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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
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dc.contributor.advisor | 彭旭明(Shie-Ming Peng) | |
dc.contributor.author | Shih-Ying Kuo | en |
dc.contributor.author | 郭世英 | zh_TW |
dc.date.accessioned | 2021-05-11T04:59:52Z | - |
dc.date.available | 2020-08-06 | |
dc.date.available | 2021-05-11T04:59:52Z | - |
dc.date.copyright | 2019-08-06 | |
dc.date.issued | 2019 | |
dc.date.submitted | 2019-08-03 | |
dc.identifier.citation | 1. C.-K. Kuo, J.-C. Chang, C.-Y. Yeh, G.-H. Lee, C.-C. Wang and S.-M. Peng , Dalton Trans., 2005, 3696–3701
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Kuo, G.-C. Huang, G.-H. Lee, C.-H. Chen, and S.-M. Peng, Chem. Commun., 2010, 46, 1338–1340 | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/handle/123456789/705 | - |
dc.description.abstract | 本篇論文使用帶有甲基的立障不對稱型萘啶酮(7-methyl-1,8-naphthyridin-2(1H)-one, Hmnpo)配基來合成出第二周期過渡金屬非螺旋性金屬串錯合物,並透過X-ray單晶繞射、循環伏安法、紫外光-可見光光譜、核磁共振儀來鑑定及探討其性質。在合成上,將立障萘啶酮配基分別加入釕(ruthenium)以及鉬(molybdenum)的相關前驅物並以萘(naphthalene)作為溶劑,於攝氏220度含氬氣的條件下進行萘燒反應8個小時,透過分層養晶(bilayer)的方式可得到第二周期過渡金屬的三核金屬串錯合物Ru3(mnpo)4Cl(PF6) (1)以及RuMoRu(mnpo)4Cl(PF6) (2)。錯合物(2)是第一個RuMoRu的三核金屬串錯合物被合成出來。透過單晶繞射的結構可以發現,四片配位基皆有脫氫的情形,並以非螺旋的形式和金屬串配位。因為配基的立障因素,其中一片配基有移位的現象發生,造成萘啶上的一個氮原子沒有和金屬配位,此金屬串並沒有失序(disorder)的情形,因此有利於結構的探討。由第二周期過渡金屬三核金屬串的分子軌域可以判斷,錯合物(1)和(2)的相近金屬離子之間的鍵級均為1.5鍵,在磁性上均為逆磁。從單晶結構可以發現,錯合物(1)及錯合物(2)的相鄰金屬離子鍵長均在2.25Å ~ 2.27Å之間,屬於1.5鍵的範圍。錯合物(2)的核磁共振圖譜以及順磁共振圖譜更顯示其逆磁的特性,此外由循環伏安法可以看出錯合物(1) 在+0.21伏特時有一個不可逆的氧化反應,而錯合物(2)在+1.10伏特以及-0.68伏特各有一個可逆的氧化還原對。 | zh_TW |
dc.description.abstract | In recent years, scientists has fascinated with the concept of single-molecole conducting wire with the advancement of nanotechnology. In this thesis, we focus on extended metal-atom chain about trinuclear second-row transition metal string complexes with bulky ligand Hmnpo (7-methyl-1,8-naphthyridin-2(1H)-one). [Ru3(mnpo)4Cl](PF6) (1) and [RuMoRu(mnpo)4Cl](PF6) (2) have been successfully synthesized. Complex 2 is the first synthesized RuMoRu trinuclear string complex. The molecular structure show that the metal-atoms chains in these complexes are nearly non-helically coordinated by four deprotonated ligands. Due to the steric effect of Hmnpo, the displacement of one of the ligands is inevitable, leaving a nitrogen atom on naphthyridine remain uncoordinated. According to the molecular orbital model of tri-metal-atom chain described previously1, the electronic configurations of both Complex 1 and 2 results in the diamagnetism and the bond order is 1.5 between adjacent metal ions. The crystal structures show that the Ru–Ru and Ru–Mo bond lengths is 2.2699(14), 2.2753(14) Å in (1) and 2.2552(12), 2.2694(13) Å in (2), respectively, which is corresponding to a bond order of 1.5 between adjacent metal as expected. NMR and EPR spectrum of (2) reveals the diamagnetism of the complexes. Cyclic voltammetry shows that Complex 1 undergoes an irreversible oxidative process at E1/2 = 0.22V, while Complex 2 exhibits two reversible redox couples. | en |
dc.description.provenance | Made available in DSpace on 2021-05-11T04:59:52Z (GMT). No. of bitstreams: 1 ntu-108-R06223174-1.pdf: 4665387 bytes, checksum: 3d852cdf04a022729024eff9451dff88 (MD5) Previous issue date: 2019 | en |
dc.description.tableofcontents | 中文摘要 i
Abstract ii 目錄 iii 圖目錄 v 表目錄 vii 第一章 緒論 1 1-1 前言 1 1-2 金屬串分子導線 2 1-2-1無架橋配基之分子金屬串錯合物 4 1-2-2有架橋配位基之分子金屬導線 6 1-3 金屬-金屬鍵結理論 9 1-3-1 雙核金屬錯合物之金屬-金屬鍵結 10 1-3-2直線型三核過渡金屬錯合物之金屬-金屬鍵結 13 1-4 金屬串錯合物之多氮配位基 16 1-4-1 多吡啶胺配位基 17 1-4-2 多萘啶胺配位基 19 1-4-3 多萘啶吡啶胺配基 21 1-5 金屬串錯合物之探討 22 1-5-1 同核金屬串錯合物 22 1-5-2 三核異金屬串錯合物 23 1-5-3 不對稱配位基金屬串錯合物 27 1-5-4 以非氮原子配位金屬串錯合物 29 1-6 研究動機 30 第二章:實驗部分 31 2-1 試藥與儀器 31 2-1-1試藥與溶劑 31 2-1-2實驗儀器 33 2-2 化合物合成 34 2-2-1 金屬前驅物的合成 34 2-2-2 配位基的合成 35 2-2-3 金屬串錯合物的合成 37 2-3 晶體數據之收集與整理 40 2-3-1 [Ru3(mnpo)4Cl](PF6) (1) 40 2-3-2 [RuMoRu(mnpo)4Cl](PF6) (2) 41 第三章:結果與討論 42 3-1晶體結構解析 42 3-1-1 [Ru3(mnpo)4Cl](PF6) (1)晶體結構解析 42 3-1-2 [RuMoRu(mnpo)4Cl](PF6) (2)晶體結構解析 46 3-2 磁性探討 51 3-3 電子吸收光譜分析 54 3-4 電化學分析 56 第四章:結論 60 參考文獻 61 附錄 光譜和晶體數據 65 | |
dc.language.iso | zh-TW | |
dc.title | 立障萘啶酮配位基之三核金屬串合成與研究 | zh_TW |
dc.title | Synthesis and Studies of Triunclear Metal String Complexes with Bulky Ligand
(7-methyl-1,8-naphthyridin-2(1H)-one) | en |
dc.date.schoolyear | 107-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 陳俊顯(Chun-Hsien Chen),王志傑(Chih-Chieh Wang) | |
dc.subject.keyword | 釕三核,金屬串,立障配位基,異三核,釕鉬釕, | zh_TW |
dc.subject.keyword | triruthenium,trinuclear,bulky ligand,heteronuclear, | en |
dc.relation.page | 78 | |
dc.identifier.doi | 10.6342/NTU201902440 | |
dc.rights.note | 同意授權(全球公開) | |
dc.date.accepted | 2019-08-05 | |
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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