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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 彭旭明 | |
| dc.contributor.author | Chi-Hui Chen | en |
| dc.contributor.author | 陳綺慧 | zh_TW |
| dc.date.accessioned | 2021-06-08T06:59:42Z | - |
| dc.date.copyright | 2009-07-03 | |
| dc.date.issued | 2009 | |
| dc.date.submitted | 2009-06-25 | |
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/26076 | - |
| dc.description.abstract | 本篇論文主要討論不對稱異核金屬串化合物(4,0)-[CuCuML4X][anion]的合成、結構、光譜、磁性和理論研究 (M 為鈀或鉑離子，L 為不對稱配基，軸向配基X 為Cl-或NCS-)。
利用實驗室傳統的萘燒法可成功地合成出六個不對稱異核金屬串錯合物，包括了(4,0)-[CuCuPd(npa)4Cl][PF6] (1) (npa- = naphthyridylphenylamido anion) 、(4,0)-[CuCuPd(npa)4(μ-NCS)Cu(NCS)2] (2) 、(4,0)-[CuCuPt(npa)4Cl][PF6] (3) 、(4,0)-[CuCuPt(npa)4(NCS)][PF6] (4)、(4,0)-[CuCuPd(ntfmpa)4Cl][PF6] (5) (ntfmpa- = naphthyridyl(4-trifluoromethylphenyl)amido anion) 和 (4,0)-[CuCuPd(nmpa)4Cl][PF6] (6) (nmpa- = naphthyridyl(4-methylphenyl)amido anion)。根據X-ray 單晶結構分析，六個錯合物的立體結構均為單一的(4,0)構型，配基上四個苯環基團皆朝向同一方向。此(4,0)構型的形成原因推測為配基上氮的配位能力差異，因為胺的氮傾向和鈀或鉑離子配位，而萘啶的氮則易和兩個銅離子配位。化合物末端的銅離子為有點扭曲的四方角錐五配位，而內部銅離子是微扭曲的四方平面配位。由於受配基上四個苯環基團的立體阻礙影響，鈀或鉑離子沒有額外的軸向配基，呈現四方平面配位結構。變溫磁化率量測結果顯示化合物兩個銅離子的未配對電子為強反鐵磁偶合，其磁交換偶合常數 (J) 分別為 -498.90 cm-1(1) 、 493.30 cm-1(2) 、 -501.24 cm-1(3) 、 -484.43 cm-1(4) 、 -520.77 cm-1(5) 和 -498.85 cm-1(6)。密度泛函數理論 計算的結果顯示銅上的未配對電子藉由空間傳遞而造成強反鐵磁偶合作用。此外，計算顯示鄰近異核金屬d 軌域之間具有高能量屏障，提示這類不對稱金屬串錯合物未來可應用在無機分子整流器方面的潛力。 | zh_TW |
| dc.description.abstract | A series of asymmetric heterometal string complexes,
(4,0)[CuCuPd(npa)4Cl][PF6] (1) (npa- = naphthyridylphenylamido anion), (4,0)-[CuCuPd(npa)4(μ-NCS)Cu(NCS)2] (2), (4,0)[CuCuPt(npa)4Cl][PF6] (3), (4,0)[CuCuPt(npa)4(NCS)][PF6] (4), (4,0)[CuCuPd(ntfmpa)4Cl][PF6] (5) (ntfmpa- = naphthyridyl(4-trifluoromethyl phenyl)amido anion) and (4,0)[CuCuPd(nmpa)4Cl][PF6] (6) (nmpa- = naphthyridyl(4-methylphenyl)amido anion), have been synthesized and studied. According to the X-ray crystallography analysis, these complexes contain a linear CuCuM ( M = Pd or Pt ) framework which is supported by four asymmetric ligands. These asymmetric ligands adopt a (4,0) arrangement. All aniline N atoms coordinated to the M atom (M = Pd or Pt) and all naphthyridine N atoms coordinated to two Cu atoms. The coordination environment of the terminal copper of 1-6 is a distorted square pyramid. The coordination environment of the inner cooper is a distorted square planar. Because of the steric hindrance, the M atom is square planar coordinated without extra axial ligand. Temperature-dependent magnetic susceptibility of 1-6 revels that unpaired electrons of two Cu atoms are antiferromagnetically coupled (J ~ 500 cm-1), which is confirmed by DFT calculations. Interestingly, the large energy barrier between the d-orbitals of neighboring heterometals suggests that these complexes may exhibit potential application as future inorganic molecular rectifiers. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-08T06:59:42Z (GMT). No. of bitstreams: 1 ntu-98-R96223103-1.pdf: 13815209 bytes, checksum: 4bf22c28f3b62a69a789ad00f287600c (MD5) Previous issue date: 2009 | en |
| dc.description.tableofcontents | 口試委員會審定書
謝誌 中文摘要......................................I 英文摘要......................................II 第一章 緒論...................................1 1-1 前言......................................1 1-2多氮配基的簡介與發展.......................5 1-2-1 多吡啶胺配基............................5 1-2-2 多萘啶胺配基............................6 1-2-3 吡啶萘啶胺混合配基......................7 1-2-4 苯環修飾之多氮配基......................7 1-3 直線型三核金屬串錯合物....................9 1-3-1 直線型三核同金屬錯合物..................9 1-3-2 直線型三核異金屬錯合物..................11 1-4 研究方向..................................15 1-4-1 不對稱型配基............................15 1-4-2 直線型異核金屬串錯合物..................16 第二章 實驗部分...............................17 2-1 試藥與儀器................................17 2-1-1 試藥與溶劑..............................17 2-1-2 儀器....................................19 2-2 實驗步驟..................................20 2-2-1 配基的合成..............................20 2-2-2 金屬串錯合物的合成......................26 第三章 結果與討論.............................33 3-1 合成......................................33 3-1-1 Hnpa、Hntfmpa、Hnmpa配基................33 3-1-2 三核異金屬串錯合物......................35 3-2 結構分析..................................36 3-3 磁性分析..................................55 3-3-1 公式介紹................................55 3-3-2 三核異金屬串錯合物磁性數據及擬合........57 3-4 理論計算分析..............................63 3-5 電化學分析和光譜電化學分析................68 第四章 總結...................................73 參考文獻......................................75 附錄 光譜與晶體數據...........................81 | |
| dc.language.iso | zh-TW | |
| dc.subject | 不對稱金屬串 | zh_TW |
| dc.subject | 異核金屬錯合物 | zh_TW |
| dc.subject | asymmetric | en |
| dc.subject | heterometal complex | en |
| dc.title | 調控不對稱異核金屬串的立體化學構型：CuCuM (M = Pd or Pt)化合物的合成與物理性質研究 | zh_TW |
| dc.title | Stereochemical Control of the Unique Conformation of Asymmetric Heterometal Strings: Synthesis, Structure and Magnetism of CuCuM (M = Pd or Pt) Compounds | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 97-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 王志傑,葉鎮宇,陳俊顯 | |
| dc.subject.keyword | 不對稱金屬串,異核金屬錯合物, | zh_TW |
| dc.subject.keyword | asymmetric,heterometal complex, | en |
| dc.relation.page | 124 | |
| dc.rights.note | 未授權 | |
| dc.date.accepted | 2009-06-26 | |
| 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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