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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 | |
dc.contributor.author | Guan-Ting Chen | en |
dc.contributor.author | 陳冠廷 | zh_TW |
dc.date.accessioned | 2021-06-15T12:59:35Z | - |
dc.date.available | 2021-07-26 | |
dc.date.copyright | 2016-07-26 | |
dc.date.issued | 2016 | |
dc.date.submitted | 2016-07-12 | |
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dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/50808 | - |
dc.description.abstract | 本論文研究目標以微調配基方式,將不對稱苯胺吡啶胺萘啶配基上修飾一苯基於吡啶之meta位置,合成配基2-phenylamino-7-(5-phenylpyridylamino)-1,8-naphthyridine (簡稱H2phaphpany),再以此配基合成新型五核鎳金屬串錯合物,進行結構分析、磁性、電化學之探討。
於高溫萘燒反應條件下,使用H2phaphpany配基與不同鎳金屬鹽類起始物,可成功得到不同構型之五核鎳金屬串錯合物(2,2)-trans [Ni5(μ5-phaphpany)4(NCS)2]、(3,1)-[Ni5(μ5-phaphpany)4Cl](PF6)、(2,2)-cis [Ni5(μ5-phaphpany)4](PF6)2。 由X-ray單晶繞射解析可知,三種五核鎳金屬串錯合物皆為不同構型,其中(2,2)-trans form為兩端皆有軸向配基;(3,1) form只有一端接上;而(2,2)-cis form則為無軸向配基之五核鎳金屬串錯合物。在鎳-氮鍵長方面,S = 0之金屬鎳離子的鎳-氮距離約為1.9 Å;S = 1之金屬鎳離子的鎳-氮距離大約為2.1 Å,皆分別與文獻中低自旋及高自旋組態之鎳-氮距離相符。磁性量測結果顯示,(2,2)-trans form之金屬串為反鐵磁性,(3,1) form則為順磁性,在300 K時,μeff 值分別為4.03 B.M.及3.33 B.M.。另外,(2,2)-cis form之金屬串我們預期為逆磁性物質。電化學方面,本實驗合成之五核鎳金屬串錯合物與未修飾苯基之五核鎳金屬串錯合物相比,在氧化還原電位上彼此間並無太大差異。 | zh_TW |
dc.description.abstract | The aim of this thesis is to modify the unsymmetrical H2phapany ligand, replacing the meta-position hydrogen atom of phenyl group. The fine-tuned ligand, H2phaphpany, was synthesized and used to synthesize new type of pentanickel metal-string complexes. Then we investigated their structural characterizations, magnetic properties, electrochemistry and UV spectra.
By using different metal salt precursors with H2phaphpany ligand at high temperature, different isomeric forms of pentanickel complexes, (2,2)-trans[Ni5(μ5-phaphpany)4(NCS)2], (3,1)-[Ni5(μ5-phaphpany)4Cl](PF6) and (2,2)-cis [Ni5(μ5-phaphpany)4](PF6)2 could be synthesized successfully. The X-ray structures show that the three pentanickel complexes are different isomeric forms where (2,2)-trans form present axial ligand at both terminal nickel atoms, (3,1) form is absence of axial ligand at one terminal nickel atom and (2,2)-cis form is absence of axial ligand at both terminal nickel atoms. In the Ni-N bond distances, low spin Ni(Ⅱ) ions display short Ni-N(~1.9 Å) bond distances, and high spin Ni(Ⅱ) ions display long Ni-N bond distances(~2.1 Å). Both of them are consistent with a low spin Ni(Ⅱ) and high spin Ni(Ⅱ) configuration in nickel metal-string complexes. The magnetic susceptibility shows that (2,2)-trans form exhibits antiferromagnetic interaction, (3,1) form exhibits paramagnetic behavior and (2,2)-cis form is expected to exhibit diamagnetic behavior. In the study of cyclic voltammetry, both two complexes comparing with pentanickel complexes of unmodified phenyl group show no significant difference. | en |
dc.description.provenance | Made available in DSpace on 2021-06-15T12:59:35Z (GMT). No. of bitstreams: 1 ntu-105-R03223141-1.pdf: 9498916 bytes, checksum: 42261b78658896542136eb121f678ad3 (MD5) Previous issue date: 2016 | en |
dc.description.tableofcontents | 中文摘要 i
英文摘要 ii 目錄 iii 圖目錄 v 表目錄 viii 第一章 緒論 1 1-1 前言 1 1-2 金屬-金屬鍵結理論 2 1-2-1 金屬錯合物 3 1-3 多氮配基與其金屬串錯合物 5 1-4 研究方向 11 第二章 實驗部分 12 2-1 試藥與儀器 12 2-1-1試藥 12 2-1-2儀器 14 2-2 實驗步驟 16 2-2-1配基合成 16 2-2-2金屬串錯合物合成 22 2-3晶體數據收集與分析 24 第三章 結果與討論 25 3-1合成討論 25 3-1-1 前驅物及H2phaphpany配基 25 3-1-2 五核鎳金屬串錯合物 26 3-2結構解析 28 3-2-1 單晶結構分析 28 3-2-2 配基的共振 34 3-2-3 晶體異構物形成 38 3-3磁性量測 46 3-3-1 磁性量測與簡介 46 3-3-2 磁性分析 51 3-4電化學分析 55 3-5電子吸收光譜 58 第四章 總結 61 參考文獻 62 附錄 光譜及晶體數據 65 | |
dc.language.iso | zh-TW | |
dc.title | 微調不對稱苯胺吡啶胺萘啶配基及其直線型五核鎳金屬串錯合物之合成與研究 | zh_TW |
dc.title | Syntheses and Studies of Linear Pentanickel Metal-String Complexes with the Fine-tune of Unsymmetrical 2-phenylamino-7-(α-pyridylamino)-1,8-naphthyridine Ligand | en |
dc.type | Thesis | |
dc.date.schoolyear | 104-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 陳俊顯,呂光烈,王志傑 | |
dc.subject.keyword | 金屬串,苯胺,微調配基, | zh_TW |
dc.subject.keyword | metal string, | en |
dc.relation.page | 102 | |
dc.identifier.doi | 10.6342/NTU201600813 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2016-07-13 | |
dc.contributor.author-college | 理學院 | zh_TW |
dc.contributor.author-dept | 化學研究所 | zh_TW |
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