MoCN83为桥基的4d4f配合物的设计 成 结构及性能分析.docx

直珏太堂亟±j金塞 直珏太堂亟±j金塞 擅要 摘要 近年氰根桥联的超分子配合物的研究已引起人们的广泛兴趣。在Nature， Science，J Am Chem Sac和Angew Chem Int Ed等杂志上报道这类配合物的研究 工作逐年增多，涉足的学科遍及配位化学、有机金属化学和材料化学等多种化 学学科以及生物学、物理学等自然学科领域。这类化合物不仅表现出结构上的 多样性，而且具有磁性、发光等多种性能。着眼于这一研究热点，考虑到该领 域4办4厂混金属配合物的研究仍属薄弱环节的现状，本论文基于【Mo(CN)8】3槔构 筑砌块设计组装了7个氰根桥联Mo．Ln(III)双金属配合物并解析了单晶结构。 所表征的4办4厂双金属配合物均具有低维结构，同时揭示了由于兀．兀堆积导致的 多种拓扑结构。并应用元素分析、红外光谱、电子光谱、变温磁化率、变场磁 化强度、场冷却磁化强度、零场冷却磁化强度和交流磁化率等技术对部分化合 物进行了表征和磁性能研究，得到了一些对分子结构和磁性设计有意义的结论。 关键词：氰根桥基，组装，晶体结构，分子磁体，兀吨堆积 AbstractRecently,supramolecular Abstract Recently,supramolecular complexes based on cyano．bridges have drawn extensive atention and the articles involving these complexes in Nature，Science，J． Am-Chem．Soc．and Angew．Chem Int Ed have yearly increased，because it concen塔 coordinated chemistry,organic。metal chemistry and material chemistry as well as biology and physics etc．Such compounds not o山show structural diversity,but also magnetic，luminescent and other properties．Although the greatest effort and success have been in the study of bimetallic 3d-3d,3d-4fcomplexes，there has been relatively little work on cyano-bridged compounds．With a view of this，this paper designs a11d assembles seven cyano-bridged Mo·Ln(III)supramolecular complexes based on 【Mo(CN)s]纠4。building blocks．The crystals of the complexes have been s觚tuI试lv characterized by X—ray crystallography and the 4d-4f mixed metal compounds with lower-dimensional structure have been obtained．In addition,various topologies structures of these complexes because of the 万呵interaction have been revealed． Some significative conclusion about molecule structure and magnetic designment have been obtained using various techniques as elementary analysis，optical spectroscopies， x。my diffraction， variable-temperature(field) magneticmeasurements。 Keywords：Cyano·bridges，assembly,crystal structures，molecular magnets，加兀 interaction lI 第一章 第一章 序言 第一节选题背景及研究的意义 配合物以其丰富多样的配位形式和空间构型已引起生物、材料、物理等众 多学科领域的格外注目，并由此形成了许多富有生命力的崭新的边缘学科【l训。 近二三十年来，配位化学的研究重点之一是以开发新颖光学、电学和磁性分子 材料