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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 彭旭明 | |
| dc.contributor.author | Ching-Yi Chuang | en |
| dc.contributor.author | 莊靜宜 | zh_TW |
| dc.date.accessioned | 2021-06-16T13:18:58Z | - |
| dc.date.available | 2023-07-26 | |
| dc.date.copyright | 2013-08-06 | |
| dc.date.issued | 2013 | |
| dc.date.submitted | 2013-07-26 | |
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/61924 | - |
| dc.description.abstract | 本論文的研究主要是根據配基微調的概念，將萘啶與傳統的多吡啶胺系統結合，並且導入具有立體障礙的磺醯基團，合成出不對稱的配基H2npts，並將此配基H2npts進一步合成為新型的五核鎳金屬串錯合物。
此不對稱配基是經由鈀金屬鹽類催化反應得到1，並由1H-NMR和ESI-Mass鑑定其結構和純度。利用配基H2npts在高溫萘燒的反應條件下，可以得到新型的五核鎳金屬串錯合錯[Ni5(npts)4]。由X-ray單晶繞射分析，其結構為(2,2)-trans form，且不具有軸向配基，所以，五個鎳金屬都為平面四邊形的配位環境。由磁性的量測，證實五核鎳金屬串錯合物[Ni5(npts)4]的兩個末端具有[Ni2]3+單元，是因為萘啶系統可以穩定低氧化態的鎳金屬，形成(Ni2)3+-Ni2+-(Ni2)3+。將磁性進行擬合，得到兩個末端的[Ni2]3+單元之間有反鐵磁作用，J = -54.46 cm-1。與過去所合成的萘啶系統相比較，當[Ni2]3+單元之間的距離增加，兩者之間的反鐵力作用力會變小，符合磁性和電化學上所得之結果。 根據電化學的分析，錯合物[Ni5(npts)4]具有三個可逆的氧化還原對，可知其為易氧化的物種，因此未來可利用氧化劑將錯合物[Ni5(npts)4]氧化，將所得到的產物進行鑑定，比較氧化前後在結構和磁性上的差異，作較系統的研究。 | zh_TW |
| dc.description.abstract | According to the idea of tuning the ligand, ligand containing the naphthyridyl group, which can stabilize the low oxidation state metal ions and bulky sulfonyl group on the end was prepared. The unsymmetrical ligand H2npts was synthesized by palladium-catalyzed reaction, and was characterized by the 1H-NMR and ESI-Mass.
The ligand H2npts was applied to synthesize linear penta-nickel metal string complex [Ni5(npts)4], 1. The complex 1 was structurally characterized to reveal that five nickel ions are in the square planar environment. Because of the steric effect of the bulky p-toluenesulfonyl group, the complex 1 is in (2,2)-trans form, with no axial ligand. The complex is described as a mixed-valence system consisting of (Ni2)3+-Ni2+-(Ni2)3+ fragment. The terminal naphthyridyl groups can stabilize the [Ni2]3+ units. From the magnetic analysis, the complex 1 shows an antiferromagnetic interaction between two (Ni2)3+ units with J = -54.46 cm-1. Comparing with researches which contain naphthyridyl groups in the past, we found that the distance between the two (Ni2)3+ units is longer, and the antiferromagnetic interaction is weaker. In the electrochemistry, the complex 1 has three pairs of reversible redox couples, one in reduction and two in oxidation. From this data, the complex 1 is easier to oxidize. In the future, we can oxidize the complex, and gain the product of two-electron oxidation. The product will be compared with the complex 1 in structure and magnetic properties. It will complete the series of the study. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-16T13:18:58Z (GMT). No. of bitstreams: 1 ntu-102-R00223146-1.pdf: 5807610 bytes, checksum: ae2fb50f6f9d15608b979e2002688396 (MD5) Previous issue date: 2013 | en |
| dc.description.tableofcontents | 口試委員會審定書 I
謝誌 II 目錄 III 圖目錄 V 表目錄 VII 摘要 VIII Abstract IX 第一章 緒論 1 1.1 前言 1 1.2 分子金屬導線 2 1.3 金屬和金屬的多重鍵理論 6 1.4 混價系統 9 1.4 多氮配基和金屬串錯合物 13 1.4.1 多氮配基簡介 13 1.4.2 金屬串錯合物簡介 16 1.5 微調金屬串系統 17 1.5.1 萘啶胺系統之金屬串錯合物 17 1.5.2 不對稱型系統之金屬串錯合物 20 1.6 研究方向 23 第二章 實驗部分 25 2.1 試藥與儀器 25 2.1.1 試藥 25 2.1.2 儀器 26 2.2 實驗步驟 29 2.2.1 配基合成之流程圖 29 2.2.2 金屬串錯合物合成之流程圖 30 2.2.3 配基之合成 31 2.2.4 金屬錯合物之合成 36 第三章 結果與討論 38 3.1 合成討論 38 3.1.1 配基之合成 38 3.1.2 直線型五核鎳金屬串之合成 41 3.2 結構分析 42 3.2.1 晶體數據之收集與處理 42 3.2.2 五核鎳金屬串錯合物[Ni5(npts)4], 1 42 3.2.2 五核鎳金屬串錯合物[Ni5(npts)4(H2O)2](PF6)2, 2 49 3.3 磁性分析 52 3.3.1 磁性簡介 52 3.3.2 五核鎳金屬串錯合物[Ni5(npts)4] (1)之磁性分析 55 3.4 電化學及光譜電化學分析 61 3.4.1 循環伏安法 61 3.4.2 光譜電化學法 63 第四章 結論 66 參考文獻 68 附錄 光譜和晶體數據 73 | |
| dc.language.iso | zh-TW | |
| dc.subject | 分子導線 | zh_TW |
| dc.subject | 混價系統 | zh_TW |
| dc.subject | 金屬串 | zh_TW |
| dc.subject | Metal String | en |
| dc.subject | Molecular Wire | en |
| dc.subject | Mixed-Valence System | en |
| dc.title | 修飾不對稱萘啶吡啶二胺配基(H2npts)及其五核金屬串錯合物之合成與研究 | zh_TW |
| dc.title | Synthesis and Studies of Pentanuclear Metal Complexes with the Modified Unsymmetrical H2npts Ligand | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 101-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 陳俊顯,王志傑,葉鎮宇,邱靜雯 | |
| dc.subject.keyword | 金屬串,分子導線,混價系統, | zh_TW |
| dc.subject.keyword | Metal String,Molecular Wire,Mixed-Valence System, | en |
| dc.relation.page | 90 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2013-07-26 | |
| dc.contributor.author-college | 理學院 | zh_TW |
| dc.contributor.author-dept | 化學研究所 | zh_TW |
| 顯示於系所單位： | 化學系 | |
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