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熱致變色自旋交叉配合物的合成與表征

發(fā)布時間:2018-02-21 06:58

  本文關(guān)鍵詞: 自旋交叉 自旋態(tài) 氮雜環(huán)配體 同質(zhì)多晶 磁構(gòu)關(guān)系 出處:《南京理工大學(xué)》2017年碩士論文 論文類型:學(xué)位論文


【摘要】:自旋交叉配合物的研究對于開發(fā)新一代分子傳感器、信息存儲器件等具有重要的意義,成為磁性研究領(lǐng)域的一個熱點方向。雖然近年來關(guān)于自旋交叉領(lǐng)域的研究已取得許多突出進(jìn)展但也存在許多問題需要突破,例如尋找更多能夠滿足工業(yè)應(yīng)用需求的自旋交叉體系,實現(xiàn)自旋交叉配合物的多功能化,自旋轉(zhuǎn)變條件的易操控性,超分子作用對自旋交叉的影響等。因此本文著眼于合成二價鐵自旋交叉配合物,并且期望通過提高體系協(xié)同效應(yīng)從而獲得具有應(yīng)用價值的自旋轉(zhuǎn)變體系。本文選用系列多齒含氮雜環(huán)類配體構(gòu)筑出了多個結(jié)構(gòu)新穎的單核配合物,對它們的結(jié)構(gòu)和自旋交叉性質(zhì)進(jìn)行了深入的探討,取得了許多有意義的進(jìn)展。全文共有四章:第一章為緒論,介紹了本論文的研究背景及當(dāng)前自旋交叉領(lǐng)域的研究進(jìn)展,重點介紹了該領(lǐng)域的幾個不同自旋交叉材料的研究概況,并對本論文的選題思想及內(nèi)容做了概述。第二章描述了系列單核配合物的合成及Fe(Ⅱ)自旋態(tài)的調(diào)控。選用具有對稱性的多氮雜環(huán)類配體bpmen(bpmen = N,N'-二甲基-N,N'-雙(2-吡啶甲基)-1,2-乙二胺)為主配體,另外我們通過輔助配體的改變進(jìn)一步調(diào)控自旋交叉性質(zhì),例如利用NCX-(X = S(1),Se(2),BH3(3),BPh3(4))單齒配體自組裝出期望能夠發(fā)生回滯型轉(zhuǎn)變的自旋交叉磁性材料。研究表明這些配合物中2a表現(xiàn)出兩步自旋轉(zhuǎn)變,且在低溫還具有LIESST效應(yīng);同時也意外合成出2a的同質(zhì)多晶態(tài)2b,其在測試溫度范圍內(nèi)始終保持高自旋狀態(tài)。在測試溫度范圍內(nèi),配合物1和3始終保持高自旋狀態(tài),而配合物4始終保持低自旋狀態(tài)。另外對它們的結(jié)構(gòu)及性質(zhì)進(jìn)行了深入的研究,并探討了結(jié)構(gòu)差異對磁性質(zhì)的影響。第三章工作是基于上一章體系的拓展,選用的bqdmen(bqdmen=N,N' 二甲基-N,N'-雙(2-喹啉甲基)-1,2-乙二胺)配體相較于bpmen在吡啶環(huán)上連上一個苯環(huán),與Fe(Ⅱ)在不同的溶劑熱條件下反應(yīng)得到了系列[Fe(bqdmen)2(NCX)_2](X = S(5),Se(6),BH_3(7))配合物。研究發(fā)現(xiàn),三個配合物在測試溫度范圍內(nèi)均表現(xiàn)出高自旋態(tài)。對它們的結(jié)構(gòu)及性質(zhì)進(jìn)行了深入的研究,并探討了自旋交叉行為消失的原因。第四章對整個論文工作進(jìn)行了簡要的總結(jié)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棆杞彉,涓斿湪浣庢俯榪樺叿鏈塋IESST鏁堝簲;鍚屾椂涔熸剰澶栧悎鎴愬嚭2a鐨勫悓璐ㄥ鏅舵,

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