热致变色自旋交叉配合物的合成与表征

发布时间：2018-02-21 06:58

  本文关键词： 自旋交叉 自旋态 氮杂环配体 同质多晶 磁构关系　出处：《南京理工大学》2017年硕士论文　论文类型：学位论文

【摘要】：自旋交叉配合物的研究对于开发新一代分子传感器、信息存储器件等具有重要的意义,成为磁性研究领域的一个热点方向。虽然近年来关于自旋交叉领域的研究已取得许多突出进展但也存在许多问题需要突破,例如寻找更多能够满足工业应用需求的自旋交叉体系,实现自旋交叉配合物的多功能化,自旋转变条件的易操控性,超分子作用对自旋交叉的影响等。因此本文着眼于合成二价铁自旋交叉配合物,并且期望通过提高体系协同效应从而获得具有应用价值的自旋转变体系。本文选用系列多齿含氮杂环类配体构筑出了多个结构新颖的单核配合物,对它们的结构和自旋交叉性质进行了深入的探讨,取得了许多有意义的进展。全文共有四章:第一章为绪论,介绍了本论文的研究背景及当前自旋交叉领域的研究进展,重点介绍了该领域的几个不同自旋交叉材料的研究概况,并对本论文的选题思想及内容做了概述。第二章描述了系列单核配合物的合成及Fe(Ⅱ)自旋态的调控。选用具有对称性的多氮杂环类配体bpmen(bpmen = N,N'-二甲基-N,N'-双(2-吡啶甲基)-1,2-乙二胺)为主配体,另外我们通过辅助配体的改变进一步调控自旋交叉性质,例如利用NCX-(X = S(1),Se(2),BH3(3),BPh3(4))单齿配体自组装出期望能够发生回滞型转变的自旋交叉磁性材料。研究表明这些配合物中2a表现出两步自旋转变,且在低温还具有LIESST效应;同时也意外合成出2a的同质多晶态2b,其在测试温度范围内始终保持高自旋状态。在测试温度范围内,配合物1和3始终保持高自旋状态,而配合物4始终保持低自旋状态。另外对它们的结构及性质进行了深入的研究,并探讨了结构差异对磁性质的影响。第三章工作是基于上一章体系的拓展,选用的bqdmen(bqdmen=N,N' 二甲基-N,N'-双(2-喹啉甲基)-1,2-乙二胺)配体相较于bpmen在吡啶环上连上一个苯环,与Fe(Ⅱ)在不同的溶剂热条件下反应得到了系列[Fe(bqdmen)2(NCX)_2](X = S(5),Se(6),BH_3(7))配合物。研究发现,三个配合物在测试温度范围内均表现出高自旋态。对它们的结构及性质进行了深入的研究,并探讨了自旋交叉行为消失的原因。第四章对整个论文工作进行了简要的总结和展望。
[Abstract]:Spin crossover complexes for the development of a new generation of molecular sensor, information storage device has great significance, has become a hot research direction in the field of magnetism. Although in recent years the research on cross field spin has made many outstanding progress but there are still many problems need to break through, such as looking for more spin crossover can meet the industrial system the needs of the application, the multifunctional spin crossover complexes, transition conditions of spin easy handling, supramolecular effects on spin crossover and so on. This article focuses on the synthesis of two valent iron spin crossover complexes, and expect to obtain synergistic effect by increasing the spin transition system has application value of the system. In this paper series multidentate Nitrogen Containing Heterocyclic Ligands of a number of novel mononuclear complexes, of their structure and properties of spin crossover The thorough study, and achieved many significant progress. This thesis consists of four chapters: the first chapter is the introduction, research background of this thesis and the current spin crossover field is introduced, focusing on the study of several different spin crossover materials in this field, and the research ideas and contents of this thesis briefly. The second chapter describes the series of mononuclear complexes and Fe (II) Regulation of spin states. By multi Nitrogen Heterocyclic Ligands with bpmen symmetry (bpmen = N, N'- two methyl -N, N'- double -1,2- (2- pyridyl methyl) ethylenediamine) as ligands, we through the auxiliary ligand the change of further regulation of spin crossover properties, such as the use of NCX- (X = S (1), Se (2), BH3 (3), BPh3 (4)) spin crossover magnetic material monodentate ligands from the group is expected to occur on the hysteresis shift. The research showed that these complexes exhibit two step 2A 鑷�鏃嬭浆鍙�,涓斿湪浣庢俯杩樺叿鏈塋IESST鏁堝簲;鍚屾椂涔熸剰澶栧悎鎴愬嚭2a鐨勫悓璐ㄥ�氭櫠妫�

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