臺灣博碩士論文加值系統

在這篇論文裡，我們介紹利用飛秒螢光上轉移方法研究偶氮苯在激發態的的光致順反異構化動力行為。研究主題包括： (i)偶氮苯在不同有機溶劑中的S1(n,p*)激發態螢光動力學行為； (ii)偶氮苯在低和高的黏性溶劑裡的螢光非等向性動力學；(iii)經由修改化學結構和 (iv)透過偶氮苯被嵌入到環糊精的環境限制，觀察旋轉禁制衍生物(或錯合物)的光致順反異構化動力行為。比較相關的實驗結果和理論，我們做出以下的結論︰偶氮苯在低黏滯性環境中，S1(n,p*)和S2(p,p*)激發態的光致順反異構化是由旋轉機制所主導。其激發態的緩解可以被描述成雙指數衰減的過程，兩個時間常數約150~350 fs 和2~4ps，其值會隨著偵測螢光波長位置增加而增加。我們也發現當旋轉的路徑在高黏滯性環境中，或化學結構的修飾下限制住時，其他路徑(例如雙反轉機制)將會開啟而有效地達成S1→S0內轉換的能量緩解過程。

In this thesis, we study the photoisomerization dynamics of azobenzene in theexcited state using femtosecond fluorescence up-conversion method.
The main topics include, (i) the dynamic behavior of S1(n,p*) excited state of azobenzene in different organic solvents; (ii) the fluorescence anisotropy of azobenzene measured in the low and high viscosity solvents; and the relaxation of excited azobenzene derivatives with the rotation pathway restrained (iii) by modified chemical structure and (iv) by confined environment which azobenzene is embedded into cyclodextrins. By comparing with previous ultrafast experiment results and theoretical calculations, we made the following conclusions: the hotoisomerization for both of S1(n,p*) or S2(p,p*) excitation of azobenzene can take place via rotation mechanism in low viscosity solvent. The fluorescence temporal profiles can be
described as bi-exponential decay in subpico- and pico-second time scale. We also found the concerted inversion mechanism can occur when rotational pathway is blocked by high viscosity solvent, or by restricted chemical structure, or by
environment confined.

中文摘要………I
英文摘要………II
誌謝………III
目錄………IV
表目錄………VII
圖目錄………VIII
第1章 簡介………1
1.1 光致變色現象簡介………1
1.2 光化學轉變………4
1.2.1 質子轉移型互變異構物………4
1.2.2 光環化-鍵斷裂生成反應………6
1.2.2.1 spiropyrans………7
1.2.2.2 Fulgides………8
1.2.2.3 Diarylethenes………9
1.2.3 Cis-trans 光致順反異構化………11
1.2.3.1 二苯乙烯………11
1.2.3.2 偶氮苯類光致變色系統………14
1.3 飛秒化學………16
1.3.1 超短脈衝雷射的發展………16
1.3.2 超快化學反應研究………16
1.3.3 化學反應的控制………20
1.4 偶氮苯簡介………22
1.4.1 偶氮苯的吸收光譜………22
1.4.2 偶氮苯的螢光及順反異構化量子產率………23
1.4.3 偶氮苯的異構化機制………28
1.5 結論………36

第2章 實驗原理與裝置………37
2.1 螢光光譜簡介………37
2.1.1 Jablonski Diagram 與去激發過程………38
2.1.2 螢光光譜與Stoke’s位移………40
2.1.3 放光與非放光的躍遷速率………41
2.1.4 螢光非等向性(Fluorescence Anisotropy)………43
2.2 飛秒雷射脈衝與飛秒光學閘門………46
2.2.1 摻鈦藍寶石雷射光譜………47
2.2.2 超短脈衝雷射振盪器………48
2.2.3 Auto-correlation………53
2.2.4 螢光上轉移技術………55
2.3 數據分析………58

第3章 反式偶氮苯在溶液中的飛秒螢光動力學研究………60
3.1 樣品製備………61
3.2 反式偶氮苯的第一激發態S1(n,p*)螢光光譜與濃度效應………61
3.3 反式偶氮苯在非極性溶液中的動力行為………63
3.4 動力學模型與分析………66
3.5 溶劑極性對動力學的影響………70
3.6 溶劑氫鍵對動力學的影響………71
3.7 溶劑黏性對動力學的影響………73
3.8 比較其他的研究結果………75
3.9 結論………76

第4章 反式偶氮苯在溶液中的飛秒螢光非等向性動力學研究………77
4.1 反式偶氮苯在非極性溶劑(正己烷)中的第一激發態S1(n,p*)非等向性螢光光譜………77
4.2 偶氮苯在S1激發態的螢光非等向性動力學模型與分析………81
4.3 結果與討論………87
4.3.1 偶氮苯在S1動力學的緩解機制………87
4.3.2 強度借用(Intensity-Borrowing)………90
4.3.3 起始驅動力在超快S1動力學中的效應………93
4.4 結論………94

第5章 旋轉禁制偶氮苯衍生物的光致順反異構化動力學研究………95
5.1 簡介………95
5.2 樣品製備………97
5.3 結果與討論………97
5.3.1 UV-Vis吸收光譜………97
5.3.2 2S-ABP………101
5.3.2.1 2S-AB動力學模型………101
5.3.2.2 2S-ABP時間解析螢光光譜分析………103
5.3.2.3 2S-ABP 的激發光譜………104
5.3.2.4 2S-ABP 的S2動力行為………106
5.3.3 DMAB與4S-ABP………108
5.3.3.1 S2動力學………108
5.3.3.2 S1動力學………110
5.3.4 AB,DMAB,2S-ABP以及4S-ABP的比較………111
5.4 結論………112

第6章 偶氮苯與環糊精主客化學之超快動力學研究………114
6.1 環糊精簡介………114
6.2 實驗方法………119
6.2.1 錯合物的製備………119
6.2.1.1 偶氮苯和a-CD錯合物的製備………119
6.2.1.2 偶氮苯和b-CD以及g-CD錯合物的製備………120
6.2.1.3 流動式樣品液槽………120
6.3 結果與討論………122
6.3.1 Steady State UV-Vis光譜………122
6.3.2 NMR光譜………123
6.3.3 光致順反異構化量子產率測量………125
6.3.4 偶氮苯在環糊精中的結構………129
6.3.5 偶氮苯與錯合物的熱順反異構化………131
6.3.6 反式偶氮苯及其錯合物之時間解析螢光光譜………133
6.3.7 順式偶氮苯及其錯合物之時間解析螢光光譜………136
6.4 結論………139

第7章 結論………141

附錄A 光致順反異構化機制………144
附錄B 反式偶氮苯在不同有機溶劑中的時間解析螢光光譜………146
附錄C 以UV-VIS吸收光譜測量偶氮苯光致順反異構化量子產率………165
附錄D 偶氮苯與環糊精錯合物的時間解析螢光光譜………176

1. Suppan, P., Chemistry and light. Royal society of chemistry: Cambridge, 1994.
2. Irie, M., Photochromism: Memories and switches - Introduction. Chemical Reviews 2000, 100, (5), 1683-1683.
3. Feringa, B. L., Molecular Switch. Wiley-VCH: Darmstadt, 2001.
4. Rau, H., Azo Compounds. Elsevier: Amsterdam ;Boston 1990; p 165-192.
5. Rau, H., Azo Compounds. Elsevier: Amsterdam ;Boston 2003; p 165-192.
6. Horspool, W. M., CRC Handbook of Organic Photochemistry and Photobiology. CRC press,: Boca Raton,, 1995.
7. Willner, I.; Rubin, S., Control of the structure and functions of biomaterials by light. Angewandte Chemie-International Edition in English 1996, 35, (4), 367-385.
8. Hadjoudis, E., Tautomerism by Hydrogen Transfer in Anils, Aci-Nitro and Related Compounds. Elsevier: Amsterdam ;Boston 1990; p 685-712.
9. Samat, A.; Lokshin, V., Organic Photochromic and Thermochromic Compounds, Volume 2, Physicochemical Studies, Biological Applications, and Thermochromism. Plenum Press: New York, 1999; p 415–466.
10. Barltrop, J. A., Principles of photochemistry. Wiley: Chichester, 1978; p 213.
11. E., F.; Y., H., J Chem. Soc. 1952, 4522-4524
12. Bertelson, R. C., Photochromism. Wiley-Interscience: 1971.
13. Hirshberg, Y., Reversible Formation and Eradication of Colors by Irradiation at Low Temperatures. A Photochemical Memory Model. Journal of the American Chemical Society 1956, 78, (10), 2304-2312.
14. M. Irie, Organic Photochromic and Thermochromic Compounds, Volume 1, Main Photochromic Families. Plenum Press: New York, 1999; p 207–222.
15. Yokoyama, Y., Fulgides for memories and switches. Chemical Reviews 2000, 100, (5), 1717-1739.
16. Irie, M.; Mohri, M., Thermally irreversible photochromic systems. Reversible photocyclization of diarylethene derivatives. The Journal of Organic Chemistry 1988, 53, (4), 803-808.
17. Irie, M., Diarylethenes for memories and switches. Chemical Reviews 2000, 100, (5), 1685-1716.
18. Higashiguchi, K.; Matsuda, K.; Kobatake, S.; Yamada, T.; Kawai, T.; Irie, M., Fatigue mechanism of photochromic 1,2-bis(2,5-dimethyl-3-thienyl)perfluorocyclopentene. Bulletin of the Chemical Society of Japan 2000, 73, (10), 2389-2394.
19. Lucas, L. N.; van Esch, J.; Kellogg, R. M.; Feringa, B. L., A new class of photochromic 1,2-diarylethenes; synthesis and switching properties of bis(3-thienyl)cyclopentenes. Chemical Communications 1998, (21), 2313-2314.
20. Xu, B. A.; Huang, Z. N.; Jin, S.; Ming, Y. F.; Fan, M. G.; Yao, S. D., Synthesis and photochromic mechanism of 3,4-bis[2,5-dimethylthiophene-3-yl]-2,5-dihydrothiophene. Journal of Photochemistry and Photobiology a-Chemistry 1997, 110, (1), 35-40.
21. Irie, M.; Lifka, T.; Kobatake, S.; Kato, N., Photochromism of 1,2-bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene in a single-crystalline phase. Journal of the American Chemical Society 2000, 122, (20), 4871-4876.
22. Morimoto, M.; Kobatake, S.; Irie, M., Multi-colored photochromic crystals of diarylethene mixtures. Advanced Materials 2002, 14, (15), 1027-1029.
23. Yamaguchi, T.; Uchida, K.; Irie, M., Asymmetric photocyclization of diarylethene derivatives. Journal of the American Chemical Society 1997, 119, (26), 6066-6071.
24. Sigman, M. E.; Barbas, J. T.; Corbett, S.; Chen, Y. B.; Ivanov, I.; Dabestani, R., Photochemical reactions of trans-stilbene and 1,1-diphenylethylene on silica gel: mechanisms of oxidation and dimerization. Journal of Photochemistry and Photobiology a-Chemistry 2001, 138, (3), 269-274.
25. Mitchell, R. H., The Metacyclophanediene-Dihydropyrene Photochromic p Switch. Eur. J. Org. Chem. 1999, 1999, (11), 2695-2703.
26. Sension, R. J.; Repinec, S. T.; Szarka, A. Z.; Hochstrasser, R. M., Femtosecond Laser Studies of the Cis-Stilbene Photoisomerization Reactions. Journal of Chemical Physics 1993, 98, (8), 6291-6315.
27. Waldeck, D. H., Photoisomerization Dynamics of Stilbenes. Chemical Reviews 1991, 91, (3), 415-436.
28. Papper, V.; Likhtenshtein, G. I., Substituted stilbenes: a new view on well-known systems - New applications in chemistry and biophysics. Journal of Photochemistry and Photobiology a-Chemistry 2001, 140, (1), 39-52.
29. Saltiel, J.; Marinari, A.; Chang, D. W.-L.; Mitchener, J. C.; Megarity, E. D., Trans-Cis Photoisomerization of the Stilbenes and a Reexamination of the Positional Dependence of the Heavy-Atom Effect. Journal of the American Chemical Society 1979, 101, 2982-2996.
30. Ho, T. I.; Su, T. M.; Hwang, T. C., A Convenient Method of Measuring Quantum Yields of Photoisomerization of Trans-Stilbene. Journal of Photochemistry and Photobiology a-Chemistry 1988, 41, (3), 293-298.
31. Repinec, S. T.; Sension, R. J.; Szarka, A. Z.; Hochstrasser, R. M., Femtosecond Laser Studies of the Cis-Stilbene Photoisomerization Reactions - the Cis-Stilbene to Dihydrophenanthrene Reaction. Journal of Physical Chemistry 1991, 95, (25), 10380-10385.
32. Wyman, G. M., THE CIS-TRANS ISOMERIZATION OF CONJUGATED COMPOUNDS. Chemical Reviews 1955, 55, 625-657.
33. J., R. D.; J., B., Photochromism. Wiley-Interscience: 1971.
34. Hartley, G. S., The Cis-Form of Azobenzene and Velocity of Thermal Cis-Trans Conversion of Azobenzene and Some Derivatives. J. Chem. Soc. 1938, 633.
35. Hagen, R.; Bieringer, T., Photoaddressable polymers for optical data storage. Advanced Materials 2001, 13, (23), 1805-1810.
36. Natansohn, A.; Rochon, P., Azobenzene-containing polymers: Digital and holographic storage. Photonic and Optoelectronic Polymers 1997, 672, 236-250.
37. Tamai, N.; Miyasaka, H., Ultrafast dynamics of photochromic systems. Chemical Reviews 2000, 100, (5), 1875-1890.
38. Sekkat, Z.; Wood, J.; Knoll, W., Reorientation Mechanism of Azobenzenes within the Trans-Double-Right-Arrow-Cis Photoisomerization. Journal of Physical Chemistry 1995, 99, (47), 17226-17234.
39. Jung, C. C.; Rutloh, M.; Stumpe, J., Waveguide spectroscopic characterization of 3D anisotropies in conventionally photooriented and annealed films of liquid crystalline and amorphous azobenzene polymers. Journal of Physical Chemistry B 2005, 109, (16), 7865-7871.
40. Paterson, J.; Natansohn, A.; Rochon, P.; Callender, C. L.; Robitaille, L., Optically inscribed surface relief diffraction gratings on azobenzene containing polymers for coupling light into slab waveguides. Applied Physics Letters 1996, 69, (22), 3318-3320.
41. Iftime, G.; Labarthet, F. L.; Natansohn, A.; Rochon, P., Control of chirality of an azobenzene liquid crystalline polymer with circularly polarized light. Journal of the American Chemical Society 2000, 122, (51), 12646-12650.
42. Yamada, K.; Otsubo, H.; Yonemura, H.; Yamada, S.; Matsuo, T., Nonlinear optical responses of dialkoxyazobenzene isomers adsorbed to interface between heptane and viologen-modified quartz plates. Chemistry Letters 1997, (5), 451-452.
43. Jiang, W. H.; Wang, G. J.; He, Y. N.; Wang, X. G.; An, Y. L.; Song, Y. L.; Jiang, L., Photo-switched wettability on an electrostatic self-assembly azobenzene monolayer. Chemical Communications 2005, (28), 3550-3552.
44. Raymo, F. M.; Tomasulo, M., Fluorescence modulation with photochromic switches. Journal of Physical Chemistry A 2005, 109, (33), 7343-7352.
45. Muraoka, T.; Kinbara, K.; Kobayashi, Y.; Aida, T., Light-driven open-close motion of chiral molecular scissors. Journal of the American Chemical Society 2003, 125, (19), 5612-5613.
46. Muraoka, T.; Kinbara, K.; Aida, T., Mechanical twisting of a guest by a photoresponsive host. Nature 2006, 440, (7083), 512-515.
47. Rulliere, C., Femtosecond laser pulses :principles and experiments. Springer: Berlin 1998.
48. Zewail, A. H., Femtochemistry: Atomic-scale dynamics of the chemical bond. Journal of Physical Chemistry A 2000, 104, (24), 5660-5694.
49. Zewail, A. H., Femtochemistry. Past, present, and future. Pure and Applied Chemistry 2000, 72, (12), 2219-2231.
50. Rosker, M. J.; Dantus, M.; Zewail, A. H., Femtosecond real-time probing of reactions. I. The technique. Journal of Chemical Physics 1989, 89, (10), 6113-6127.
51. Herek, J. L.; Pedersen, S.; Banares, L.; Zewail, A. H., Femtosecond Real-Time Probing of Reactions .9. Hydrogen-Atom Transfer. Journal of Chemical Physics 1992, 97, (12), 9046-9061.
52. Materny, A.; Herek, J. L.; Cong, P.; Zewail, A. H., Femtosecond Real-Time Probing of Reactions .16. Dissociation with Intense Pulses. Journal of Physical Chemistry 1994, 98, (13), 3352-3360.
53. Herek, J. L.; Materny, A.; Zewail, A. H., Femtosecond Control of an Elementary Unimolecular Reaction from the Transition-State Region. Chemical Physics Letters 1994, 228, (1-3), 15-25.
54. Fujino, T.; Arzhantsev, S. Y.; Tahara, T., Femtosecond time-resolved fluorescence study of photoisomerization of trans-azobenzene. Journal of Physical Chemistry A 2001, 105, (35), 8123-8129.
55. Malkin, S.; Fischer, E., Temperature Dependence of Photoisomerization .2. Quantum Yields of Cis ]--] Trans Isomerizations in Azo-Compounds. Journal of Physical Chemistry 1962, 66, (12), 2482-2486.
56. Bortolus, P.; Monti, S., Cis-Trans Photoisomerization of Azobenzene - Solvent and Triplet Donor Effects. Journal of Physical Chemistry 1979, 83, (6), 648-652.
57. Shinkai, S.; Nakaji, T.; Nishida, Y.; Ogawa, T.; Manabe, O., Photoresponsive Crown Ethers. 1. Cis-Trans Isomerism of Azobenzene as a Tool to Enforce Conformational Changes of Crown Ethers and Polymers’. J. Am. Chem. SOC 1980, 102, 5860-5865.
58. Shinkai, S., Switch-functionalized systems in biomimetic chemistry. Pure & Appl. Chem 1987, 59, (3), 425-430.
59. Rau, H.; Luddecke, E., On the Rotation-Inversion Controversy on Photoisomerization of Azobenzenes. Experimental Proof of Inversion. Journal of the American Chemical Society 1982, 104, 1616-1620.
60. Rau, H., Further evidence for rotation in the p,p* and inversion in the n,p* photoisomerization of azobenzenes. J. Photochem. Photobiol. A 1984, 26, 221.
61. Rau, H.; Yu-Quan, S., Photoisomerization of sterically hindered azobenzenes. J. Photochem. Photobiol. A 1988, 42, 321.
62. Shinkai, S.; Miyazaki, K.; Nakashima, M.; Manabe, O., Photoresponsive Crown Ethers .15. Synthesis and Properties of a New Photoresponsive Crown Ether with a Fluorescent Stilbene-Cap. Bulletin of the Chemical Society of Japan 1985, 58, (3), 1059-1060.
63. Liu, R. S. H.; Hammond, G. S., Examples of hula-twist in photochemical cis-trans isomerization. Chemistry-a European Journal 2001, 7, (21), 4536-4544.
64. Liu, R. S. H.; Yang, L. Y.; Hirata, C.; Liu, J.; Ho, T. I., Hula-twist. A stereoselective and regioselective photoisomerization reaction mechanism. Journal of the Chinese Chemical Society 2006, 53, (1), 227-232.
65. Rau, H.; Waldner, I., A non-rotatory isomerization path in ethene derivatives? Investigation of a stilbenophane and protonated azobenzenophanes ("pseudo-stilbenophanes"). Physical Chemistry Chemical Physics 2002, 4, (10), 1776-1780.
66. Ciminelli, C.; Granucci, G.; Persico, M., Are azobenzenophanes rotation-restricted? Journal of Chemical Physics 2005, 123, (17), -.
67. Lu, Y. C.; Diau, E. W. G.; Rau, H., Femtosecond fluorescence dynamics of rotation-restricted azobenzenophanes: new evidence on the mechanism of trans -> cis photoisomerization of azobenzene. Journal of Physical Chemistry A 2005, 109, (10), 2090-2099.
68. Shen, Y. Q.; Rau, H., The Environmentally Controlled Photoisomerization of Probe Molecules Containing Azobenzene Moieties in Solid Poly(Methyl Methacrylate). Makromolekulare Chemie-Macromolecular Chemistry and Physics 1991, 192, (4), 945-957.
69. Curtin, D. Y.; Grubbs, E. J.; McCarty, C. G., Uncatalyzed syn-anti Isomerization of Imines, Oxime Ethers,and Haloimines. J. Am. Chem. SOC 1966, 88, (12), 2775-2786.
70. Fischer, E., Photosensitized Isomerization of Azobenzene. Journal of the American Chemical Society 1968, 90, (3), 796-797.
71. Ronayett.J; Arnaud, R.; Lemaire, J., Isomerization Photosensitized by Dyes and Photoreduction of Azobenzene in Solution .2. Canadian Journal of Chemistry-Revue Canadienne De Chimie 1974, 52, (10), 1858-1867.
72. Monti, S.; Orlandi, G.; Palmieri, P., Features of the Photochemically Active State Surfaces of Azobenzene. Chemical Physics 1982, 71, (1), 87-99.
73. Monti, S.; Gardini, E.; Bortolus, P.; Amouyal, E., The Triplet-State of Azobenzene. Chemical Physics Letters 1981, 77, (1), 115-119.
74. Cattaneo, P.; Persico, M., An ab initio study of the photochemistry of azobenzene. Physical Chemistry Chemical Physics 1999, 1, (20), 4739-4743.
75. Ishikawa, T.; Noro, T.; Shoda, T., Theoretical study on the photoisomerization of azobenzene. Journal of Chemical Physics 2001, 115, (16), 7503-7512.
76. Diau, E. W. G., A new trans-to-cis photoisomerization mechanism of azobenzene on the S-1(n,pi*) surface. Journal of Physical Chemistry A 2004, 108, (6), 950-956.
77. Lednev, I. K.; Ye, T. Q.; Hester, R. E.; Moore, J. N., Femtosecond time-resolved UV-visible absorption spectroscopy of trans-azobenzene in solution. Journal of Physical Chemistry 1996, 100, (32), 13338-13341.
78. Lednev, I. K.; Ye, T. Q.; Matousek, P.; Towrie, M.; Foggi, P.; Neuwahl, F. V. R.; Umapathy, S.; Hester, R. E.; Moore, J. N., Femtosecond time-resolved UV-visible absorption spectroscopy of trans-azobenzene: dependence on excitation wavelength. Chemical Physics Letters 1998, 290, (1-3), 68-74.
79. Lednev, I. K.; Ye, T. Q.; Abbott, L. C.; Hester, R. E.; Moore, J. N., Photoisomerization of a capped azobenzene in solution probed by ultrafast time-resolved electronic absorption spectroscopy. Journal of Physical Chemistry A 1998, 102, (46), 9161-9166.
80. Nagele, T.; Hoche, R.; Zinth, W.; Wachtveitl, J., Femtosecond photoisomerization of cis-azobenzene. Chemical Physics Letters 1997, 272, (5-6), 489-495.
81. Hamm, P.; Ohline, S. M.; Zinth, W., Vibrational cooling after ultrafast photoisomerization of azobenzene measured by femtosecond infrared spectroscopy. Journal of Chemical Physics 1997, 106, (2), 519-529.
82. Fujino, T.; Tahara, T., Picosecond time-resolved Raman study of trans-azobenzene. Journal of Physical Chemistry A 2000, 104, (18), 4203-4210.
83. Fujino, T.; Arzhantsev, S. Y.; Tahara, T., Femtosecond/picosecond time-resolved spectroscopy of trans-azobenzene: Isomerization mechanism following S-2(pp*)<- S-0 photoexcitation. Bulletin of the Chemical Society of Japan 2002, 75, (5), 1031-1040.