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  • 學位論文

含甲咪配位基與雙醯胺吡啶配位基之配位高分子研究

Study on Coordination Polymers supported by Formamidinate and Bis-Pyridyl-Bis-Amide Ligands

指導教授 : 陳志德

摘要


本論文主要分別探討含甲咪配位基與雙酼胺吡啶配位基之配位高分子的結構與特性。 第一部分是藉由鈐木反應合成出4-(pyridin-4-yl)aniline做為起始物,再和triethyl orthoformate與醋酸銅在THF溶劑下以一步水熱合成法反應得到化合物{Cu4(OAc)4(4-pyanf)2}n, 1。 第二部分以起始物4-aminopyridine或4-(aminomethyl)pyridine 和triethyl orthoformate與氯化鈷在THF溶劑下以一步水熱合成法反應得到化合物{[Co(4-pyf)Cl}·THF}n, 2和{[CoCl2(4-Hmpyf)]·0.5THF}n, 3。 第三部分以N,N’-二-(4-吡啶)癸二醯二胺(L)與苯二乙酸輔助配位基搭配二價鈷金屬藉由水熱法合成{Co(L)0.5(1,2-PDA)(H2O)}n (1,2-PDA = 1,2-phenylenediacetic acid),4,與{Co(L)1.5(1,3-PDA)}n (1,3-PDA = 1,3-phenylenediacetic acid),5。 這些化合物藉由單晶X-ray繞射儀來鑑定其結構,更進一步藉由元素分析儀、粉末X-ray繞射儀、熱重分析儀來研究化合物的特性以及針對化合物4、5對甲基藍的光降解特性來研究。化合物1為一同時具有不同價數雙核銅的一維配位高分子。化合物2是第一個藉由甲咪配位基所形成的鈷金屬三維配位高分子,並具有sqc5603的拓譜學結構。化合物3為一維的配位高分子。化合物4為二維的配位高分子,並具有sql的拓譜學結構。化合物5為一個5-fold 交互貫穿且多聚連鎖的三維結構,每個單元具有(48,62)的拓譜學。

關鍵字

配位高分子

並列摘要


This thesis discusses the structures and properties of coordination polymers supported by formamidine and formamidinate ligands. Part I, Suzuki coupling was used to synthesize 4-(pyridin-4-yl)aniline, which was then reacted with triethyl orthoformate and copper(II) acetate in THF by one-pot solvothermal reaction to afford coordination polymer {Cu4(OAc)4(4-pyanf)2}n, 1. Part II, one-pot solvothermal reaction of 4-aminopyridine or 4-(aminomethyl)pyridine with triethyl orthoformate and cobalt chloride in THF afforded coordination polymers {[Co(4-pyf)Cl}·THF}n, 2 and {[CoCl2(4-Hmpyf)]·0.5THF}n, 3. Part III, two Co(II) coordination polymers containing N,N’-bis(4-pyridyl)sebacoamide (L) and isomeric phenylenediacetate ligands, {Co(L)0.5(1,2-PDA)(H2O)}n (1,2-PDA = 1,2-phenylenediacetic acid), 4, {Co(L)1.5(1,3-PDA)}n (1,3-PDA = 1,3-phenylenediacetic acid), 5, have been synthesized by hydrothermal reactions. Their structures have been determined by single-crystal X-ray diffraction analyses and characterized by elemental analyses, powder x-ray diffraction and thermal gravimetric analysis. The photocatalytic activities of complexes 4 and 5 on methyl blue are also reported. Complex 1 is a dinuclear 1D coordination polymer with different valence copper ion. Complex 2 is the first 3D Co(II) coordination polymer supported by formamidine ligand that shows sqc5603 topology. Complex 3 is a 1D loop chain structure. Complex 4 is a 2D structure with sql topology. Complex 5 is a 3D structure which shows a unique polycatenation of 5-fold interpenetration and each net has the (48,62) topology.

並列關鍵字

Coordination polymer

參考文獻


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