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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 詹益慈(Yi-Tsu Chan) | |
| dc.contributor.author | Kai-Yu Cheng | en |
| dc.contributor.author | 程凱煜 | zh_TW |
| dc.date.accessioned | 2021-06-08T02:45:38Z | - |
| dc.date.copyright | 2018-01-04 | |
| dc.date.issued | 2017 | |
| dc.date.submitted | 2017-11-15 | |
| dc.identifier.citation | 1. Lehn, J.-M., Angew. Chem. Int. Ed. 1988, 27, 89.
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L., Adv. Synth. Catal. 2012, 354, 1529. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/20339 | - |
| dc.description.abstract | 在近代化學中，超分子化學引起了許多化學家的興趣，在這個領域之中研究者致力於研究分子間的作用力。在這個研究基礎上，我們可以系統化地去設計以金屬與配體所建構的金屬籠狀化合物，在本研究之中，我們合成了一系列以1,10-鄰二氮菲為建構單元的配基，在不同幾何形狀配基的錯合實驗之中，我們發現到以1,1′-聯-2-奈酚為建構單元的配基具有可調整的骨架，在混入不同的金屬離子後，可以成功地形成雙金屬的籠狀化合物，並利用核磁共振儀與質譜分析鑑定其結構，另外，具有光學活性的1,1′-聯-2-奈酚的配基在混入金屬離子後可以產生光學選擇性的金屬籠狀化合物，我們也混合金屬與不同聯結位置的1,10-鄰二氮菲為建構單元的配基，預期結果可產生自排序的選擇性錯合.
超分子化學也被視為可以了解與生物系統的工具，為了仿造生物體中酵素的功能，我們合成了具有內修飾的金屬籠狀化合物去測試催化反應，在一系列的實驗之後，我們發現在[Zn2{(S)-L11}3]催化之下，苯甲醛衍生物與丙二腈可以在非鹼性的溫合條件下進行克腦文蓋爾縮合反應，此外，這個金屬籠狀化合物的催化劑還具有可回收性以及對反應物有尺寸的選擇性。 | zh_TW |
| dc.description.abstract | Supramolecular chemistry dealing with noncovalent interactions between molecules is an attractive topic in the modern chemistry. On the basis of design principles for coordination-driven self-assembly of metallocages, a series of phenanthroline-based ligands were prepared. Through a systematic study on ligand geometry, the ligand with a rotatable BINOL core was found to afford matallocages upon coordination to Zn(II), Cd(II) and Fe(II), which were characterized by NMR spectroscopy and ESI-MS spectrometry. Besides, chiral BINOL-based ligands complexed with metal ions resulted in chiral self-sorting. Moreover, the narcissistic self-sorting process of metallocages was observed with ligands differing in the substitution positions of phenanthroline.
Supramolecular metallocages could be considered as a good platform for mimicking biological systems. To this end, endo-functionalized metallocages were introduced to catalytic reactions. In the results of Knoevenagel condensation reactions, [Zn2{(S)-L11}3] showed catalytic activity for a series of benzaldehyde substrates with malononitrile under mild conditions as well as reusability and molecular-size selectivity. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-08T02:45:38Z (GMT). No. of bitstreams: 1 ntu-106-R03223111-1.pdf: 6600416 bytes, checksum: ea0732becd48a6b4af3cae9c9e79f541 (MD5) Previous issue date: 2017 | en |
| dc.description.tableofcontents | 中文摘要 I
Abstract II Table of Contents IV Table of Figures VIII Table of Tables XXI Table of Schemes XXII Chapter 1. Introduction 1 1-1 Supramolecular Chemistry 1 1-1-1 Metal Coordination Complexes in Supramolecules 3 1-1-2 1,10-Phenanthroline-Based Supramolecules 5 1-2 Metallocages 6 1-2-1 Design Principles of Metallocages 7 1-2-2 Triple Helical Structures 9 1-2-3 Chiral system 10 1-3 Supramolecular Catalytic Systems 13 1-4 Chiral BINOL-Based Building Blocks in Supramolecular Catalysis 15 1-4-1 BINOL Used in Supramolecules 16 1-4-2 BINOL-Based Catalyst in Supramolecules 17 1-4-3 Cage-Catalyzed Knoevenagel Condensation 18 1-5 Characterization Methods 19 1-6 Motivation and Goals 20 1-6-1 Design of Metallocages 20 1-6-2 Design and Synthesis of Ligands 21 1-6-3 Application of Metallocages 22 Chapter 2. Design and Synthesis of Bisphenanthroline-Based Metallocages 23 2-1 Design and Synthesis of Ligands 23 2-2 Design and Synthesis of M2L3 Cages: Metal Coordination Studies 29 Chapter 3. Design, Synthesis, and Properties of Enantiopure Metallocages 36 3-1 Design and Synthesis of BINOL Bridged Ligands 36 3-1-1 Design and Synthesis of Ligands 37 3-2 Design and Synthesis of Enantiopure Metallocages 39 3-2-1 Enantiopure Metallocages Assembled from (S)-L8 and (S)-L10 39 3-2-2 Enantiopure Metallocages Constructed from (S)-L9, (S)-L11, (S)-L12, and (S)-L13 46 Chapter 4. Application in Knoevenagel Condensation 58 4-1 Control Tests for Knoevenagel Condensation 59 4-2 Substrate Scope 66 4-3 Proposed Mechanism 71 Chapter 5. Conclusions 73 Chapter 6. Supporting information 76 6-1 General procedure 76 6-2 Synthesis and Characterization of Organic Compounds 79 6-2-1 Synthesis of 5-ethynylphenanthroline, L1, and L2 79 6-2-2 Synthesis of 3 and L3 83 6-1-1 Synthesis of L5 and L6 84 6-1-2 Synthesis of L7 86 6-1-3 Synthesis of (R)-8, (S)-8, (rac)-8, and (S)-11. 87 6-1-4 Synthesis of L8-(S)-L11. 90 6-1-5 Synthesis of 3-Phen, (S)-L12 and (S)-L13 94 6-1-6 Characterization 98 6-3 Complex formation and characterization 117 6-2-1 Synthesis method of complex 118 6-2-2 Characterization 126 6-4 Self-Sorting Experiments 149 6-4-3 Experimental Procedure for the Self-Sorting of (S)-L9 and (S)-L12. 149 6-5 Experiments for Catalysis 149 6-5-1 Typical procedure for catalysis 149 6-5-2 Determination of Binding Constant 152 6-5-3 Experiments of Substrate Selectivity 153 6-5-4 Experimental Procedure for Substrate Scope 155 List of Abbreviation 169 References 171 | |
| dc.language.iso | en | |
| dc.title | "設計與合成含1,10-鄰二氮菲配基之金屬籠狀化合物及其在克腦文蓋爾縮合反應的催化應用" | zh_TW |
| dc.title | Design and Synthesis of Bisphenanthroline-Based Metallocages for Catalysis of Knoevenagel Condensation | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 106-1 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 蔡福裕(Fu-Yu Tsai),王朝諺(Tiow-Gan Ong) | |
| dc.subject.keyword | 自組裝,金屬籠狀化合物,自排序錯合,1,1′-聯-2-奈酚,克腦文蓋爾縮合反應, | zh_TW |
| dc.subject.keyword | self-assembly,metallocage,self-sorting,BINOL,Knoevenagel condensation, | en |
| dc.relation.page | 178 | |
| dc.identifier.doi | 10.6342/NTU201704368 | |
| dc.rights.note | 未授權 | |
| dc.date.accepted | 2017-11-15 | |
| 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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