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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 周必泰 | zh_TW |
| dc.contributor.advisor | Pi-Tai Chou | en |
| dc.contributor.author | 林彥定 | zh_TW |
| dc.contributor.author | Yan-Ding Lin | en |
| dc.date.accessioned | 2025-07-09T16:17:40Z | - |
| dc.date.available | 2025-07-10 | - |
| dc.date.copyright | 2025-07-09 | - |
| dc.date.issued | 2025 | - |
| dc.date.submitted | 2025-06-25 | - |
| dc.identifier.citation | Ch. 1
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| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/97661 | - |
| dc.description.abstract | 本論文針對激發態分子內質子轉移（ESIPT）反應及其光物理行為進行探討，研究對象涵蓋三類具代表性的分子系統：具氫鍵結構的茚酮衍生物、3-羥基黃酮互變異構體，以及具有雙氫鍵結構的紅光OLED發光材料。每個系統分別展現ESIPT在機械誘導、互變異構與固態發光效率等方面的獨特性。
第一章中，我們研究一系列具備RR'N–H···O=C類型分子內氫鍵的茚酮衍生物，透過改變R'基團的電子接受能力，有效調控氫鍵強度與ESIPT效率。其中，化合物4（R' = COCF₃）展現出新穎的機械力誘導型ESIPT現象，即在固態晶體中僅藉由機械應力促使ESIPT產生。提供一種新的ESIPT調控途徑。 第二章探討一種3-羥基黃酮衍生物PRA-3HC，該分子在溶液中以兩種互變異構體共存，分別具有雙氫鍵（N1-H）與單氫鍵（N2-H）結構。此系統可用於研究基態異構化、溶劑依賴的激發態質子轉移（ESIPT）行為，以及氫鍵在光穩定性中的角色。在特定激發條件下觀察到的放大自發輻射（ASE）現象，提供了一個敏感的手段來探測激發態動力學與分子構型分布。透過與單甲基取代物（N1-Me與N2-Me）的比較研究，進一步揭示了氫鍵排列對穩定性與光物理性質的影響。 第三章中，我們開發出一系列雙氫鍵型ESIPT發光分子DPNA、DPNA-F與DPNA-tBu，這些分子產生快速且高效率的ESIPT，並獨特地以KK態單一型式發光。其發光波長超過650奈米，呈現深紅色窄頻光譜，並具備高光致發光量子產率（PLQY）。基於此材料，我們製作出紅光有機發光二極體（OLED），在外部量子效率（EQE）、色純度與穩定性方面均達到優異表現，成功滿足BT.2020色域標準對紅光顯示的要求。 總結而言，本論文展現了透過分子內氫鍵設計與調控，能有效掌握並調變ESIPT系統之光物理性質，為未來ESIPT材料在高效顯示器、光電元件與感測技術中的應用提供了堅實的理論基礎與實驗指引。 | zh_TW |
| dc.description.abstract | This thesis investigates excited-state intramolecular proton transfer (ESIPT) phenomena and their photophysical properties through three distinct classes of compounds: hydrogen-bonded indanone derivatives, 3-hydroxyflavone-based tautomers, and red-emitting OLED materials with dual hydrogen bonds. Each system highlights different aspects of ESIPT, including mechanically induced activation, tautomer-dependent photostability, and efficient solid-state emission.
In Chapter 1, a series of indanone derivatives bearing RR’N-H…O=C-type intramolecular hydrogen bonds was developed. By introducing different electron-withdrawing groups (R’), we successfully modulated the strength of the hydrogen bond and the ESIPT efficiency. And compound 4 (R’ = COCF₃) demonstrated a remarkable and previously unobserved phenomenon: mechanically induced ESIPT in the crystalline state. This behavior was attributed to its non-centrosymmetric crystal packing and strong intramolecular hydrogen bonding, highlighting a new strategy for activating ESIPT via external mechanical force. Chapter 2 examines a 3-hydroxyflavone analogue, PRA-3HC, which exists as a dynamic equilibrium between two tautomers: one featuring dual intramolecular (N1–H) hydrogen bonds, and the other containing a single (N2–H) hydrogen bond. This system allows investigation into ground-state isomerization, solvent-dependent ESIPT behavior, and the role of hydrogen bonding in photostability. The occurrence of amplified spontaneous emission (ASE) under certain excitation conditions provides a sensitive probe of the excited-state dynamics and structural population. Comparative studies using monomethylated analogues (N1-Me and N2-Me) further reveal how specific hydrogen-bonding patterns influence both stability and photophysical properties. Chapter 3 presents a newly developed family of ESIPT-active emitters, DPNA, DPNA-F, and DPNA-tBu designed to support dual intramolecular hydrogen bonds and facilitate highly efficient ESIPT in the solid state. These materials exhibit fast ESIPT kinetics and generate narrowband deep-red emission exclusively from the KK tautomeric form, with emission maxima beyond 650 nm. The compounds also display high photoluminescence quantum yields, making them ideal candidates for use in organic light-emitting diodes (OLEDs). Devices based on these emitters show high external quantum efficiency (EQE), minimal efficiency roll-off, and emission profiles that meet the BT.2020 color standard for red-light emission. Overall, this work demonstrates how rational molecular design focused on hydrogen-bond engineering can be used to precisely control ESIPT behavior, photostability, and emission properties. These findings provide valuable insight into the structure–property relationships in ESIPT systems and pave the way for future developments in organic photonics and optoelectronics. | en |
| dc.description.provenance | Submitted by admin ntu (admin@lib.ntu.edu.tw) on 2025-07-09T16:17:40Z No. of bitstreams: 0 | en |
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| dc.description.tableofcontents | CONTENTS
口試委員會審定書 i 誌謝 ii 中文摘要 iii ABSTRACT iv CONTENTS vi LIST OF FIGURES ix LIST OF TABLES xv LIST OF SCHEMES xvi Chapter 1 The Indanone N–H Type Excited-State Intramolecular Proton Transfer (ESIPT); the Observation of a Mechanically Induced ESIPT Reaction 1 1.1 Introduction 1 1.2 Material and Methods 4 1.2.1 Synthetic Strategies and Protocols 4 1.2.2 Experimental Setup for Steady-State and Time-Resolved Spectroscopy 4 1.3 Results and Discussion 5 1.3.1 Structural Characterization 5 1.3.2 Steady-State Spectroscopy and Theoretical Approach 7 1.3.3 ESIPT Dynamic/ Time-Resolved Photophysical Properties 11 1.3.4 Triboluminescence Behavior 14 1.4 Conclusion 19 1.5 References 20 Chapter 2 A New ESIPT Family Pyrazole-substituted 3-Hydroxychromones: Versatile Hydrogen-bonding Properties, Intense Proton Transfer Tautomer Emission and Amplified Spontaneous Emission 22 2.1 Introduction 23 2.2 Material and methods 27 2.2.1 Experimental Setup for Steady-State and Time-Resolved Spectroscopy 27 2.3 Results and Discussion 28 2.3.1 Synthesis and characterization. 28 2.3.2 Ground-State Tautomeric Ratio Determination. 31 2.3.3 Steady-State Approach. 38 2.3.4 ESIPT Dynamics 43 2.3.5 Amplified Spontaneous Emission (ASE). 45 2.3.6 Versatility of Different Hydrogen Bonding 47 2.4 Conclusion 49 2.5 Appendix 51 2.5.1 NMR spectrum 51 2.6 Reference 58 Chapter 3 Multiple Enol–Keto Isomerization and Excited-State Unidirectional Intramolecular Proton Transfer Generate Intense, Narrowband Red OLEDs 60 3.1 Introduction 61 3.2 Material and Methods 65 3.2.1 Synthetic Routes for DPNA-Based Materials 65 3.2.2 Characterization Methods for Photophysical Property Evaluation 65 3.2.3 Transient Grating Photoluminescence (TGPL) 66 3.3 Synthesis and Structural Characterization 67 3.3.1 Synthesis and Characterization 67 3.3.2 Photophysical Properties 68 3.3.3 Transient Grating Photoluminescence for Investigating Early Dynamic Processes 80 3.3.4 Device Fabrication and Performance 85 3.4 Conclusion 90 3.5 References 91 LIST OF FIGURES Figure 1-1. The molecular packing of compounds 1–4 demonstrates distinct structural arrangements, where compounds 1–3 adopt a centrosymmetric configuration, with an inversion center indicated by an orange dot. In contrast, compound 4 features a non-centrosymmetric packing pattern, setting it apart from the others.7 6 Figure 1-2. Single crystal structure of (a) 1, (b) 2, (c) 3, and (d) 4, green dash line denotes as N—O=C distances (Å). 7 Figure 1-3. The absorption (dashed) and emission (solid) spectra of compounds 1 (blue), 2 (red), 3 (black), and 4 (green) measured in cyclohexane at 295 K. Excitation was performed at the lowest-energy absorption peak of each compound.7 8 Figure 1-4. Electron density difference maps upon excitation for compounds (a) 1, (b) 2, (c) 3, and (d) 4. The diagrams illustrate regions where electron density diminishes (in blue) and accumulates (in red) as a result of the electronic transition. For clarity, the ground and first excited states are labeled as S₀ and S₁ for the normal configuration, and S₀’ and S₁’ for the corresponding tautomeric structures.7 10 Figure 1-5. Fluorescence up-conversion lifetimes for (a) 1, (b) 2, (c) 3, and (d) 4 in CYH are presented. Emission wavelengths of 400 nm and 600 nm were monitored, with the results shown in blue and red, respectively, while the IRF is represented by the black line. Exponential decay fits are displayed as solid lines. In the inset, time-resolved decay profiles in the pico-nanosecond range are shown for 1 and 2, observed at 400 nm (blue trace) and 600 nm (red trace), alongside the IRF (black line). Excitation wavelength used: 300 nm.7 13 Figure 1-6. (a) Emission spectra of compound 4, displaying its photoluminescence in CYH (red line) and in the powdered solid state (blue line), alongside the triboluminescence (TL) observed when the crystal is mechanically stimulated (black line). (b) Photograph of compound 4 captured under standard room lighting conditions, showing its appearance in ambient light. (c) Compound 4 under UV irradiation at 365 nm. (d) An image capturing the TL phenomenon of compound 4 when its crystal is ground inside a sample vial using a spatula. (e) A schematic representation depicting the TL mechanism, corresponding to Figure 1-6(d).7 16 Figure 2-1. Molecular structure of PRA-3HC derived from 3HF consisting of two pyrazole tautomers N1-H, N2-H and their N-methylated analogs N1-Me and N2-Me. For 3-position -OHs, all shown in their most stable conformations. 26 Figure 2-2. (a) The X-ray crystallographic structure of PRA-3HC. The distance is measured from N2’ to O. (b) Catemer structure in the crystal and its side view. Intramolecular H-bonds are highlighted in red, while intermolecular ones are highlighted in blue. The distances are measured from N/O-“H” to “N/O.” (c) Top view of two selected packed catemer chains (I and II) with hypothesized orientation of permanent dipole moments highlighted for two stacked molecules in the center. (d) Side view of the packing. The distances are measured from N2’ (top molecule) to C5 (bottom molecule) for chain I and II. The displacement ellipsoids are drawn at the 50% probability level, and the H atoms are drawn as spheres of arbitrary radius. 31 Figure 2-3. The energy diagram of PRA-3HC. M062x/6-311+G(d,p) PCM in (a) CYH, (b) TOL, (c) DCM, and (d) ACN. 36 Figure 2-4. The energy diagram of N1-Me. M062x/6-311+G(d,p) PCM in (a) CYH, (b) TOL, (c) DCM, and (d) ACN. 37 Figure 2-5. The energy diagram of N2-Me. M062x/6-311+G(d,p) PCM in (a) CYH, (b) TOL, (c) DCM, and (d) ACN. 38 Figure 2-6. Absorption and emission spectra of PRA-3HC in CYH, TOL, and DCM. 39 Figure 2-7. The absorption and excitation spectra of PRA-3HC dissolved in DCM (ca. 10-5 M). 42 Figure 2-8. TCSPC measurements of PRA-3HC (top), N1-Me (mid), and N2-Me (bottom) in CYH, TOL, and DCM the red line denotes as tautomer form, and the gray line is IRF (λex: 365 nm). 44 Figure 2-9. Fluorescence up-conversion measurements of PRA-3HC (top), N1-Me (middle), and N2-Me (bottom) in TOL (a, c, e) and DCM (b, d, f), monitored at 550 nm. 45 Figure 2-10. Absorption (dashed line), emission (orange), and ASE spectra (red) of (a) PRA-3HC in TOL for steady-state spectra and in DCM/TOL (1:1) for ASE spectra, (b) N1-Me, and (c) N2-Me in TOL. 47 Figure 2-11. ASE spectra under different continuous irradiation time of (a) PRA-3HC in TOL/DCM (1:1), (b) N1-Me, and (c) N2-Me in TOL. 49 Figure 2-12. Enlarged 1H NMR spectra of PRA-3HC in (a) CD2Cl2, (b) CD3CN and (c) DMSO-d6. 51 Figure 2-13. 1H NMR spectra of (a) 3HF1, (b) 3HF2 for comparison and (c) N1-Me, (d) N2-Me in CDCl3. Red highlights OH---O=C H-bonding of 3HF1, 3HF2, N1-Me and their chemical shifts, while blue highlights OH---N type of N2-Me. 52 Figure 2-14. Comparison of the 1H NMR spectra of (a) N1-Me, (b) PRA-3HC and (c) N2-Me in CD2Cl2. The two pyrazole ring C-H signals are denoted as α and β. 53 Figure 2-15. Comparison of the 1H NMR spectra of (a) N1-Me, (b) PRA-3HC and (c) N2-Me in CD3CN. The two pyrazole ring C-H signals are denoted as α and β. 53 Figure 2-16. Comparison of the 1H NMR spectra of (a) N1-Me, (b) PRA-3HC and (c) N2-Me in DMSO-d6. The two pyrazole ring C-H signals are denoted as α and β. 54 Figure 2-17. (a) The X-ray crystallographic structure of N2-Me (ic23165), the dihedral angle and 3-O to pyridinyl N distance are denoted as 9.29° and 2.684 Å, respectively. (b), (c) its packings, distance between two parallel molecules is denoted as 3.460 Å. The displacement ellipsoids are drawn at the 50% probability level, and the H atoms are drawn as spheres of arbitrary radius. 55 Figure 3-1. The UV-Vis spectra of DPNA in toluene are presented. The shaded areas in the figure correspond to the simulated vibronic absorption spectra of the KK, EK, and EE isomers, obtained after geometry optimization. The relative intensities were adjusted independently for each species to best match the experimental data.26 69 Figure 3-2. The steady-state spectrum of (a) DPNA (b) DPNA-F and (c) DPNA-tBu are dissolved in toluene (~ 1 × 10-5 M). 70 Figure 3-3. The decay lifetime of each sample was measured by TCSPC. Data for DPNA, DPNA-F, and DPNA-tBu in TOL (mon. 650 nm). 71 Figure 3-4. (a) Proposed isomeric forms of DPNA. (b) Computed energy levels (in eV) of these isomers (EE, EK, and KK) optimized at the ground state and excited state (S₀ and S₁) were obtained via vertical transitions using the Franck–Condon approximation to simulate absorption behavior.26 75 Figure 3-5. The simulated absorption spectra of DPNA.26 77 Figure 3-6. The temperature-dependent absorption spectrum of DPNA were examined in a 1:1 volumetric mixture of methylcyclohexane and TOL. To illustrate the thermodynamic behavior, the inset shows a Van’t Hoff plot depicting the relationship between ln Keq and the inverse of temperature (1/T), derived from absorbance measurements at 530 and 578 nm. For clearer visualization of temperature-dependent absorbance variations, the spectra were scaled to a reference point at 633 nm.26 78 Figure 3-7. Energy Diagram of EE, EK and KK forms at S0-optimized, noted as “@S0-opt”, of (a) DPNA-F and (b) DPNA-tBu.26 80 Figure 3-8. Schematic of the TGPL instrumentation: MPC indicates the multi-plate continuum generator; HWP, the half-wave plate; TFP, thin-film polarizer; SHG and THG represent second- and third-harmonic generation, respectively; PM stands for parabolic mirrors; BS, beam splitter; PL, photoluminescence; and ICCD refers to the intensified charge-coupled device.26 81 Figure 3-9. (Top left) Contour map illustrating the evolution of TGPL. (Top right) Relaxation kinetics at 660 (red) and 620 nm (orange) emission, alongside IRF in gray. (Bottom) Temporal spectral evolution of DPNA-tBu dissolved in TOL (λex: 515 nm).26 83 Figure 3-10. A schematic depiction illustrates the hypothesized kinetic pathway for ground-state isomerization and the proton transfer processes occurring in the excited-state of DPNA-tBu in TOL.26 85 Figure 3-11. (a) Schematic representation of the energy levels in the OLED devices investigated in this work, (b) plots illustrating the relationships among current density, voltage, and luminance (J−V−L), (c) graphs depicting EQE and PE as functions of luminance, and (d) EL spectra for devices utilizing DPNA, DPNA-F, and DPNA-tBu as terminal emitters.26 86 Figure 3-12. (a) J-V-L characteristics, (b) EQE–PE–L characteristics, (c) the spectral overlap between emission (OS1) and absorbance (DPNA in Tol), and (d) EL spectra at various voltages. Device structure: ITO/ HATCN (5nm)/ TAPC (30nm)/ TCTA (10nm)/ DMIC-TRz: OS1(10 wt%) (20nm)/ TmPyPB (70nm)/ Liq/ Al.26 88 Figure 3-13. (a-c) EQE–PE–L characteristics, and (d-f) the normalized EL spectra of DPNA, DPNA-F, and DPNA-tBu devices.26 89 | - |
| dc.language.iso | en | - |
| dc.subject | 機械力誘導放光 | zh_TW |
| dc.subject | 放大自發輻射 | zh_TW |
| dc.subject | 激發態分子內質子轉移 | zh_TW |
| dc.subject | ASE | en |
| dc.subject | ESIPT | en |
| dc.subject | Mechanoluminescence | en |
| dc.title | 激發態質子轉移的光譜和動力學研究：機械力誘導發光、放大自發發射和窄帶發射OLED應用 | zh_TW |
| dc.title | Spectroscopic and Dynamic Studies of Excited-State Proton Transfer: Mechanically Induced Luminescence, and Amplified Spontaneous Emission, and Narrowband Emission OLED Applications | en |
| dc.type | Thesis | - |
| dc.date.schoolyear | 113-2 | - |
| dc.description.degree | 碩士 | - |
| dc.contributor.oralexamcommittee | 洪文誼;何美霖 | zh_TW |
| dc.contributor.oralexamcommittee | Wen-Yi Hung;Mei-Lin Ho | en |
| dc.subject.keyword | 激發態分子內質子轉移,機械力誘導放光,放大自發輻射, | zh_TW |
| dc.subject.keyword | ESIPT,Mechanoluminescence,ASE, | en |
| dc.relation.page | 93 | - |
| dc.identifier.doi | 10.6342/NTU202501315 | - |
| dc.rights.note | 未授權 | - |
| dc.date.accepted | 2025-06-26 | - |
| dc.contributor.author-college | 理學院 | - |
| dc.contributor.author-dept | 化學系 | - |
| dc.date.embargo-lift | N/A | - |
| 顯示於系所單位： | 化學系 | |
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