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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 彭旭明(Shie-Ming Peng) | |
| dc.contributor.author | Gin-Chen Huang | en |
| dc.contributor.author | 黃俊程 | zh_TW |
| dc.date.accessioned | 2021-06-13T15:39:36Z | - |
| dc.date.available | 2013-07-16 | |
| dc.date.copyright | 2008-07-16 | |
| dc.date.issued | 2008 | |
| dc.date.submitted | 2008-07-08 | |
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/37705 | - |
| dc.description.abstract | Our group was devoted to the research of metal string complexes. We believe that the thinnest metal wire may be applied to practical applications in the future. The dipyridylamide ligand (Hdpa) has been used to stabilize homo-trinuclear metal string complexes. A series of homo-trinuclear M3(dpa)4X2 complexes have been studied in detail in past decades. A new type of heterometallic framework, combining in a linear arrangement with a ruthenium dimer and a third metal atom, either Cu or Ni has been synthesized and studied thoroughly. The metal frameworks of Ru2Cu(dpa)4Cl2, of its mono-oxidized counterpart [Ru2Cu(dpa)4Cl2]PF6, and of their nickel homologues, Ru2Ni(dpa)4Cl2 and [Ru2Ni(dpa)4Cl2]PF6 are nonsymmetric, in spite of a severe disorder affecting the metal positions. This nonsymmetric structure was further confirmed by NMR spectroscopy. The [Ru2M]6+ framework of Ru2Cu(dpa)4Cl2 and Ru2Ni(dpa)4Cl2 was shown from spectroelectrochemical analysis and DFT calculations to exist in the form of a mixed-valent [Ru2]5+ moiety coupled to a formally M+ hetero-metal. The magnetism and redox chemistry were also studied in this work.
The study of naphthyridyl modified polypyridylamide analogues is a new direction in our group. Many interesting properties have been unveiled in our recent research. Naphthyridyldiamide ligand is one of the analogues. Studying the metal complexes formed with this ligand helps us to understand more about the characterizations of these series ligands. Ni4(DAniDANy)4 and [Ni4(DAniDANy)4]PF6 has been synthesized. Structure analysis of [Ni4(DAniDANy)4]PF6 shows the decreasing of metal-metal bond lengths which corresponds to oxidation of the metal-based sigma anti-bonding. The strong IVCT band in UV-VIS spectrum was assigned to the one electron excitation from the occupied σ* to the unoccupied σ* orbital. EPR spectrum and magnetic susceptibility study shows that this complex has one unpaired electron and located on metal ions. DFT study on both complex Ni4(DAniDANy)4 and [Ni4(DAniDANy)4]PF6 is consistent with the experimental result. Hetero asymmetric tetranuclear Ru2Ni2(DAniDANy)3(OAc)2Cl was successfully synthesized. The UV-VIS spectrum of Ru2Ni2(DAniDANy)3(OAc)2Cl shows IVCT band at 890nm which is similar with [Ru2]5+. Magnetic and DFT studies show that the three unpaired electrons delocalized over the ruthenium ions. OTTLE study shows that the IVCT band does not disappear in both oxidation and reduction process. The reduction and oxidation processes occur on the Ni2 moiety. We also synthesized the [Ru2Ni2(DAniDANy)3(OAc)2]PF6. Structural analysis shows that the removal of axial ligand results the contraction of Ni-Ni, Ni-Ru and Ru-Ru distances. This can be explained by the fact that the d orbital energy of Ru2 and Ni2 is different. The coordinated chloride will raise the energy of Ru2 and causes the poor overlap between dimers. When the axial chloride was removed, the overlap of σ orbitals becomes better and the bonding interaction enhances. The cluster compounds, ferromagnetic Co3(DAniDANy)3 and antiferromagnetic Ru2(Hdphdany)2(dphdany)2, were studied due to its interesting magnetic ehavior. The magnetic orbitals of Co3(DAniDANy)3 and Ru2(dphdany)2(Hdphdany)2 consist of metal-ligand antibonding. In both complexes, the ligand directs the antiferromagnetic coupling via superexchange between neighboring nitrogen atoms. The origin of the observed ferromagnetism in Co3(DAniDANy)3 is due to the orthogonal magnetic orbitals of central and terminal Co ions. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-13T15:39:36Z (GMT). No. of bitstreams: 1 ntu-97-D94223022-1.pdf: 18650233 bytes, checksum: e1f9815b50de74429efce47366191aa7 (MD5) Previous issue date: 2008 | en |
| dc.description.tableofcontents | Contents
Abstract i Chapter 1 : Introduction 1 1-1 Metal-metal bonding theory 2 1-1-1 Bonding mode in dinuclear case 2 1-1-2 Bonding interaction in dinuclear case 3 1-1-3 Extension from dinuclear to multinuclear case 6 1-2 Metal String complexes 10 1-2-1 Oligo–α–pyridylamine ligand 10 1-2-2 Fine tuning of oligo–α–pyridylamine : Naphthyridine Substituent 12 1-3 Asymmetric heterometal string complexes 15 1-4 Research direction 16 Chapter 2 : Experimental Section 17 2-1 Techniques 17 2-2 Sample preparation 19 Chapter 3 : Asymmetric Trinuclear Hetero-Metal String Complexes 34 3-1 Synthesis 34 3-2 Crystal structures 35 3-3 NMR spectrum 41 3-4 Electrochemistry 42 3-5 Computational study 45 3-6 Near-IR spectra 49 3-7 Magnetic measurements and EPR spectrum 52 3-8 Conductivity study 58 3-9 Conclusions 61 Chapter 4 : Metal Complexes with Naphthyridine-Functionalized Amide Ligands 63 4-1 Synthesis 63 4-2 Ni4(DAniDANy)4 and [Ni4(DAniDANy)4]PF6 66 4-2-1 Comparison of ligands 66 4-2-2 Crystal Structures 67 4-2-3 Electrochemistry study 69 4-2-4 EPR spectrum and magnetism 72 4-2-5 DFT study 73 4-3 Ru2Ni2(DAniDANy)3(OAc)2Cl and [Ru2Ni2(DAniDANy)3(OAc)2]PF6 76 4-3-1 Crystal structures 76 4-3-2 Electrochemistry 78 4-3-3 Magnetism 82 4-3-4 DFT study 84 4-4 Trinuclear Co3(DAniDANy)3 87 4-4-1 Crystal structure 87 4-4-2 Electrochemistry 89 4-4-3 Magnetism 90 4-4-4 DFT study 92 4-5 Dinuclear Ru2(Hdphdany)2(dphdany)2 99 4-5-1 Crystal structure 99 4-5-2 Electrochemistry 100 4-5-3 Magnetism and 1H NMR 101 4-5-4 Computational study 103 4-6 Conclusions 110 References 112 APPEDIX | |
| dc.language.iso | en | |
| dc.subject | 分子導線 | zh_TW |
| dc.subject | 金屬線 | zh_TW |
| dc.subject | 導電度 | zh_TW |
| dc.subject | 金屬串 | zh_TW |
| dc.subject | 無機錯合物 | zh_TW |
| dc.subject | inorgnaic compound | en |
| dc.subject | metal wire | en |
| dc.subject | conductance | en |
| dc.subject | molecule wire | en |
| dc.subject | metal string | en |
| dc.title | 不對稱三核混金屬串與萘啶二胺配基之系列錯合物之合成、結構與物理性質研究 | zh_TW |
| dc.title | Synthesis, Crystal Structures, Physical Properties and DFT Studies of a Series of Linear Asymmetric Hetero-Trinuclear Complexes and Metal Clusters with Naphthyridine-Functionalized Amide Ligands | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 96-2 | |
| dc.description.degree | 博士 | |
| dc.contributor.oralexamcommittee | 金必耀(Bih-Yaw Jin),陳俊顯(Chun-hsien Chen),葉鎮宇(Chen-Yu Yeh),王 瑜(Wang Yu),瑪麗亞馬德琳 羅曼(Rohmer Marie-Maleleine),比那 馬克(Marc Benard) | |
| dc.subject.keyword | 導電度,無機錯合物,分子導線,金屬串,金屬線, | zh_TW |
| dc.subject.keyword | conductance,inorgnaic compound,molecule wire,metal string,metal wire, | en |
| dc.relation.page | 114 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2008-07-08 | |
| 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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