有機－無機混合配位基化合物之合成、結構鑑定與物性探討; Synthesis, Crystal Structures and Properties of Organic-Inorganic Hybrid Compounds

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題名:	有機－無機混合配位基化合物之合成、結構鑑定與物性探討;Synthesis, Crystal Structures and Properties of Organic-Inorganic Hybrid Compounds
作者:	王志銘;Chih-Min Wang
貢獻者:	化學研究所
關鍵詞:	有機無機混成;金屬磷酸鹽;coordination poolymor;organic-inorganic hybrid;metal phosphate
日期:	2003-06-23
上傳時間:	2009-09-22 10:10:18 (UTC+8)
出版者:	國立中央大學圖書館
摘要:	摘要本論文採用中溫水熱法合成5個新穎結構的金屬磷酸鹽化合物，我們將化合物分類如下： Ⅰ·含對位尼古丁酸配位基 (INT = isonicotinic acid)的金屬磷酸鹽化合物。 CuVO2(HINT)(PO4) Zn2(HINT)2(HPO4)2 (1) (2) Ⅱ·含4,4’-bipyridine的金屬磷酸或砷酸鹽化合物。 CuVO2(4,4'-bpy)(PO4) CuVO2(4,4'-bpy)(AsO4) (3) (4) (H24,4'-bpy)[(VO2)4(PO4)2] (5) 以上化合物均由單晶X-光繞射儀鑑定結構，X-光能量散佈光譜儀(EDX)測得過渡金屬及磷等元素，X-光粉末繞射初步分析化合物的新穎性及純度，熱重分析(TGA)判斷化合物的熱穩定性及有機分子的存在，元素分析(EA)確定化合物中碳、氫、氮元素的比例。第1系列中介紹2個化合物，這2個化合物是首次利用對位尼古丁酸合成的金屬磷酸鹽化合物。化合物1為混金屬銅、釩的磷酸鹽化合物，其中銅氧多面體共邊連成鏈狀，釩氧、磷氧多面體間共角連結並以μ3形式和銅氧多面體連結形成1層，對位尼古丁酸則利用1端的酸基以bidentate的形式配位在銅原子上，另1端的氮原子則被質子化 (protonated)使整個有機分子垂吊在層間。化合物2是磷酸鋅的化合物，對位尼古丁酸利用酸基的1端以monodentate的形式配位在鋅原子上，另1端的氮原子則被質子化垂吊在層間，並以固態核磁共振 (NMR)證實磷酸根及有機分子在結構中的形式，此2個化合物於第2章中詳細描述與討論。第2系列中介紹3個含4,4’-bipyridine的金屬磷酸或砷酸鹽化合物。化合物3、4是等結構 (isostructure)的化合物，具有3維柱狀結構的銅、釩混金屬磷酸或砷酸鹽化合物，並以超導量子干涉磁量儀 (SQUID)測量磁性並確定化合物中金屬的價數。化合物5由4個釩原子形成的釩原子團簇和磷酸分子連接成二維的層狀化合物，其中4,4’-bipyridine的氮都被質子化，在結構裡扮演模版的角色，此3個化合物於第3章及第4章中詳加描述與討論。 Abstract In the thesis, we report five novel metal phosphates have been syn- thesized under hydrothermal conditions and structurally characterized by single X-ray diffaction. Type Ⅰ:The first mixed-metal phosphate and metal phosphate incorporate isonicotinate ligand, CuVO2(HINT)(PO4), 1; Zn2(HINT)2(HPO4)2, 2. Type Ⅱ:Two mixed metal organic-inorganic hybrid compounds, CuVO2(4,4’-bipyridine)(PO4), 3; CuVO2(4,4’-bipyridine)(AsO4), 4, have a pillared layer structure. Type Ⅲ:The clustered vanadium phosphate, (4,4’H2bipyridine)[(VO2)4(PO4)2], 5, was a layer structure. The formulations were confirmed by single-crystal X-ray diffraction, Energy-dispersive X-ray fluorescence spectroscopy (EDS), powder X-ray diffraction, thermogravimetric analysis (TGA), elemental analysis (EA), magnetic susceptibility measurements, and solid state NMR spectroscopy. The compound 1 was the first mixed-metal phosphate. The structure consists of 2D neutral sheets of bimetallic oxide layers with the isonicotinate ligand being coordinated to copper in a bidentate fashion as a pendent group. The compound 2 was a noval zinc phosphate combined with isonicotinate ligand. Each Zn is tetrahedrally coordinated by three phosphate groups and one carboxylate group of the ligand in a mono- dentate fashion. So two compounds 1 and 2 being successfully synthesiz- ed would be the start for the study of the Metals/isonicotinate ligand/ phosphate system. The compounds 3 and 4 were isostructure linked through 4,4’-bipyridine pillars into a 3D framework. The compound 5 was a novel vanadium phosphate with V4O84+ clusters. The structure consists of phosphate-bridged vanadium (Ⅴ) clusters to form a layer structure in the presence of the protonated 4,4’-H2bipyridine as the structure-directing agent.
顯示於類別:	[化學研究所] 博碩士論文

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