請用此 Handle URI 來引用此文件：
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/101547完整後設資料紀錄
| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 王建隆 | zh_TW |
| dc.contributor.advisor | Chien-Lung Wang | en |
| dc.contributor.author | 羅偉源 | zh_TW |
| dc.contributor.author | Wei-Yuan Lo | en |
| dc.date.accessioned | 2026-02-11T16:15:55Z | - |
| dc.date.available | 2026-02-12 | - |
| dc.date.copyright | 2026-02-11 | - |
| dc.date.issued | 2026 | - |
| dc.date.submitted | 2026-01-31 | - |
| dc.identifier.citation | 1.Lehn, J.-M. Supramolecular Chemistry. Science 1993, 260 (5115), 1762-1763.
2.Lehn, J.-M. Perspectives in Chemistry—Steps towards Complex Matter. Angew. Chem. Int. Ed. 2013, 52 (10), 2836-2850. 3.Lehn, J.-M. Supramolecular Chemistry—Scope and Perspectives Molecules, Supermolecules, and Molecular Devices (Nobel Lecture). Angew. Chem. Int. Ed. 1988, 27 (1), 89-112. 4.Lehn, J.-M. Perspectives in Supramolecular Chemistry—From Molecular Recognition towards Molecular Information Processing and Self-Organization. Angew. Chem. Int. Ed. 1990, 29 (11), 1304-1319. 5.Lehn, J.-M. Toward Self-Organization and Complex Matter. Science 2002, 295 (5564), 2400-2403. 6.Hunter, C. A.; Sanders, J. K. M. The nature of .pi.-.pi. interactions. J. Am. Chem. Soc. 1990, 112 (14), 5525-5534. 7.Martinez, C. R.; Iverson, B. L. Rethinking the term “pi-stacking”. Chem. Sci. 2012, 3 (7), 2191-2201. 8.Claessens, C. G.; Stoddart, J. F. π–π INTERACTIONS IN SELF-ASSEMBLY. J. Phys. Org. Chem. 1997, 10 (5), 254-272. 9.Yao, Z.-F.; Wang, J.-Y.; Pei, J. Control of π–π Stacking via Crystal Engineering in Organic Conjugated Small Molecule Crystals. Cryst. Growth Des. 2018, 18 (1), 7-15. 10.Thakuria, R.; Nath, N. K.; Saha, B. K. The Nature and Applications of π–π Interactions: A Perspective. Cryst. Growth Des. 2019, 19 (2), 523-528. 11.Das, A.; Ghosh, S. Supramolecular Assemblies by Charge-Transfer Interactions between Donor and Acceptor Chromophores. Angew. Chem. Int. Ed. 2014, 53 (8), 2038-2054. 12.Wu, J.-R.; Wu, G.; Li, D.; Yang, Y.-W. Macrocycle-Based Crystalline Supramolecular Assemblies Built with Intermolecular Charge-Transfer Interactions. Angew. Chem. Int. Ed. 2023, 62 (14), e202218142. 13.Li, Y.; Liu, T.; Liu, H.; Tian, M.-Z.; Li, Y. Self-Assembly of Intramolecular Charge-Transfer Compounds into Functional Molecular Systems. Acc. Chem. Res. 2014, 47 (4), 1186-1198. 14.Goetz, K. P.; Vermeulen, D.; Payne, M. E.; Kloc, C.; McNeil, L. E.; Jurchescu, O. D. Charge-transfer complexes: new perspectives on an old class of compounds. J. Mater. Chem. C 2014, 2 (17), 3065-3076. 15.Ko, Y. H.; Kim, E.; Hwang, I.; Kim, K. Supramolecular assemblies built with host-stabilized charge-transfer interactions. Chem. Commun. 2007, (13), 1305-1315. 16.Zhu, W.; Zheng, R.; Zhen, Y.; Yu, Z.; Dong, H.; Fu, H.; Shi, Q.; Hu, W. Rational Design of Charge-Transfer Interactions in Halogen-Bonded Co-crystals toward Versatile Solid-State Optoelectronics. J. Am. Chem. Soc. 2015, 137 (34), 11038-11046. 17.Kumar, M.; Venkata Rao, K.; George, S. J. Supramolecular charge transfer nanostructures. Phys. Chem. Chem. Phys. 2014, 16 (4), 1300-1313. 18.Zhu, W.; Zheng, R.; Fu, X.; Fu, H.; Shi, Q.; Zhen, Y.; Dong, H.; Hu, W. Revealing the Charge-Transfer Interactions in Self-Assembled Organic Cocrystals: Two-Dimensional Photonic Applications. Angew. Chem. Int. Ed. 2015, 54 (23), 6785-6789. 19.Gujrati, M. D.; Kumar, N. S. S.; Brown, A. S.; Captain, B.; Wilson, J. N. Luminescent Charge-Transfer Complexes: Tuning Emission in Binary Fluorophore Mixtures. Langmuir 2011, 27 (11), 6554-6558. 20.Bartlett, P. N.; Tong, X. Q. Dissolution Processes at TTF−TCNQ Single-Crystal Electrodes: A Dynamic in Situ Electrochemical Scanning Tunneling Microscopy Study. J. Phys. Chem. B 1997, 101 (42), 8540-8549. 21.Baharfar, M.; Hillier, A. C.; Mao, G. Charge-Transfer Complexes: Fundamentals and Advances in Catalysis, Sensing, and Optoelectronic Applications. Adv. Mater. 2024, 36 (42), 2406083. 22.Miyasaka, H. Control of Charge Transfer in Donor/Acceptor Metal–Organic Frameworks. Acc. Chem. Res. 2013, 46 (2), 248-257. 23.Ottolenghi, M. Charge-transfer complexes in the excited state. Laser photolysis studies. Acc. Chem. Res. 1973, 6 (5), 153-160. 24.Miyasaka, H.; Ojima, S.; Mataga, N. Femtosecond-picosecond laser photolysis studies of the ion pair formation process in the excited state of the charge-transfer complex in solution. J. Phys. Chem. 1989, 93 (9), 3380-3382. 25.Ni, W.; Gurzadyan, G. G.; Ma, L.; Hu, P.; Kloc, C.; Sun, L. Ultrafast Tuning of Various Photochemical Pathways in Perylene–TCNQ Charge-Transfer Crystals. J. Phys. Chem. C 2020, 124 (25), 13894-13901. 26.Zhang, J.; Xu, W.; Sheng, P.; Zhao, G.; Zhu, D. Organic Donor–Acceptor Complexes as Novel Organic Semiconductors. Acc. Chem. Res. 2017, 50 (7), 1654-1662. 27.Zhu, L.; Geng, H.; Yi, Y.; Wei, Z. Charge transport in organic donor–acceptor mixed-stack crystals: the role of nonlocal electron–phonon couplings. Phys. Chem. Chem. Phys. 2017, 19 (6), 4418-4425. 28.Madhu, M.; Ramakrishnan, R.; Vijay, V.; Hariharan, M. Free Charge Carriers in Homo-Sorted π-Stacks of Donor–Acceptor Conjugates. Chem. Rev. 2021, 121 (13), 8234-8284. 29.Kouwer, P. H. J.; Mehl, G. H. Hierarchical organisation in shape-amphiphilic liquid crystals. J. Mater. Chem. 2009, 19 (11), 1564-1575. 30.Li, W.-S.; Yamamoto, Y.; Fukushima, T.; Saeki, A.; Seki, S.; Tagawa, S.; Masunaga, H.; Sasaki, S.; Takata, M.; Aida, T. Amphiphilic Molecular Design as a Rational Strategy for Tailoring Bicontinuous Electron Donor and Acceptor Arrays: Photoconductive Liquid Crystalline Oligothiophene−C60 Dyads. J. Am. Chem. Soc. 2008, 130 (28), 8886-8887. 31.Wang, C.-L.; Zhang, W.-B.; Van Horn, R. M.; Tu, Y.; Gong, X.; Cheng, S. Z. D.; Sun, Y.; Tong, M.; Seo, J.; Hsu, B. B. Y.; et al. A Porphyrin–Fullerene Dyad with a Supramolecular “Double-Cable” Structure as a Novel Electron Acceptor for Bulk Heterojunction Polymer Solar Cells. Adv. Mater. 2011, 23 (26), 2951-2956. 32.Zhang, W.-B.; Yu, X.; Wang, C.-L.; Sun, H.-J.; Hsieh, I. F.; Li, Y.; Dong, X.-H.; Yue, K.; Van Horn, R.; Cheng, S. Z. D. Molecular Nanoparticles Are Unique Elements for Macromolecular Science: From “Nanoatoms” to Giant Molecules. Macromolecules 2014, 47 (4), 1221-1239. 33.Yamamoto, Y.; Zhang, G.; Jin, W.; Fukushima, T.; Ishii, N.; Saeki, A.; Seki, S.; Tagawa, S.; Minari, T.; Tsukagoshi, K.; et al. Ambipolar-transporting coaxial nanotubes with a tailored molecular graphene–fullerene heterojunction. Proc. Natl. Acad. Sci. U.S.A 2009, 106 (50), 21051-21056. 34.Black, H. T.; Perepichka, D. F. Crystal Engineering of Dual Channel p/n Organic Semiconductors by Complementary Hydrogen Bonding. Angew. Chem. Int. Ed. 2014, 53 (8), 2138-2142. 35.Kosco, J.; Moruzzi, F.; Willner, B.; McCulloch, I. Photocatalysts Based on Organic Semiconductors with Tunable Energy Levels for Solar Fuel Applications. Adv. Energy Mater. 2020, 10 (39), 2001935. 36.Li, K.; Peng, B.; Peng, T. Recent Advances in Heterogeneous Photocatalytic CO2 Conversion to Solar Fuels. ACS Catal. 2016, 6 (11), 7485-7527. 37.Chen, X.; Shen, S.; Guo, L.; Mao, S. S. Semiconductor-based Photocatalytic Hydrogen Generation. Chem. Rev. 2010, 110 (11), 6503-6570. 38.Wasielewski, M. R. Photoinduced electron transfer in supramolecular systems for artificial photosynthesis. Chem. Rev. 1992, 92 (3), 435-461. 39.Lei, K.; Wang, D.; Ye, L.; Kou, M.; Deng, Y.; Ma, Z.; Wang, L.; Kong, Y. A Metal-Free Donor–Acceptor Covalent Organic Framework Photocatalyst for Visible-Light-Driven Reduction of CO2 with H2O. ChemSusChem 2020, 13 (7), 1725-1729. 40.Li, W.; Huang, X.; Zeng, T.; Liu, Y. A.; Hu, W.; Yang, H.; Zhang, Y.-B.; Wen, K. Thiazolo[5,4-d]thiazole-Based Donor–Acceptor Covalent Organic Framework for Sunlight-Driven Hydrogen Evolution. Angew. Chem. Int. Ed. 2021, 60 (4), 1869-1874. 41.Li, Z.; Deng, T.; Ma, S.; Zhang, Z.; Wu, G.; Wang, J.; Li, Q.; Xia, H.; Yang, S.-W.; Liu, X. Three-Component Donor−π–Acceptor Covalent–Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution. J. Am. Chem. Soc. 2023, 145 (15), 8364-8374. 42.Lan, X.; Li, H.; Liu, Y.; Zhang, Y.; Zhang, T.; Chen, Y. Covalent Organic Framework with Donor1-Acceptor-Donor2 Motifs Regulating Local Charge of Intercalated Single Cobalt Sites for Photocatalytic CO2 Reduction to Syngas. Angew. Chem. Int. Ed. 2024, 63 (31), e202407092. 43.Schweizer, T.; Kubach, H.; Koch, T. Investigations to characterize the interactions of light radiation, engine operating media and fluorescence tracers for the use of qualitative light-induced fluorescence in engine systems. Automotive and Engine Technology 2021, 6 (3), 275-287. 44.Lakowicz, J. R. Principles of fluorescence spectroscopy; Springer, 2006. 45.Greenland, B. W.; Bird, M. B.; Burattini, S.; Cramer, R.; O'Reilly, R. K.; Patterson, J. P.; Hayes, W.; Cardin, C. J.; Colquhoun, H. M. Mutual binding of polymer end-groups by complementary π–π-stacking: a molecular “Roman Handshake”. Chem. Commun. 2013, 49 (5), 454-456. 46.Lamers, B. A. G.; van Son, M. H. C.; de Graaf, F. V.; van den Bersselaar, B. W. L.; de Waal, B. F. M.; Komatsu, K.; Sato, H.; Aida, T.; Berrocal, J. A.; Palmans, A. R. A.; et al. Tuning the donor–acceptor interactions in phase-segregated block molecules. Mater. Horiz. 2022, 9 (1), 294-302. 47.Mallia, A. R.; Salini, P. S.; Hariharan, M. Nonparallel Stacks of Donor and Acceptor Chromophores Evade Geminate Charge Recombination. J. Am. Chem. Soc. 2015, 137 (50), 15604-15607. 48.Philip, A. M.; Kuriakose, F.; Hariharan, M. Unsolicited Photoexcited-State Pathways Relegate the Long-Lived Charge Separation in Self-Assembled Nucleobase–Arene Conjugate. J. Phys. Chem. C 2017, 121 (42), 23259-23267. 49.Philip, A. M.; Mallia, A. R.; Hariharan, M. Prolonged Charge Separated States in Twisted Stacks of All-Carbon Donor and Acceptor Chromophores. J. Phys. Chem. Lett. 2016, 7 (22), 4751-4756. 50.Sebastian, E.; Hariharan, M. Null Exciton-Coupled Chromophoric Dimer Exhibits Symmetry-Breaking Charge Separation. J. Am. Chem. Soc. 2021, 143 (34), 13769-13781. 51.Xu, S.; Chen, S.; Li, Y.; Gao, Q.; Luo, X.; Li, M.; Ren, L.; Wang, P.; Liu, L.; Wang, J.; et al. Dual Function of Naphthalenediimide Supramolecular Photocatalyst with Giant Internal Electric Field for Efficient Hydrogen and Oxygen Evolution. Small 2024, 20 (32), 2400344. 52.Huang, T.-F.; Lin, K.-J.; Zhuang, Y.-R.; Sun, Y.-E.; Lin, W.-C.; Li, C.-H.; Lin, C.-C.; Chang, E.-C.; Chang, C.-L.; Liu, Y.-C.; et al. Flexible, nonfused sulfone functionalized polymer with enhanced active site access for photocatalytic sacrificial hydrogen evolution. Sci. Adv. 11 (30), eadx1629. 53.Huang, T.-F.; Zhuang, Y.-R.; Chang, C.-L.; Huang, C.-L.; Lin, W.-C.; Jiang, Z.-C.; Ting, L.-Y.; Mekhemer, I. M. A.; Sun, Y.-E.; Kidkhunthod, P.; et al. Indanone-based conjugated polymers enabling ultrafast electron transfer for visible light-driven hydrogen evolution from water. J. Mater. Chem. A 2024, 12 (6), 3633-3643. 54.Lin, W.-C.; Jayakumar, J.; Chang, C.-L.; Ting, L.-Y.; Elsayed, M. H.; Abdellah, M.; Zheng, K.; Elewa, A. M.; Lin, Y.-T.; Liu, J.-J.; et al. Effect of energy bandgap and sacrificial agents of cyclopentadithiophene-based polymers for enhanced photocatalytic hydrogen evolution. Appl. Catal. B: Environ. 2021, 298, 120577. 55.Wu, X.; Van Waeyenberg, J.; Vangestel, D.; Sels, B. The overlooked solvent effects: a reconsideration of the paradigm in semiconductor photocatalysis. Energy Environ. Sci. 2025, 18 (3), 1191-1204. | - |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/101547 | - |
| dc.description.abstract | 本研究旨在探討如何透過分子幾何設計與非共價作用力精準操控予體–受體（D–A）分子的自組裝、晶體堆疊及光物理與光催化功能。以 Pyrene–NDI 為模型系統，我們設計三種代表性構型：正交（o-NPC）、線性（l-NPC）及摺疊（f-NPC），並分析其在固態及共晶體系中的堆疊模式。結構分析顯示，幾何限制與 π–π 堆疊、CH–π 以及電荷轉移（charge-transfer）作用力的協同作用，可引導分子形成單通道或雙通道結構，其中雙通道排列可能有利於予體與受體之間的電子與電洞分離。光物理測試（吸收、穩態與時間解析光致放光）顯示，電荷轉移發光能量與壽命隨分子堆疊方式而異，反映出不同超分子結構下的電荷傳輸行為差異。進一步的光催化實驗表明，雙通道結構的 D–A 分子在可見光驅動下展現增強的反應活性。本研究提出一種結合分子幾何設計與非共價作用力的策略，用以調控 D–A 超分子自組裝行為，並進一步影響其光物理性質與光催化表現，為有機光電與光催化材料之設計提供新的設計思路。 | zh_TW |
| dc.description.abstract | This study aims to elucidate how molecular geometry design and non-covalent interactions can be employed to precisely control the self-assembly, crystal stacking, and photophysical and photocatalytic functions of donor–acceptor (D–A) molecules. Using the Pyrene–NDI system as a model, three representative conformations—orthogonal (o-NPC), linear (l-NPC), and folded (f-NPC)—were designed, and their stacking behaviors in the solid state and co-crystal systems were systematically investigated. Structural analyses reveal that the synergistic effects of geometric constraints, π–π stacking, CH–π interactions, and charge-transfer (CT) interactions direct the formation of single-channel or double-cable architectures, in which the double-cable arrangement may facilitate the separation of electrons and holes between donor and acceptor units. Photophysical studies, including absorption, steady-state, and time-resolved photoluminescence measurements, demonstrate that the CT emission energies and lifetimes are strongly dependent on the molecular stacking modes, while structural features further suggest a favorable influence on electron transport efficiency. Moreover, photocatalytic experiments show that D–A molecules adopting double-cable architectures exhibit enhanced visible-light-driven catalytic activity. This work provides a molecular design strategy that integrates geometry and non-covalent interactions to modulate supramolecular assembly, photophysical behavior, and photocatalytic performance of D–A systems, offering valuable insights for the development of organic optoelectronic and photocatalytic materials. | en |
| dc.description.provenance | Submitted by admin ntu (admin@lib.ntu.edu.tw) on 2026-02-11T16:15:55Z No. of bitstreams: 0 | en |
| dc.description.provenance | Made available in DSpace on 2026-02-11T16:15:55Z (GMT). No. of bitstreams: 0 | en |
| dc.description.tableofcontents | 口試委員審定書 i
誌謝 ii 摘要 iv Abstract v 目次 vi 圖次 ix 式圖次 xiii 表次 xiv 第一章 緒論 1 1.1超分子化學（Supramolecular Chemistry） 1 1.2電荷轉移作用力與 π–π 作用力 2 1.2.1 π–π 作用力 2 1.2.2電荷轉移作用 3 1.3雙通道（Double-Cable）晶體結構 6 1.4光催化與電荷轉移系統應用 7 第二章 研究動機 10 第三章 實驗結果與討論 14 3.1分子合成 14 3.2分子化學結構鑑定 16 3.2.1 o-NPC化學結構鑑定 16 3.2.2 f-NPC化學結構鑑定 18 3.2.3 l-NPC化學結構鑑定 21 3.3 自組裝結構解析 23 3.3.1 l-NPC 之自組裝結構解析 23 3.3.2 f-NPC 之自組裝結構解析 25 3.3.3 o-NPC 之自組裝結構解析 27 3.3.4 o-NPC:Guest 之自組裝結構解析 30 3.4溶液態光物理性質 32 3.5固態光物理性質 37 3.6光催化產氫 39 第四章 結論 45 第五章 實驗部分 47 5.1 試藥來源 47 5.2 量測儀器 47 5.2.1核磁共振光譜儀 (Nuclear Magnetic Resonance, NMR) 47 5.2.2質譜儀 (Mass Spectrometer) 48 5.2.3紫外 / 可見光光譜儀(Ultraviolet / Visible Spectro Photometer) 49 5.2.4光致放光光譜 (Photoluminescent spectroscopy) 49 5.2.5熱重分析儀 (Thermogravimetric Analysis, TGA) 50 5.2.6偏振光學顯微鏡 (Polarized Optical Microscopy, POM) 50 5.2.7廣角X光散射 (Wide-Angle X-ray Scattering, WAXS) 51 5.2.8單晶X光繞射 (Single-crystal X-ray diffraction, SCXRD) 51 5.2.9模擬X光粉末繞射圖 (Simulated XRD powder patterns) 51 5.2.10紫外光電子能譜 (Ultraviolet Photoelectron Spectroscopy, UPS) 52 5.2.11氣相層析儀 (Gas Chromatography) 測試 52 5.2.12太陽光模擬光源 (Solar Simulator) 52 5.2.13計算方法 (Computational Details) 53 5.3 分子合成 53 5.3.1前驅物Hex-NMI之合成 53 5.3.2 o-NPC之合成 55 5.3.3 NMI-OH之合成 56 5.3.4 f-NPC之合成 57 5.3.5 NMI-COOH之合成 58 5.3.6 l-NPC之合成 59 附錄 60 參考資料 74 | - |
| dc.language.iso | zh_TW | - |
| dc.subject | 予體–受體分子 | - |
| dc.subject | 超分子自組裝 | - |
| dc.subject | 雙通道結構 | - |
| dc.subject | 電荷轉移 | - |
| dc.subject | 光物理性質 | - |
| dc.subject | 光催化 | - |
| dc.subject | Donor–acceptor molecules | - |
| dc.subject | Supramolecular self-assembly | - |
| dc.subject | Double-cable structure | - |
| dc.subject | Charge transfer | - |
| dc.subject | Photophysical properties | - |
| dc.subject | Photocatalysis | - |
| dc.title | 正交分子幾何塑造電荷轉移拓撲：建立超分子功能的極簡結構途徑 | zh_TW |
| dc.title | Orthogonal Molecular Geometry to Emergent Charge-Transfer Topologies: A Minimal Pathway toward Supramolecular Function | en |
| dc.type | Thesis | - |
| dc.date.schoolyear | 114-1 | - |
| dc.description.degree | 碩士 | - |
| dc.contributor.oralexamcommittee | 周必泰;莊偉綜;王迪彥;賴英煌 | zh_TW |
| dc.contributor.oralexamcommittee | Pi-Tai Chou;Wei-Tsung Chuang;Di-Yan Wang;Ying-Huang Lai | en |
| dc.subject.keyword | 予體–受體分子,超分子自組裝雙通道結構電荷轉移光物理性質光催化 | zh_TW |
| dc.subject.keyword | Donor–acceptor molecules,Supramolecular self-assemblyDouble-cable structureCharge transferPhotophysical propertiesPhotocatalysis | en |
| dc.relation.page | 78 | - |
| dc.identifier.doi | 10.6342/NTU202600454 | - |
| dc.rights.note | 同意授權(限校園內公開) | - |
| dc.date.accepted | 2026-02-03 | - |
| dc.contributor.author-college | 理學院 | - |
| dc.contributor.author-dept | 化學系 | - |
| dc.date.embargo-lift | 2031-01-29 | - |
| 顯示於系所單位： | 化學系 | |
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