配体

In complex 1,Cucan be described as a four-coordinated square planar geometry.Compound 8 is the sodium salt of plumbagin and exists as ionic compound.Compounds 9-16 are the rare earth complexes of plumbagin with La,Y,Dy,Sm,Gd,Nd,Erand Eu.Compound 17 is binuclear Y complex.18 is mononuclear Ycomplex with plumbagin and another ligand from Plumbago Zeylanica.Compounds 19-21 are the ternary complexes with plumbagin and 2,2\'-bpy and phen as assistant ligand.In 19, the geometry of Cucan be described as five-coordinated distorted square pyramid that exists in a dimer through the weak bonding,and 1-D chain structure is formed by intermolecular hydrogen bonds.

化合物1的单晶结构分析表明1具有四配位平面四边形结构，化合物8是白花丹素的Na盐，以离子化合物形式存在；化合物9～16为白花丹素的La，Y，Dy，Sm，Gd，Nd，Er，Eu的稀土金属配合物；化合物17是白花丹素的双核钇结构；化合物18为白花丹素的单核钇结构，该配合物除了含白花丹素外，还有来自白花丹植物中的另一个单体化合物也参与配位；化合物19～21是以2，2\'-联吡啶和邻菲咯啉等含N配体为辅助配体，具有白花丹素—含N配体—金属离子的三元配合物，化合物19是白花丹素和2，2\'-联吡啶与Cu的配合物，具有五配位的四方锥构型，通过Cu…O弱的成键作用形成二聚体，再通过分子间的氢键作用进一步形成一维链状结构，化合物20和化合物21是白花丹素分别与2，2\'-联吡啶和邻菲咯啉的Zn配合物，都具有六配位八面体构型的双核锌配合物，呈一维链状结构，化合物20中链与链之间的大量氢键将一维链扩展成二维层，分子间的π-π堆积作用进一步形成三维结构。

The auxiliary can be recovered in high yield (81%) only by filtering and recrystallization. Besides, some other aldehydes have been chosen to test the enantioselectivity of N,N\'-dibenzyl tartamide, in comparison with two other allylaborates reagents developed previously by Roush and Brown, respectively. The results show that %e.e. of homoallylic alcohol is superior to that of the former, and approaches the Brown reagent.

产物经S_N2反应得瑞格列萘中间体-甲基烯丙基-2-氯苯基-叠氮甲烷(17)；同时，将筛选出的新型手性配体N-苄基酒石酸二酰胺用于其他几种醛(正丁醛，异戊醛和环己醛)的不对称烯丙基化反应，并与广泛应用的Roush配体(22)和Brown配体(27)相比较，发现其立体选择性优于Roush配体，并接近Brown配体，但明显具有可回收利用的优势。

The novel complex (1) in which both benzylic nitrogens and heteroaromatic ones to the same metal ion with the rigid ligand imposed by the large heteroaromatic moiety first time was synthesized; a 2: 1 (ligand: metal ions) type complex which has steric resistance and strong thermochemical driving force was obtained. The crystal structures of characteristic ligand (LA4) and complexes (4, 7, 10), in which one cell includes two moieties: there exist minute difference in coordinated bonds and angles despite the same metal ions with the same ligand, were obtained. It shows that several stable conformation in one complex cell.

首次合成了含邻菲罗啉的具有较大刚性的四氮配体中四个氮原子全部与同一金属离子配位的配合物的晶体结构；得到了一个在空间上存在位阻作用的配体与金属离子2：1结构的晶体；解析了具有特色的一个配体（LA4）和三个配合物（4、7和10）的晶体结构，其中的配体与金属离子的配位作用显示出细微的差异，表明在同一金属配合物的晶胞中，可以同时存在着多个稳定的构象。

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。

The molecular designs and synthesis of triarylamine-based picolinic acid derivatives used as ancillary ligands, and their cyclometalated iridium complexes used as red-and green-emitters, as well as optoelectronics properites of these compounds were investigated in order to solve current problems of organic/polymeric electroluminescent materials and devices.

本论文针对目前有机/聚合物电致磷光材料和器件存在的问题，开展了新型三芳胺吡啶羧酸类辅助配体及其红光和绿光环金属铱配合物电致磷光材料的分子设计、合成和光电性能研究，主要包括：(1)设计、合成了三种新型的三芳胺吡啶羧酸类双齿阴离子型辅助配体；(2)以三芳胺吡啶羧酸衍生物作为双齿阴离子型辅助配体，合成得到了两个系列的红光和绿光环金属铱配合物；(3)研究了三芳胺吡啶羧酸类辅助配体分子结构对环金属配合物的紫外吸收和光致发光性能的影响；(4)以环金属配合物为客体，聚芴和恶二唑衍生物为主体，制作了聚合物电磷光器件，研究了含三芳胺吡啶羧酸类辅助配体、环金属配合物客体材料和聚合物主体材料等分子结构对电致发光性能的影响。

The main contributions of this thesis are:(1) Seven mononuclear complexes of tetradentate ligand NTB have been obtained using N〓 or SCN〓 as the additional ligand;(2) Seventeen binuclear complexes of Fe , Zn , Co , Cu have been designed and the complexes of Co , Cu exhibit antiferromagnetic properties;(3) Changing the bridged-ligand such as PO〓, CO〓, o-phth, mai, Ag (CN 〓, Au 〓, etc , fourteen tetranuclear complexes of polypridine ligand have been synthesized;(4) Two antiferromagnetic 1D chain complexes of KH〓pdc ligand have been prepared from hydrothermal reactions; in addition, one ferromagnetic 1D chain copper complex of tpdp which is bridged by oxalate has been obtained.

本论文的主要贡献为：(1)合成了配体NTB的七个新型单核配合物；(2)合成了十七个铁、锌、钴及铜系列混桥双核配合物，其中双核钴和双核铜配合物为反铁磁偶合；(3)选用多吡啶配体tpdp和TPA，改变桥联配体，合成了十个四核配合物；(4)选择配体KH〓pdc，采用水热合成方法得到了反铁磁性一维链状锰、铜配合物；以草酸根为桥联配体，合成了配体tpdp的一维链状铜配合物，该化合物为铁磁偶合，文献较少报道。

In order to investigate the relationship between the open-chain ligands and metal ions, and the possibility of the metal complexes used as electroluminescent materials, a new naphthol schiff base ligand which is a open-chain crown and its four transition metal complexes, a new amide type tripodal ligand containing heterocyclic ring, two tripodal ligands (H〓L〓 and H〓L〓) containing phenol schiff bases and their rare earth complexes were synthesized and characterized.

为了进一步研究和探讨开链配体与金属离子的配位作用，以及金属配合物作为电致发光材料的可能性，我们设计合成了含萘酚环的Schiff碱开链冠醚H〓L〓及四种过渡金属(Zn、Ni、Co、Cu)配合物，两个含酚羟基的Schiff碱三足配体H〓L〓和H〓L〓及稀土配合物，一个含杂环的酰胺型三足配体L〓，培养了配体L〓的单晶，确定了其晶体结构。

Mass spectrometry results revealed that the pair of eluents respresented a pair of ternary copper complexes with mixed ligands, providing the first experimental evidence. These complexes are diastereoisomer in nature. The optimized configuration of the diastereoisomer was predicted by theoretical calculation.

质谱实验结果表明，拆分组分是一对铜混合配体复合物离子，其中的一个配体是提供手性环境的流动相添加物，另一配体是待拆分物质的某一构型对映体，这对铜混合配体复合物离子本质上属于非对映异构体。

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。

The central 5, 5'-disubstituted bipyridine units of each ligand coordinate theNi or Fe ion, while all the terminal 6-monosubstituted bipyridine units of the ligands keep free of coordination, as the result trinuclear triple-stranded helicate 〓 can not form. This is considered to be caused by the steric hindrance of the methylene substituents α to the chelating nitrogens of the terminal bipyridine units and the strain caused by linkage mode.

配体L〓与Ag作用得到〓，两个配体链相互缠绕着两个Ag离子周围形成双股螺旋结构并以头尾式排列(见图3)，由于配体中位于配位N原子α或β位的末端甲基或次甲基取代基的空间位阻阻碍了头对头式异构体的形成，也正是由于配体头尾式排列而使Ag双股螺旋得以形成，这一结果表明该螺旋体的组装过程中自发地采取了空间阻碍尽可能小的那个构型。

This one mode pays close attention to network credence foundation of the businessman very much.

这一模式非常关注商人的网络信用基础。

Cell morphology of bacterial ghost of Pasteurella multocida was observed by scanning electron microscopy and inactivation ratio was estimated by CFU analysi.

扫描电镜观察多杀性巴氏杆菌细菌幽灵和菌落形成单位评价遗传灭活率。