorenyl have been synthesized.

合成了含胡椒醛二甲基缩醛基和二茂基稀土金属有机配合物。采用Schlenk技术，在干燥纯氩气保护下进行。将溴代胡椒醛二甲基缩醛基锂盐与二茂基一氯稀土（Ln：Yb，Dy，Pr，La，Sm）反应，形成5个新的文献未曾报道的稀土金属有机配合物。

The copper atom is in a planar coordination site of [N_2O_2] and it devites from the mean plane by only 0.80 pm. Byπ-πstacking interactions, a alabastrine structure was obtained.(2)Schiff-base complex [Cu(H_2O)]·H_2O, where H3GS is the 3-carboxyl -salicylidene glycine, was synthesized and characterized by elemental analysis, IR spectra and single-crystal analysis. The crystal belongs to monoclinic system, space group P2(1)/c, a=848.46(3)pm, b=681.54(3)pm, c=1967.16(8)pm,β=95.8210(10)°, Z=4, R_1=0.0279, wR_2=0.0724. The copper atom is in a square-pyramidal field with the base

结果表明该晶系属单斜晶系，空间群P2(1)/c，晶胞参数：a=848.46(3)pm，b=681.54(3)pm，c=1967.16(8)pm，α=90°，β=95.8210(10)°，γ=90°，Z=4，R_1=0.0279，wR_2=0.0724，Cu原子位于轻微变形的四方锥场底心，底面被氮原子、酚氧原子、甘氨酸羧基的一个氧原子和一个水分子氧原子占据，而甘氨酸羧基的另一个氧原子占据相邻分子的锥顶，因而形成一维链状结构；合成了单核双聚配合物Na_2[Cu_2_2]·2H_2O ，铜三核配合物Cu_3_2·5H_2O和铜锌异三核配合物ZnCu_2_2·5H_2O，并用元素分析，IR光谱，电子光谱和磁化率测定对配合物的组

New ruthenium benzylidene complexes benzylidene[1,3-bis(2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene] [k~2-diphenylphosphinoacetato] monochlororuthenium (46), benzylidene[1,3-bis(2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene][k~2-3-propionato]monochlororuthenium (47), benzylidene[1,3-bis(2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene] [k~2-2-benzonato]monochlororuthenium (48) featured five-membered, flexible six-membered and rigidsix-membered chelating rings respectively are prepared by reactions of complex 41 withcorresponding sodium phosphino-carboxylates. It is confirmed by X-ray crystallographicanalysis that the coordination geometries of complexes 46 and 47 are distorted squarepyramids with phosphino-carboxylate ligands chelating to ruthenium, and the coordinationbetween ruthenium and benzylidene ligands are strengthened.

用二苯基瞵乙酸盐、二苯基膦丙酸盐、二苯基膦苯甲酸盐与钌卡宾配合物41反应合成了三个新的钌卡宾配合物：含五元膦-氧螯合环的1，3-二-(2，6-二甲苯基)-4，5-二氢咪唑基1-苯亚甲基--一氯合钌(46)、含六元柔性膦-氧螯合环的[1，3-二-(2，6-二甲苯基)-4，5-二氢咪唑基1-苯亚甲基--一氯合钌(47)及含六元刚性膦-氧螯合环的[1，3-二-(2，6-二甲苯基)-4，5-二氢咪唑基]-苯亚甲基--一氯合钌(48)。X射线单晶衍射分析证明，配合物46、47都为变形的四方锥构型，膦-氧与钌形成螯合配位，其中苯亚甲基与钌的配位得以加强。

From the structural analysis of three praseodymium complexes, we could draw a conclusion that as the dentate arms of carboxyl group on ligands elongating, the coordination numbers of Pr and the coordination modes of ligands increase, and the mean distances between metallic atoms of metallic helices existing in these complexes augment.2. By altering 5-substituting group of isophthalic acid three series of lanthanide complexes 8～19 with 5-methylisophthalic acid and 5-nitroisophthalic acid have been prepared.

从得到的三个配体的镨配合物的结构分析可以看出，随配体的羧基齿臂的增长，Pr的配位数逐渐增大，配体的配位模式增多，配合物中存在的螺旋金属链中的金属间平均距离增大。2、通过改变间苯二甲酸配体的5位取代基，制备了5-甲基间苯二甲酸和5-硝基间苯二甲酸的三个系列稀土羧酸配合物8～19。

In order to get the information of interaction between metal complex and DNA and select metal complexes which can cleave DNA effectively, twenty seven transition metal complexes containing O/N coordinate atoms have been synthesized in this thesis. We report the synthesis, crystal structure and properties of the complexes. One of the complexes is the first μ〓-oxalato tetranuclear Cu complex, in which there is ferromagnetic interaction between the copper atoms bridged by oxalate ions. Two trinuclear copper complexes containing partial cubane Cu〓O〓 cores have been synthesized and discussed the magnetic properties.

为了解金属配合物与DNA的相互作用及筛选能有效切割DNA的金属配合物，为无机药物合成及应用提供基础信息，本文利用十个含N、O原子的多齿配体设计合成了二十七个未见文献报道的过渡金属配合物，并解析了它们的晶体结构：其中包括首例μ〓-草酸根的四核铜配合物；合成了两个具有μ〓-OH〓三核缺角立方烷结构的Cu配合物；以HCBP衍生物为配体合成了七个过渡金属配合物；以SCN〓、N〓，C〓O〓等为桥联配体，以dmpyen为端基配体合成了十一个配合物。

All the ligands and complexes have been characterized with ~1H-NMR, MS and EA.X-Ray single crystal diffraction reveals that zirconium complex containing the tert-butyl substituted N_2O_2 ligand is an oxo- and hydroxyl-bridged dinuclear structure, which is possibly formed by partial hydrolysis of chlorides at one of the zirconium centers. A tetranuclear zirconium complex has been obtained and chacaterized, which is formed by complete hydrolysis of the chlorides at the zirconium centers.

通过研究配合物的单晶结构，我们发现叔丁基取代的不对称N_2O_2配体与ZrCl_4反应生成的锆配合物为氧桥和羟基桥连接的双核锆配合物，中间过程涉及单核锆配合物中氯原子部分水解，并得到氯原子部分水解的双核锆配合物和全部水(来源：8e6eAB67C论文网www.abclunwen.com)解的四核锆配合物的晶体结构，在晶体培养过程中发现双核锆配合物能够以手性自发拆分结晶析出。

Complexes 7-12, 16, 22 and 23 are dimeric molybdatesor dimeric tungstates, the central metal with citrate or malate in a molar ratio of 1:1. Theanions of these complexes have two metal atoms and two ligands. Each ligand acts as atridentate fashion via theirα-alkoxy,α-carboxy andβ-carboxy groups coordinated to eachmetal atom. Complex 13 is a monomeric molybdate. The citrate ligand coordinates tomolybdenum with itsα-alkoxy,α-carboxy andβ-carboxy groups in a tridentate mode.

其配阴离子中都含有2个金属原子和2个配体，且配体均以α-烷氧基、α-羧基和β-羧基氧与中心金属三齿配位。13是单核柠檬酸钼配合物，柠檬酸也以α-烷氧基、α-羧基和β-羧基氧与钼三齿配位。17和21分别为苹果酸钼、柠檬酸钨单核配合物，其中苹果酸、柠檬酸配体均以α-烷氧基氧和α-羧基氧与金属双齿配位。

According to the clear water experiment, aeration performance of the new equipment is good with high total oxygen transfer coefficient and oxygen utilization ratio.

曝气设备的动力效率在叶轮转速为120rpm～150rpm时取得最大值，此时氧利用率和充氧能力也具有较高值。

The environmental stability of that world - including its crushing pressures and icy darkness - means that some of its most famous inhabitants have survived for eons as evolutionary throwbacks, their bodies undergoing little change.

稳定的海底环境─包括能把人压扁的压力和冰冷的黑暗─意谓海底某些最知名的栖居生物已以演化返祖的样态活了万世，形体几无变化。