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研究生： 簡伯任
Jian, Bo-Ren
論文名稱： 三價鈰配位聚合物的合成、結構、熱分析及磁性
Synthesis, Structures, Thermal Analyses and Magnetic Properties of Cerium(III) Coordination Polymers
指導教授： 許桂芳
Hsu, Kuei-Fang
學位類別： 碩士
Master
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2007
畢業學年度： 95
語文別： 中文
論文頁數： 116
中文關鍵詞： 配位聚合物 、開放性骨架 、水熱法合成 、鑭系
外文關鍵詞： Coordination Polymer, Solvothermal Synthesis, Open framework, Lanthanide
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    • 本論文利用溶劑熱法合成出五個具有孔洞骨架的鑭系配位聚合物，分別為[Ce2(H2O)2(C2O4)(CO3)2]•2H2O (1)、[Ce2(H2O)4(C2O4)(C4H4O4)2]•4H2O (2)、[Ce2(H2O)2(C4H4O4)3] (3)、[Ce2(H2O)2(C4H4O4)3]•H2O (4)及 NH4[Ce(H2O)(C2O4)(SO4)] (5)。
    在結構1中，碳酸根配位基與鈰離子配位構成二維網狀結構，此網狀結構再藉由草酸根配位基支撐而構成三維骨架結構。在結構2中，丁二酸根配位基類似在結構1中碳酸根配位基的位置，此構成較開闊的網狀結構，然後再由草酸根配位基支撐而構成具有孔洞的骨架結構。在結構3和4中，其骨架是由丁二酸根配位基連接CeO8(H2O)多面體鏈而構成三維骨架結構。在結構5中，CeO8(H2O)多面體是藉由硫酸根配位基橋接構成一維直鏈，此直鏈再由草酸根配位基集結在一起而構成一開放骨架結構。結構1的脫水相〝[Ce2(H2O)2(C2O4)(CO3)2]〞及結構2的脫水相〝[Ce2(C2O4)(C4H4O4)2]〞仍維持結構的穩定。此外，這五個配位聚合物存在反鐵磁的行為。

    Five new lanthanide coordination polymers adopting porous frameworks have been prepared by the solvothermal reactions, which are [Ce2(H2O)2(C2O4)(CO3)2]•2H2O (1), [Ce2(H2O)4(C2O4)(C4H4O4)2]•4H2O (2), [Ce2(H2O)2C4H4O4)3] (3), [Ce2(H2O)2(C4H4O4)3]•H2O (4) and NH4[Ce(H2O)(C2O4)(SO4)] (5). In 1, the carbonate ligands assemble with cerium ions to form a two-dimensional network. The networks are then pillared by oxalate ligands into a three-dimensional framework. In 2, succinate ligands resemble to the positions of carbonate ligands in 1 to form a related network. The network again pillar by the oxalate ligands into a porous polymeric framework. In 3 and 4, the frameworks are composed of CeO8(H2O) polyhedra chains, which are linked by succinate ligands into three-dimensional frameworks. In 5, CeO8(H2O) polyhedra are bridged through the sulfate ligands to form one-dimensional chains. The chains are fused together by the oxalate ligands into an open framework. The dehydrated phase of 〝[Ce2(H2O)2(C2O4)(CO3)2]〞 from 1 and 〝[Ce2(C2O4)(C4H4O4)2]〞 from 2 remain stability. Furthermore, antiferromagnetic behaviors exist in the five coordination polymers.

    第一章 緒論……………………………………………………1 1-1 簡介………………………………………………1 1-2 合成方法…………………………………………3 1-3 結構鑑定與性質分析……………………………4 1-3-1單晶X-光繞射與晶體結構鑑定……………4 1-3-2 X-光能量散佈光譜儀………………………6 1-3-3粉末X-光繞射分析…………………………6 1-3-4元素分析……………………………………6 1-3-5熱重量/微差熱分析…………………………6 1-3-6超導量子干涉磁化儀………………………7 1-4 實驗儀器與藥品…………………………………9 1-5 研究成果…………………………………………10 第二章 三價鈰草酸-碳酸鹽及三價鈰草酸-丁二酸鹽化合物16 2-1 前言………………………………………………16 2-2 合成………………………………………………18 2-3 單晶X-光繞射分析………………………………19 2-4 化合物的結構描述與討論………………………21 2-5 化合物的性質探討………………………………23 2-5-1粉末X-光繞射(PXRD)分析………………………23 2-5-2元素分析(EA)……………………………………23 2-5-3熱重量/微差熱分析(TGA/DTA)…………………23 2-5-4超導量子干涉磁化儀(SQUID)磁性分析………25 2-6 結論………………………………………………28 第三章 三價鈰丁二酸鹽化合物………………………………39 3-1 前言………………………………………………39 3-2 合成………………………………………………40 3-3 單晶X-光繞射分析………………………………41 3-4 化合物的結構描述與討論………………………43 3-5 化合物的性質探討………………………………46 3-5-1粉末X-光繞射(PXRD)分析…………………46 3-5-2元素分析(EA)………………………………46 3-5-3熱重量/微差熱分析(TGA/DTA)……………46 3-5-4超導量子干涉磁化儀(SQUID)磁性分析…48 3-6 結論………………………………………………50 第四章 三價鈰草酸-硫酸鹽化合物……………………………62 4-1前言…………………………………………………62 4-2 合成………………………………………………63 4-3 單晶X-光繞射分析………………………………64 4-4 化合物的結構描述與討論………………………65 4-5 化合物的性質探討………………………………67 4-5-1粉末X-光繞射(PXRD)分析…………………67 4-5-2元素分析(EA)………………………………67 4-5-3熱重量/微差熱分析(TGA/DTA)……………67 4-5-4超導量子干涉磁化儀(SQUID)磁性分析…68 4-6 結論………………………………………………70 參考文獻……………………………………………………………77 附錄…………………………………………………………………84 附錄A 化合物的結構解析、原子位置、平均熱擾動參數、選擇性鍵長、鍵序和及 鍵角資料表……………………………………………84 附錄B 化合物實測及計算之粉末X-光繞射圖………………107

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