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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 楊吉水 | zh_TW |
| dc.contributor.advisor | Jye-Shane Yang | en |
| dc.contributor.author | 鄭詩穎 | zh_TW |
| dc.contributor.author | Shih-Ying Cheng | en |
| dc.date.accessioned | 2024-08-20T16:11:21Z | - |
| dc.date.available | 2024-08-21 | - |
| dc.date.copyright | 2024-08-20 | - |
| dc.date.issued | 2024 | - |
| dc.date.submitted | 2024-08-07 | - |
| dc.identifier.citation | 1. Yam, V. W.-W.; Cheng, E. C.-C., Highlights on the recent advances in gold chemistry—a photophysical perspective. Chem. Soc. Rev. 2008, 37 (9), 1806-1813.
2. Schmidbaur, H.; Raubenheimer, H. G., Excimer and exciplex formation in gold (I) complexes preconditioned by aurophilic interactions. Angew. Chem. Int. Ed. 2020, 59 (35), 14748-14771. 3. Yam, V. W.-W.; Wong, K. M.-C., Luminescent molecular rods—transition-metal alkynyl complexes. Molecular wires and electronics 2005, 1-32. 4. Mingos, D. M. P.; Yau, J.; Menzer, S.; Williams, D. J., A gold (I)[2] catene. Angew Chem. Int. Ed. Engl. in English 1995, 34 (17), 1894-1895. 5. Yip, S. K.; Cheng, E. C. C.; Yuan, L. H.; Zhu, N.; Yam, V. W. W., Supramolecular Assembly of Luminescent Gold (i) Alkynylcalix [4] crown‐6 Complexes with Planar η2, η2‐Coordinated Gold (i) Centers. Angew. Chem. Int. Ed. 2004, 43 (37), 4954-4957. 6. Koshevoy, I. O.; Chang, Y.-C.; Karttunen, A. J.; Selivanov, S. I.; Janis, J.; Haukka, M.; Pakkanen, T.; Tunik, S. P.; Chou, P.-T., Intensely luminescent homoleptic alkynyl decanuclear gold (I) clusters and their cationic octanuclear phosphine derivatives. Inorg. Chem. 2012, 51 (13), 7392-7403. 7. Xu, G. T.; Chang, X. Y.; Low, K. H.; Wu, L. L.; Wan, Q.; Shu, H. X.; To, W. P.; Huang, J. S.; Che, C. M., Self‐Assembly of Molecular Trefoil Knots Featuring Pentadecanuclear Homoleptic AuI‐, AuI/AgI‐, or AuI/CuI‐Alkynyl Coordination. Angewandte Chemie 2022, 134 (21), e202200748. 8. Puddephatt, R., Gold catenanes. J. Organomet. Chem. 2015, 792, 13-24. 9. Chui, S. S.; Ng, M. F.; Che, C. M., Structure Determination of Homoleptic AuI, AgI, and CuI Aryl/Alkylethynyl Coordination Polymers by X‐ray Powder Diffraction. Chem. Eur. J 2005, 11 (6), 1739-1749. 10. Yao, L.-Y.; Yam, V. W.-W., Dual Emissive Gold (I)–Sulfido Cluster Framework Capable of Benzene–Cyclohexane Separation in the Solid State Accompanied by Luminescence Color Changes. J. Am. Chem. Soc. 2021, 143 (6), 2558-2566. 11. Seki, T.; Sakurada, K.; Muromoto, M.; Ito, H., Photoinduced single-crystal-to-single-crystal phase transition and photosalient effect of a gold (I) isocyanide complex with shortening of intermolecular aurophilic bonds. Chem. Sci. 2015, 6 (2), 1491-1497. 12. Sakurada, K.; Seki, T.; Ito, H., Mechanical path to a photogenerated structure: ball milling-induced phase transition of a gold (I) complex. CrystEngComm 2016, 18 (38), 7217-7220. 13. Koshevoy, I. O.; Lin, C.-L.; Karttunen, A. J.; Haukka, M.; Shih, C.-W.; Chou, P.-T.; Tunik, S. P.; Pakkanen, T. A., Octanuclear gold (I) alkynyl-diphosphine clusters showing thermochromic luminescence. Chem. Commun. 2011, 47 (19), 5533-5535. 14. VR, S.; Shalaev, V., AROMATIC-HYDROCARBONS-NEW ARYN-2, 3-DEHYDROTRIPTYCENE IN REACTION WITH ANTHRACENE. Doklady Akademii Nauk SSSR 1974, 216 (1), 110-112. 15. Chiu, C. W.; Yang, J. S., Photoluminescent and Photoresponsive Iptycene‐Incorporated π‐Conjugated Systems: Fundamentals and Applications. ChemPhotoChem 2020, 4 (8), 538-563. 16. Matsunaga, Y.; Yang, J. S., Multicolor Fluorescence Writing Based on Host–Guest Interactions and Force‐Induced Fluorescence‐Color Memory. Angew. Chem. Int. Ed. 2015, 54 (27), 7985-7989. 17. Hsu, L.-Y.; Maity, S.; Matsunaga, Y.; Hsu, Y.-F.; Liu, Y.-H.; Peng, S.-M.; Shinmyozu, T.; Yang, J.-S., Photomechanochromic vs. mechanochromic fluorescence of a unichromophoric bimodal molecular solid: multicolour fluorescence patterning. Chem. Sci. 2018, 9 (48), 8990-9001. 18. Lin, C.-J.; Liu, Y.-H.; Peng, S.-M.; Shinmyozu, T.; Yang, J.-S., Excimer–monomer photoluminescence mechanochromism and vapochromism of pentiptycene-containing cyclometalated platinum (II) complexes. Inorg. Chem. 2017, 56 (9), 4978-4989. 19. Hsu, Y.-F.; Chen, S.-Y.; Maity, S.; Liu, Y.-H.; Peng, S.-M.; Yang, J.-S., A polymorphic pentiptycene-containing gold (I) isocyanide complex: solvent-and conformation-dependent supramolecular luminescence. Dalton Trans. 2020, 49 (44), 15602-15606. 20. Hsu, Y.-F.; Wu, T.-W.; Kang, Y.-H.; Wu, C.-Y.; Liu, Y.-H.; Peng, S.-M.; Kong, K. V.; Yang, J.-S., Porous Supramolecular Assembly of Pentiptycene-Containing Gold (I) Complexes: Persistent Excited-State Aurophilicity and Inclusion-Induced Emission Enhancement. Inorg. Chem. 2022, 61 (30), 11981-11991. 21. Carlson, T. F.; Fackler Jr, J., Raman spectroscopic investigations of dinuclear gold ylide complexes; further relationships of Au–Au bond lengths versus Au–Au stretching frequencies. J. Organomet. Chem. 2000, 596 (1-2), 237-241. 22. 康伃璇. 含五苯荑之全同配位炔基金(I)團簇及錯合物之晶體結構及刺激響應發光性質研究. 2022. 23. Zhu, X.-Z.; Chen, C.-F., Iptycene quinones: Synthesis and structure. J. Org. Chem. 2005, 70 (3), 917-924. 24. Yang, J.-S.; Yan, J.-L.; Hwang, C.-Y.; Chiou, S.-Y.; Liau, K.-L.; Gavin Tsai, H.-H.; Lee, G.-H.; Peng, S.-M., Probing the intrachain and interchain effects on the fluorescence behavior of pentiptycene-derived oligo (p-phenyleneethynylene) s. J. Am. Chem. Soc. 2006, 128 (43), 14109-14119. 25. Liang, J.; Chen, Z.; Yin, J.; Yu, G.-A.; Liu, S. H., Aggregation-induced emission (AIE) behavior and thermochromic luminescence properties of a new gold (I) complex. Chem. Commun. 2013, 49 (34), 3567-3569. 26. Aguiló, E.; Moro, A. J.; Gavara, R.; Alfonso, I.; Pérez, Y.; Zaccaria, F.; Guerra, C. l. F.; Malfois, M.; Baucells, C.; Ferrer, M., Reversible self-assembly of water-soluble Gold (I) complexes. Inorg. Chem. 2018, 57 (3), 1017-1028. 27. Omary, M. A.; Rawashdeh-Omary, M. A.; Gonser, M. A.; Elbjeirami, O.; Grimes, T.; Cundari, T. R.; Diyabalanage, H. V.; Gamage, C. S. P.; Dias, H. R., Metal effect on the supramolecular structure, photophysics, and acid− base character of trinuclear pyrazolato coinage metal complexes. Inorg. Chem. 2005, 44 (23), 8200-8210. 28. Nishina, N.; Yamamoto, Y., Gold-catalyzed intermolecular hydroamination of allenes: first example of the use of an aliphatic amine in hydroamination. Synlett 2007, 2007 (11), 1767-1770. | - |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/94859 | - |
| dc.description.abstract | 超分子自組裝為現今當紅的議題，其中金(I)受到相對論效應影響，使其具有強的親金屬作用力，這也使金(I)錯合物在光物理性質上有豐富的表現。其中，依靠親金作用力所以引導出的金團簇廣受關注，已經有許多文獻深入探討這些金團簇的結構與性質。然而，全同配位炔基金(I)團簇(AuC2R)n研究至今僅四篇文獻提出明確的金(I)團簇結構，主要是因為(AuC2R)n通常具有強烈的分子作用力，使其難溶於溶劑中，因此結構鮮少被鑑定。儘管如此，全同配位炔基金(I)團簇在合成不同金(I)錯合物中卻被廣泛應用。
本研究將龐大的H形骨架五苯荑配體引入金(I)炔基錯合物系統中，合成出新的多核全同配位炔基金(I)團簇[AuPa]n。通過不同的結晶條件，獲得了多種晶體。第一類晶體由四核金(I)團簇[AuPa]4與六核金(I)團簇[AuPa]6組成，命名為[AuPa]4+6；第二類晶體由兩個不同之六核金(I)團簇[AuPa]6組成，命名為[AuPa]6+6；第三類晶體由三個不同之六核金(I)團簇[AuPa]6組成，命名為[AuPa]6+6+6。 本研究與先前文獻的不同之處在於，引入五苯荑配體後，即可引導出不同金(I)核數排列的晶體，且[AuPa]n 展現了豐富的刺激響應性質及多重光色變化。這些性質可以通過溫度變化、照光誘導、溶劑薰致和機械研磨處理進行顏色上的轉變，這也是第一個具有刺激響應性質的全同配位炔基金(I)團簇，並給予出明確的兩種金(I)核數結構。此外，我們利用拉曼光譜證實，這些變化是由於激發態下金(I)-金(I)作用力增強所致。 | zh_TW |
| dc.description.abstract | Supramolecular self-assembly is currently a popular topic in chemistry. Due to the influence of relativistic effects on gold(I) complexes, they exhibit strong aurophilicity interactions, resulting in rich photophysical properties. Among them, gold clusters with aurophilicity interactions have garnered significant attention. Despite this interest, research on homoleptic alkynyl gold(I) clusters (AuC2R)n has been limited. This limitation is mainly due to the strong aurophilic interactions in (AuC2R)n, resulting in poor solubility in solvents and challenging structural characterization. Consequently, there are only a few studies that have clearly defined the structures of these gold(I) clusters. Nevertheless, homoleptic alkynyl gold(I) clusters are extensively used in synthesizing various gold(I) complexes.
In this study, we introduced a bulky H-shaped pentiptycene ligand into the gold(I) alkynyl complex system, synthesizing new homoleptic alkynyl gold(I) clusters, named as [AuPa]n. Through varying crystallization conditions, we obtained several types of crystals. The first type includes a tetranuclear gold(I) cluster [AuPa]4 and a hexanuclear gold(I) cluster [AuPa]6, termed [AuPa]4+6. The second type consists of two distinct hexanuclear gold(I) clusters [AuPa]6, named [AuPa]6+6. The third type includes three distinct hexanuclear gold(I) clusters [AuPa]6, referred to as [AuPa]6+6+6. The distinguishing feature of our work, compared to previous studies, lies in the introduction of the pentiptycene ligand, which leads to the formation of crystals with varying size of gold(I). Moreover, [AuPa]n exhibits a wide range of stimulus-responsive properties and multicolor luminochromism. These properties can be triggered by temperature changes, light irradiation, solvent vapor exposure, and mechanical grinding, marking the first instance of stimuli-responsive behavior observed in homoleptic alkynyl gold(I) clusters. Our study provides clear structural determinations of these clusters. Additionally, Raman spectroscopy confirmed that these changes are due to enhanced gold(I)-gold(I) interactions in the excited state. | en |
| dc.description.provenance | Submitted by admin ntu (admin@lib.ntu.edu.tw) on 2024-08-20T16:11:20Z No. of bitstreams: 0 | en |
| dc.description.provenance | Made available in DSpace on 2024-08-20T16:11:21Z (GMT). No. of bitstreams: 0 | en |
| dc.description.tableofcontents | 口試委員會審定書 i
謝誌 ii 摘要 v Abstract vi 目次 viii 圖次 x 表次 xvii 附圖目次 xviii 附表目次 xix 第一章 緒論 1 1-1 金(I)錯合物的簡介 1 1-2 金(I)錯合物的結構與光物理性質 3 1-2-1 炔基金(I)錯合物 3 1-2-2 全同配體金(I)錯合物 4 1-2-3 金(I)錯合物刺激響應性質與單晶到單晶的轉變 11 1-3 含五苯荑材料刺激響應光物理性質 18 1-3-1 五苯荑的簡介 18 1-3-2 五苯荑的應用 19 1-4 研究動機 28 第二章 結果與討論 29 2-1 目標金(I)錯合物的合成 29 2-2 目標金(I)錯合物之結構鑑定 30 2-3 目標金(I)錯合物之溶液態下光物理性質 49 2-4 目標金(I)錯合物之固態光物理性質 52 2-5 目標金(I)錯合物之光致放光變色 57 2-6 目標金(I)錯合物之力致放光變色 62 2-7 目標金(I)錯合物之薰致放光變色 64 2-8 目標金(I)錯合物之熱致放光變色 71 2-9 目標金(I)錯合物以拉曼光譜儀觀測其刺激響應性質 72 2-10 目標金(I)錯合物之光機械行為 77 2-11 目標金(I)錯合物之聚集體光物理性質 78 第三章 結論 88 第四章 實驗部分 90 4-1 實驗藥品與溶劑 90 4-2 實驗儀器 92 4-3 實驗方法 96 4-3-1 樣品製備 96 4-3-2 合成步驟 97 4-3-3 養晶條件 101 參考文獻 102 附錄:含五苯荑之金屬錯合物的晶體與發光性質研究：全同配位炔基金(I)團簇與銅(I)錯合物 123 附錄第一章 緒論 123 1-1 銅錯合物的簡介 123 1-2 銅(I)錯合物的簡介 124 1-2-1 銅(I)錯合物的性質 124 1-2-2 單核銅(I)錯合物 131 1-2-2-3 二配位銅(I)錯合物 138 1-2-3 銅(I)錯合物刺激響應性質 141 1-3 含五苯荑之含氮雜環碳烯的研究 146 1-4 研究動機 147 附錄第二章 結果與討論 149 2-1 目標銅(I)錯合物的合成 149 2-2 目標銅(I)錯合物之結構鑑定 150 2-3 目標銅(I)錯合物之光物理性質 156 附錄第三章 結論 160 附錄第四章 實驗部分 160 4-1 實驗藥品與溶劑 160 4-3-1 合成步驟 161 4-3-2 養晶條件 165 附錄參考資料 166 | - |
| dc.language.iso | zh_TW | - |
| dc.subject | 刺激響應性質行為 | zh_TW |
| dc.subject | 親金作用力 | zh_TW |
| dc.subject | 炔基配體 | zh_TW |
| dc.subject | 金 | zh_TW |
| dc.subject | 金屬團簇 | zh_TW |
| dc.subject | 多重放光變色 | zh_TW |
| dc.subject | stimuli-responsive behavior | en |
| dc.subject | metal cluster | en |
| dc.subject | gold | en |
| dc.subject | alkynyl ligand | en |
| dc.subject | aurophilic interaction | en |
| dc.subject | multicolor luminochromism | en |
| dc.title | 含五苯荑之全同配位炔基金(I)團簇的刺激響應性質與多重光色變化研究 | zh_TW |
| dc.title | Pentiptycene-Containing Homoleptic Alkynyl Gold (I) Clusters Exhibit Multi-Stimuli and Multicolored Luminochromism | en |
| dc.type | Thesis | - |
| dc.date.schoolyear | 112-2 | - |
| dc.description.degree | 碩士 | - |
| dc.contributor.oralexamcommittee | 彭旭明;孫世勝;林哲仁 | zh_TW |
| dc.contributor.oralexamcommittee | Shie-Ming Peng;Shih-Sheng Sun;Che-Jen Lin | en |
| dc.subject.keyword | 金屬團簇,金,炔基配體,親金作用力,多重放光變色,刺激響應性質行為, | zh_TW |
| dc.subject.keyword | metal cluster,gold,alkynyl ligand,aurophilic interaction,multicolor luminochromism,stimuli-responsive behavior, | en |
| dc.relation.page | 188 | - |
| dc.identifier.doi | 10.6342/NTU202403889 | - |
| dc.rights.note | 同意授權(限校園內公開) | - |
| dc.date.accepted | 2024-08-11 | - |
| dc.contributor.author-college | 理學院 | - |
| dc.contributor.author-dept | 化學系 | - |
| dc.date.embargo-lift | 2029-08-01 | - |
| 顯示於系所單位： | 化學系 | |
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