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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
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dc.contributor.advisor | 周必泰(Pi-Tai Chou) | |
dc.contributor.author | Meng-Chi Chen | en |
dc.contributor.author | 陳孟圻 | zh_TW |
dc.date.accessioned | 2021-05-17T15:59:41Z | - |
dc.date.available | 2020-02-04 | |
dc.date.available | 2021-05-17T15:59:41Z | - |
dc.date.copyright | 2020-02-04 | |
dc.date.issued | 2020 | |
dc.date.submitted | 2020-02-03 | |
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Kawanishi, Y.; Kitamura, N.; Tazuke, S., Coulombic Effect on Photoinduced Electron-Transfer Reactions between Phenothiazines and Viologens. J Phys Chem-Us 1986, 90 (11), 2469-2475. 38. Yang, S.; Liu, J.; Zhou, P.; He, G., Solvent effects on 3-keto-1H-pyrido[3,2,1-kl]phenothiazine fluorescence in polar and protic solvents. J Phys Chem B 2011, 115 (36), 10692-8. 39. Caspar, J. V.; Meyer, T. J., Application of the Energy-Gap Law to Nonradiative, Excited-State Decay. J Phys Chem-Us 1983, 87 (6), 952-957. 40. Cummings, S. D.; Eisenberg, R., Tuning the excited-state properties of platinum(II) diimine dithiolate complexes. Journal of the American Chemical Society 1996, 118 (8), 1949-1960. 41. Chen, W.; Chen, C. L.; Zhang, Z.; Chen, Y. A.; Chao, W. C.; Su, J.; Tian, H.; Chou, P. T., Snapshotting the Excited-State Planarization of Chemically Locked N,N'-Disubstituted Dihydrodibenzo[a,c]phenazines. J Am Chem Soc 2017, 139 (4), 1636-1644. 42. 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dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/7117 | - |
dc.description.abstract | 無論在藥物、染料敏化太陽能電池,或是有機發光二極體上,硫二苯胺(phenothiazine,PTZ)都有許多的應用。但由於它螢光量子產率低(在環己烷中小於1%),在應用上受到部分限制。有趣的是,當這個低螢光量子產率與硝基(-NO2),一個普遍公認螢光淬滅體,結合形成3-硝基硫二苯胺(3-nitrophenothiazine,PTZ-NO2)時,竟有極高的螢光量子產率(在環己烷中100%)。為了更進一步調查此現象及其背後的物理化學機制,我們設計並合成了一系列的C3取代硫二苯胺來做比較,其中取代基包含拉電子的腈基(-CN)、甲醯基(-CHO),及硝基(-NO2),以及推電子的甲氧基(-OMe)。與無取代的硫二苯胺及加了推電子基的硫二苯胺相比,拉電子基造成螢光量子產率明顯提高。在化學計算的幫助之下,我們發現π到π*的電子躍遷在PTZ及PTZ-OMe中是部分禁制躍遷,因其π*與硫上的未鍵結軌域混合;相反地,由於拉電子基降低了LUMO的能量,使它不再與未鍵結軌域混合,而造成π到π*變為容許躍遷。此研究展示了如何利用分子設計一窺PTZ中HOMO跟LUMO的能量,進而達到高螢光量子產率。 | zh_TW |
dc.description.abstract | Phenothiazine (PTZ) is a versatile compound that possesses many applications in pharmaceutical chemistry, dye-sensitized solar cell, etc. However, its weak-fluorescent character (quantum yields less than 1% in toluene) impedes its further applications. Besides, the nitro group (-NO2) is widely considered as a fluorescence quencher. Interestingly, we can obtain a highly fluorescent chromophore by combining these two moieties, forming 3-nitrophenothiazine (PTZ-NO2). To make a fair comparison, a series of PTZ substituted with various electron-withdrawing groups (cyano -CN and formyl -CHO) and electron-donating group (methoxy -OMe) group at C3-position was designed and synthesized. As we observed, the three molecules with different electron-withdrawing groups exhibit brilliant quantum yields compared with the non-substituted PTZ and electron-donating group substituted derivative. With the aid of computational approaches, the results reveal that the electronic transitions in PTZ and PTZ-OMe are partially forbidden π to π* transition, in which the π* orbital is mixed with the nonbonding orbital character of the sulfur atom. On the contrary, the transitions in the electron-withdrawing substituted analogies show allowed π to π* transition, which is due to the addition of electron-withdrawing group lowering the energy level of LUMO to diminish their mixing with non-bonding orbitals. This work demonstrates a judicious chemical design to exploit the energy level of HOMO and LUMO in PTZ analogies to achieve the high quantum yields. | en |
dc.description.provenance | Made available in DSpace on 2021-05-17T15:59:41Z (GMT). No. of bitstreams: 1 ntu-109-R06223192-1.pdf: 3557932 bytes, checksum: 6d9b89554f96f393f4b31d70aea08206 (MD5) Previous issue date: 2020 | en |
dc.description.tableofcontents | Contents
I. Introduction 15 II. Motivation 17 III. Experiments 18 A. Synthesis 18 B. Absorbance 19 C. Photoluminescence 19 D. Quantum yield 20 E. Time-Correlated Single Photon Counting (TCSPC) 21 F. Extinction coefficient 21 G. Thermal vapor deposition 22 IV. Results and Discussion 24 A. Structural Characterization 24 V. Solid state photophysical property of PTZ-NO2 24 A. Photophysical properties 25 B. Cyclic voltammetry analysis 28 C. Computational approaches 30 VI. Conclusion 33 VII. Spectra, computed frontier orbitals, and additional tables 34 A. Absorption and Fluorescence in cyclohexane, toluene and dichloromethane 34 B. Absorption and Fluorescence in toluene, ethanol, and acetonitrile 35 VIII. Extinction coefficient in toluene 36 A. Experimental Stokes shift 36 B. Excited-state-optimized and ground-state-optimized structure and orbital 37 C. Fluorescence decay 38 D. Quantum yield, Lifetime, and rate constant 41 IX. Supplementary Information 42 A. Compound appearance 42 B. Solid spectrum of PTZ-NO2 42 C. Synthesis procedure 43 1. Synthesis of PTZ-NO2 43 2. Synthesis of PTZ-NH2 45 3. Synthesis of PTZ-CHO 47 4. Synthesis of PTZ-CN 49 5. Synthesis of DPA-OMe 51 6. Synthesis of PTZ-OMe 53 D. Cyclic Voltammetry 55 1. Cyclic Voltammetry graph 55 2. HOMO LUMO energy 56 E. Computational approach 57 1. Ground state and excited state optimized structure 59 2. Ground state optimized orbital 59 3. Distance definition of rc, rD+, and rA- 59 F. Crystal data and structure refinement 60 1. Crystallography of PTZ-OMe 60 2. Crystallography of PTZ 62 3. Crystallography of PTZ-CHO 64 4. Crystallography of PTZ-NO2 66 X. Reference 68 Content of Figure, Scheme, and Table Figure 1. Normalized absorption and photoluminescence spectra of five entitled molecules. Notes that red, yellow, and green lines represent toluene (TOL), ethanol (EtOH), and acetonitrile (ACN), respectively. 34 Figure 2. Normalized absorption and photoluminescence spectra of five entitled molecules. Notes that orange, blue, and purple lines represent toluene (TOL), ethanol (EtOH), and acetonitrile (ACN), respectively. 35 Figure 3. Excited-state-optimized structure (1st row), ground-state-optimized structure (2nd row), as well as excited-state-optimized HOMO (3rd row) and LUMO (4th row) orbitals of the titled molecules computed by m062x/6-31+g(d,p) with cyclohexane as solvent. 37 Scheme 1. Chemical structures of phenothiazine and analogues modified at C3-position. 17 Scheme 2. Synthesis route of five entitled molecules. 18 Table 1. Excitation wavelength and standard dye of titled molecules 19 Table 2. Experimental and calculated optical characteristics for the titled molecules a 25 Table 3. Electrochemical properties and free energy of photoinduced electron transfer of the three entitled molecules with charge transfer. 28 Figure S1. Molar absorption coefficients of five entitled molecule measured in toluene. 36 Figure S2. Fluorescence decay spectrum of PTZ-OMe in five different solvent. 38 Figure S3. Fluorescence decay spectrum of PTZ in five different solvent. 38 Figure S4. Fluorescence decay spectrum of PTZ-CN in five different solvent. 39 Figure S5. Fluorescence decay spectrum of PTZ-CHO in five different solvent. 39 Figure S6. Fluorescence decay spectrum of PTZ-NO2 in five different solvent. 40 Figure S7. The appearance of entitled compounds under regular indoor light. 42 Figure S8. (a) Absorption spectra of PTZ-NO2 in toluene (brown dash) and in 110 nm film made by vacuum deposition. Orange solid line is the PL spectrum of PTZ-NO2 in s toluene. Green, Blue, and Purple dot lines are PL spectra of PTZ-NO2 in solid film and powder form excited by different light source and collected by different detector. There are no meaningful peaks observed in solid PL spectrum of PTZ-NO2. No florescence when shine with hand-held UV light. (b) Appearance of PTZ-NO2 in toluene. (c) Appearance of PTZ-NO2 in 300 nm thick vacuum deposited film. 42 Figure S9. 1H NMR of PTZ-NO2. 44 Figure S10. 13C NMR of PTZ-NO2. 44 Figure S11. 1H NMR of PTZ-NH2. 46 Figure S12. 13C NMR of PTZ-NH2. 46 Figure S13. 1H NMR of PTZ-CHO. 48 Figure S14. 13C NMR of PTZ-CHO. 48 Figure S15. 1H NMR of PTZ-CN. 50 Figure S16. 13C NMR of PTZ-CN. 50 Figure S17. 1H NMR of DPA-OMe. 52 Figure S18. 13C NMR of DPA-OMe. 52 Figure S19. 1H NMR of PTZ-OMe. 54 Figure S20. 13C NMR of PTZ-OMe. 54 Figure S21. Cyclic voltammograms of five entitled molecules. Reduction curves of PTZ derivatives are irreversible since they are easily oxidized. 55 Figure S22. Ground state and excited state optimized structure, with bending angle shown. Red plane was calculated from six carbons in the left benzene ring, green plane was calculated from six carbons in the right benzene ring, and the bending angle was defined as the smaller angle between red and green plane. 59 Figure S23. Ground state optimization of LUMO (upper) and HOMO (lower) orbitals for PTZ-OMe, PTZ, PTZ-CN, PTZ-CHO, and PTZ-NO2 in cyclohexane. 59 Figure S24. Ground state optimized structures in dichloromethane with the definition of rc, rD+, and rA-. A centroid of 22 atoms without the substituted group was calculated as D, the red sphere; another centroid of the substituted group was calculated as A, the green sphere. rc is the DA distance, rD+ is the DC3 distance, and rA- is the C3A distance. 59 Figure S25. X-ray crystal structure of PTZ-OMe. 61 Figure S26. X-ray crystal structure of PTZ. 63 Figure S27. X-ray crystal structure of PTZ-CHO. 65 Figure S28. X-ray crystal structure of PTZ-NO2. 67 Scheme S1. Synthetic route of PTZ-NO2. 43 Scheme S2. Synthetic route of PTZ-NH2. 45 Scheme S3. Synthetic route of PTZ-CHO. 47 Scheme S4. Synthetic route of PTZ-CN. 49 Scheme S5. Synthetic route of DPA-OMe. 51 Scheme S6. Synthetic route of PTZ-OMe. 53 Table S1. Stokes shifts of five titled molecule in five different solvent a in unit of wavenumber calculated from the experimental peak wavelength of absorbance and photoluminescence spectrum. 36 Table S2. Excitation, monitoring wavelength as well as quantum yield, lifetime, and rate constate of the entitled molecules. 41 Table S3. HOMO LUMO energy calculated from CV and PL data. Usually, HOMO=-4.8+EoxiD-EoxiFc and LUMO=-4.8+EredA-EredFc. However, PTZ is easily oxidized when measuring reduction potential, so the calculation of LUMO was adjusted as LUMO=HOMO+EPL onset, where EPL onset is the energy converted from the wavelength of onset of PL spectra, which is 420 nm is our case. 56 Table S4. Calculated wavelength (λ), oscillator strength (f) and orbital transition for five entitled molecules with m062x. 57 Table S5. Calculated wavelength (λ), oscillator strength (f) and orbital transition for five entitled molecules with b3lyp. 58 Table S5. Crystal data and experimental details for PTZ-OMe. 60 Table S6. Crystal data and experimental details for PTZ. 62 Table S7. Crystal data and experimental details for PTZ-CHO. 64 Table S8. Crystal data and experimental details for PTZ-NO2. 66 | |
dc.language.iso | en | |
dc.title | 3號位取代硫二苯胺的初步光物理特性 | zh_TW |
dc.title | Rudimentary photophysical property of selected 3-substituted phenothiazines | en |
dc.type | Thesis | |
dc.date.schoolyear | 108-1 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 張鎮平(Chen-Pin Chang),亞歷山大.旦陳哥(Alexander Demchenko) | |
dc.subject.keyword | 硫二苯胺,硝基,量子產率,螢光, | zh_TW |
dc.subject.keyword | phenothiazine,nitro,quantum yield,fluorescence, | en |
dc.relation.page | 71 | |
dc.identifier.doi | 10.6342/NTU201904352 | |
dc.rights.note | 同意授權(全球公開) | |
dc.date.accepted | 2020-02-03 | |
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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