我們使用時間解析螢光技術，研究兩個以矽烷基 (SiMe2) 作為間隙物且具有立體規則性 (regioregular) 之電子傳遞共聚物單體DA與雙聚體ADDA分子，其中給體D與受體A分別為aniline以及trans-stilbene之發色團。由於單一矽烷基與π-系統沒有電子共軛，可以視為絕緣間隙物，共聚物的光物理性質會類似於其相對應的單體，而烷基則可以增加共聚物在有機溶劑中的溶解度。以266 nm波長飛秒雷射光源激發，共聚物單體與雙聚體之螢光訊號在最初有一個迅速的1-5 ps的衰減成分和接近系統響應函數的快速上升訊號~ 0.4 ps (τ_v^A)，接著以四個自然指數衰減，其時間常數分別為數十個至一百個皮秒 (〖 τ〗_B, 〖 τ〗_C)，數個奈秒 (〖 τ〗_o^A, τ_Re^CT)。τ_v^A指認為分子的振動能態鬆弛與溶劑能量穩定化(solvation)的過程。而〖 τ〗_B 則指認為光異構化與電荷轉移途徑的生命期，〖 τ〗_o^A則指認為trans-stilbene色團 S1激發態的螢光生命期，其中〖 τ〗_B與溶劑的黏度和極性呈現出線性關係，證實在trans-stilbene S1激發態構型緩解為主要的緩解途徑之一。〖 τ〗_C, τ_Re^CT則與溶劑極性呈現出反向線性關係，吾人指認〖 τ〗_C, τ_Re^CT分別為電荷分離態激發態的生成與重合生命期。皮秒時間解析螢光指出 DA與ADDA中電荷傳遞與異構化的速率分別為 (130 ps)-1以及 (126 ps)-1，並分別以(4.3 ns)-1以及 (4.2 ns)-1的速率進行電子重合，與文獻中的結果相符。電子傳遞主要是透過鍵與鍵電子耦合作用力，而 DA與 ADDA中電子傳遞速率的無差異，則暗示兩種共聚物內部的給體–受體之間具有相似的偶合作用力。本實驗結果顯示以矽烷基為間隙物的共聚物小分子，由於合成相當簡易與有效的電子傳遞，在光引誘電子傳遞材料之應用方面具有很好的發展潛力。

1. Diels, J.-C.; Rudolph, W., Ultrashort Laser Pulse Phenomena; Academic press, 2006.
2. Rose, T. S.; Rosker, M. J.; Zewail, A. H., Femtosecond Real‐Time Probing of Reactions. Iv. The Reactions of Alkali Halides. The Journal of Chemical Physics 1989, 91, 7415-7436.
3. Zewail, A. H., Femtochemistry: Atomic-Scale Dynamics of the Chemical Bond Using Ultrafast Lasers (Nobel Lecture). Angew. Chem., Int. Ed. 2000, 39, 2586-2631.
4. Yoshizawa, M.; Kubo, M.; Kurosawa, M., Ultrafast Photoisomerization in Dcm Dye Observed by New Femtosecond Raman Spectroscopy. Journal of Luminescence 2000, 87–89, 739-741.
5. Hannappel, T.; Burfeindt, B.; Storck, W.; Willig, F., Measurement of Ultrafast Photoinduced Electron Transfer from Chemically Anchored Ru-Dye Molecules into Empty Electronic States in a Colloidal Anatase Tio2 Film. J. Phys. Chem. B 1997, 101, 6799-6802.
6. Kavarnos, G. J., Fundamental Concepts of Photoinduced Electron Transfer. In Photoinduced Electron Transfer I, Springer: 1990; pp 21-58.
7. Marcus, R. A.; Sutin, N., Electron Transfers in Chemistry and Biology. Biochimica et Biophysica Acta (BBA) - Reviews on Bioenergetics 1985, 811, 265-322.
8. Hush, N. S., Adiabatic Theory of Outer Sphere Electron-Transfer Reactions in Solution. Transactions of the Faraday Society 1961, 57, 557-580.
9. Ohta, K.; Closs, G. L.; Morokuma, K.; Green, N. J., Stereoelectronic Effects in Intramolecular Long-Distance Electron Transfer in Radical Anions as Predicted by Ab-Initio Mo Calculations. J. Am. Chem. Soc. 1986, 108, 1319-1320.
10. Benniston, A. C.; Harriman, A., Charge on the Move: How Electron-Transfer Dynamics Depend on Molecular Conformation. Chem. Soc. Rev. 2006, 35, 169-179.
11. Closs, G. L.; Miller, J. R., Intramolecular Long-Distance Electron Transfer in Organic Molecules. Science 1988, 240, 440-447.
12. Mataga, N.; Chosrowjan, H.; Shibata, Y.; Yoshida, N.; Osuka, A.; Kikuzawa, T.; Okada, T., First Unequivocal Observation of the Whole Bell-Shaped Energy Gap Law in Intramolecular Charge Separation from S2 Excited State of Directly Linked Porphyrin-Imide Dyads and Its Solvent-Polarity Dependencies. Journal of the American Chemical Society 2001, 123, 12422-12423.
13. Mataga, N.; Taniguchi, S.; Chosrowjan, H.; Osuka, A.; Yoshida, N., Ultrafast Charge Separation and Radiationless Relaxation Processes from Higher Excited Electronic States of Directly Linked Porphyrin–Acceptor Dyads. Photoch Photobio Sci 2003, 2, 493-500.
14. Mataga, N.; Chosrowjan, H.; Taniguchi, S.; Shibata, Y.; Yoshida, N.; Osuka, A.; Kikuzawa, T.; Okada, T., Ultrafast Charge Separation from the S2 Excited State of Directly Linked Porphyrin-Imide Dyads: First Unequivocal Observation of the Whole Bell-Shaped Energy-Gap Law and Its Solvent Dependencies. The Journal of Physical Chemistry A 2002, 106, 12191-12201.
15. Ramos, A. M.; Meskers, S. C. J.; van Hal, P. A.; Knol, J.; Hummelen, J. C.; Janssen, R. A. J., Photoinduced Multistep Energy and Electron Transfer in an Oligoaniline−Oligo(P-Phenylene Vinylene)−Fullerene Triad. The Journal of Physical Chemistry A 2003, 107, 9269-9283.
16. Kaletaş, B. K.; Dobrawa, R.; Sautter, A.; Würthner, F.; Zimine, M.; De Cola, L.; Williams, R. M., Photoinduced Electron and Energy Transfer Processes in a Bichromophoric Pyrene−Perylene Bisimide System. The Journal of Physical Chemistry A 2004, 108, 1900-1909.
17. Miura, T.; Urano, Y.; Tanaka, K.; Nagano, T.; Ohkubo, K.; Fukuzumi, S., Rational Design Principle for Modulating Fluorescence Properties of Fluorescein-Based Probes by Photoinduced Electron Transfer. J. Am. Chem. Soc. 2003, 125, 8666-8671.
18. Deisenhofer, J.; Norris, J. R., Photosynthetic Reaction Center; Academic Press, 1993; Vol. 1.
19. Blankenship, R. E.; Madigan, M. T.; Bauer, C. E., Anoxygenic Photosynthetic Bacteria; Springer, 1995; Vol. 2.
20. Green, B.; Parson, W. W., Light-Harvesting Antennas in Photosynthesis; Springer, 2003; Vol. 13.
21. Chang, C. H.; Tiede, D.; Tang, J.; Smith, U.; Norris, J.; Schiffer, M., Structure of Rhodopseudomonas Sphaeroides R-26 Reaction Center. FEBS Letters 1986, 205, 82-86.
22. Chen, C.-H.; Huang, Y.-C.; Liao, W.-C.; Lim, T.-S.; Liu, K.-L.; Chen, I. C.; Luh, T.-Y., Controlling Conformations in Alternating Dialkylsilylene-Spaced Donor–Acceptor Copolymers by a Cooperative Thorpe–Ingold Effect and Polymer Folding. Chemistry – A European Journal 2012, 18, 334-346.
23. Miller, R. D.; Michl, J., Polysilane High Polymers. Chem. Rev. 1989, 89, 1359-1410.
24. West, R.; David, L. D.; Djurovich, P. I.; Stearley, K. L.; Srinivasan, K. S. V.; Yu, H., Phenylmethylpolysilanes: Formable Silane Copolymers with Potential Semiconducting Properties. J. Am. Chem. Soc. 1981, 103, 7352-7354.
25. Birot, M.; Pillot, J.-P.; Dunogues, J., Comprehensive Chemistry of Polycarbosilanes, Polysilazanes, and Polycarbosilazanes as Precursors of Ceramics. Chem. Rev. 1995, 95, 1443-1477.
26. Fang, M.-C.; Watanabe, A.; Matsuda, M., Emission Spectra of Σ-Π-Conjugated Organosilicon Copolymers Consisting of Alternating Dimethylsilylene and Aromatic Units. Macromolecules 1996, 29, 6807-6813.
27. Moreau, C.; Serein-Spirau, F.; Létard, J.-F.; Lapouyade, R.; Jonusauskas, G.; Rullière, C., Third-Order Nonlinear Optical Properties in the Excited State of Well-Defined Thiophene-Dimethylsilyl Co-Oligomers. The Journal of Physical Chemistry B 1998, 102, 1487-1497.
28. Kwak, G.; Masuda, T., Photoisomerization and Emission Properties of Trans‐and Cis‐Poly (Dimethylsilylenephenylenevinylene) Macromolecular rapid communications 2001, 22, 846-849.
29. Luh, T.-Y.; Cheng, Y.-J., Alternating Divinylarene–Silylene Copolymers. Chem. Commun. 2006, 4669-4678.
30. Waluk, J., Conformational Analysis of Molecules in Excited States; John Wiley & Sons, 2000; Vol. 22.
31. Abramavicius, D.; Gulbinas, V.; Valkunas, L.; Shiu, Y.-J.; Liang, K. K.; Hayashi, M.; Lin, S. H., Molecular Twisting and Relaxation in the Excited State of Triarylpyrylium Cations. The Journal of Physical Chemistry A 2002, 106, 8864-8869.
32. Mondal, J. A.; Ghosh, H. N.; Ghanty, T. K.; Mukherjee, T.; Palit, D. K., Twisting Dynamics in the Excited Singlet State of Michler's Ketone. The Journal of Physical Chemistry A 2006, 110, 3432-3446.
33. Sluch, M. I.; Godt, A.; Bunz, U. H.; Berg, M. A., Excited-State Dynamics of Oligo (P-Phenyleneethynylene): Quadratic Coupling and Torsional Motions. Journal of the American Chemical Society 2001, 123, 6447-6448.
34. Cailleau, H.; Baudour, J.-L.; Meinnel, J.; Dworkin, A.; Moussa, F.; Zeyen, C. M. E., Double-Well Potentials and Structural Phase Transitions in Polyphenyls. Faraday Discussions of the Chemical Society 1980, 69, 7-18.
35. Troisi, A.; Ratner, M. A.; Nitzan, A., Vibronic Effects in Off-Resonant Molecular Wire Conduction. The Journal of chemical physics 2003, 118, 6072-6082.
36. Weiss, E. A.; Tauber, M. J.; Kelley, R. F.; Ahrens, M. J.; Ratner, M. A.; Wasielewski, M. R., Conformationally Gated Switching between Superexchange and Hopping within Oligo-P-Phenylene-Based Molecular Wires. Journal of the American Chemical Society 2005, 127, 11842-11850.
37. Iwata, K.; Hamaguchi, H.-o., Microscopic Mechanism of Solute−Solvent Energy Dissipation Probed by Picosecond Time-Resolved Raman Spectroscopy. The Journal of Physical Chemistry A 1997, 101, 632-637.
38. Lewis, G. N.; Magel, T. T.; Lipkin, D., The Absorption and Re-Emission of Light by Cis- and Trans-Stilbenes and the Efficiency of Their Photochemical Isomerization. Journal of the American Chemical Society 1940, 62, 2973-2980.
39. Saltiel, J.; Megarity, E. D.; Kneipp, K. G., The Mechanism of Direct Cis-Trans Photoisomerization of the Stilbenes. Journal of the American Chemical Society 1966, 88, 2336-2338.
40. Saltiel, J., Perdeuteriostilbene. The Role of Phantom States in the Cis-Trans Photoisomerization of Stilbenes. Journal of the American Chemical Society 1967, 89, 1036-1037.
41. Courtney, S. H.; Kim, S. K.; Canonica, S.; Fleming, G. R., Rotational Diffusion of Stilbene in Alkane and Alcohol Solutions. Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics 1986, 82, 2065-2072.
42. Peters, K. S.; Freilich, S. C.; Lee, J., Picosecond Dynamics of Trans-Stilbene Photodimerization. The Journal of Physical Chemistry 1993, 97, 5482-5485.
43. Abrash, S.; Repinec, S.; Hochstrasser, R., The Viscosity Dependence and Reaction Coordinate for Isomerization of Cis‐Stilbene. The Journal of Chemical Physics 1990, 93, 1041-1053.
44. Leonard, J. D.; Gustafson, T. L., Solvent−Solute Interactions Probed by Picosecond Transient Raman Spectroscopy:  Vibrational Relaxation and Conformational Dynamics in S1 Trans-4,4‘-Diphenylstilbene. The Journal of Physical Chemistry A 2001, 105, 1724-1730.
45. Pienta, N.; Fox, M.; Chanon, M., Photoinduced Electron Transfer. Part C, Elsevier, Amsterdam 1988, 445.
46. Wasielewski, M. R., Photoinduced Electron Transfer in Supramolecular Systems for Artificial Photosynthesis. Chem. Rev. 1992, 92, 435-461.
47. Berlman, I., Handbook of Florescence Spectra of Aromatic Molecules; Elsevier, 2012.
48. Kohler, G.; Getoff, N., Excitation Energy Effects on the Fluorescence Quantum Yield in Solution. Deactivation Pathways for Aromatic Amines. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases 1980, 76, 1576-1584.
49. Yu, Z.; Li, J.; O'Connor, D. B.; Wang; Barbara, P. F., Large Resonant Stokes Shift in Cds Nanocrystals. J. Phys. Chem. B 2003, 107, 5670-5674.
50. Köhler, G., Solvent Effects on the Fluorescence Properties of Anilines. Journal of Photochemistry 1987, 38, 217-238.
51. Lewis, F. D.; Hougland, J. L.; Markarian, S. A., Formation and Anomalous Behavior of Aminonaphthalene−Cinnamonitrile Exciplexes. The Journal of Physical Chemistry A 2000, 104, 3261-3268.
52. Oosterbaan, W. D.; Koeberg, M.; Piris, J.; Havenith, R. W. A.; van Walree, C. A.; Wegewijs, B. R.; Jenneskens, L. W.; Verhoeven, J. W., N,N-Dialkylanilines:  The S1 State Absorption Spectrum and Efficient Intramolecular Triplet−Triplet Energy Transfer to an Olefinic Bond. The Journal of Physical Chemistry A 2001, 105, 5984-5989.
53. Perichet, G.; Chapelon, R.; Pouyet, B., Emission and Intersystem Crossing Quantum Yields of Aniline Solutions: Photostationary State Diagram. Journal of Photochemistry 1980, 13, 67-74.
54. Mataga, N.; Kaifu, Y.; Koizumi, M., Solvent Effects Upon Fluorescence Spectra and the Dipolemoments of Excited Molecules. Bulletin of The Chemical Society of Japan 1956, 29, 465-470.
55. Williams, R. M., Fullerenes as Electron Accepting Components in Supramolecular and Covalently Linked Electron Transfer Systems, 1996.
56. Ricks, A. B.; Solomon, G. C.; Colvin, M. T.; Scott, A. M.; Chen, K.; Ratner, M. A.; Wasielewski, M. R., Controlling Electron Transfer in Donor−Bridge−Acceptor Molecules Using Cross-Conjugated Bridges. Journal of the American Chemical Society 2010, 132, 15427-15434.
57. Bialkowski, S., Photothermal Spectroscopy Methods for Chemical Analysis; John Wiley & Sons, 1996; Vol. 134.
58. Reichardt, C., Solvatochromic Dyes as Solvent Polarity Indicators. Chemical Reviews 1994, 94, 2319-2358.
59. Lippert, E., Spektroskopische Bestimmung Des Dipolmomentes Aromatischer Verbindungen Im Ersten Angeregten Singulettzustand. Zeitschrift für Elektrochemie, Berichte der Bunsengesellschaft für physikalische Chemie 1957, 61, 962-975.
60. Dlott, D. D., Vibrational Energy Redistribution in Polyatomic Liquids: 3d Infrared–Raman Spectroscopy. Chemical Physics 2001, 266, 149-166.
61. Deng, Y.; Stratt, R. M., Vibrational Energy Relaxation of Polyatomic Molecules in Liquids: The Solvent’s Perspective. The Journal of Chemical Physics 2002, 117, 1735-1749.
62. Abrash, S.; Repinec, S.; Hochstrasser, R. M., The Viscosity Dependence and Reaction Coordinate for Isomerization of Cis‐Stilbene. The Journal of Chemical Physics 1990, 93, 1041-1053.
63. Rice, J. K.; Baronavski, A., Ultrafast Studies of Solvent Effects in the Isomerization of Cis-Stilbene. The Journal of Physical Chemistry 1992, 96, 3359-3366.
64. Liao, W.-C.; Chen, W.-H.; Chen, C.-H.; Lim, T.-S.; Luh, T.-Y., Photoinduced Electron Transfer as a Probe for the Folding Behavior of Dimethylsilylene-Spaced Alternating Donor–Acceptor Oligomers and Polymers. Macromolecules 2013, 46, 1305-1311.