甲基吡啶乙炔紫質之電化學，電聚合及其反應機構

Electrochemistry, Electro-Polymerization and the Mechanism of N-Methyl-Pyridylethynyl Porphyrins

黃淞洲(Sung-Chou Huang)

指導教授 ： 林敬堯

國立暨南國際大學/科技學院/應用化學系/碩士(2008年)

摘要

過去幾年，本實驗室已經成功地在 free-base 5, 15-biphenylporphrine 的 10 和 20 (meso) 位置上接上一個或兩個 N-methyl-2、3 或 4-pyridylethynyl 取代基，合成出一系列新穎的寡電子紫質。本論文主要針對於他們的電化學性質及光譜電化學性質做更進一步探討。
由於 N-methyl-pyridylethynyl 是一個很強的拉電子取代基，故可以使紫質之紫外光-可見光光譜明顯地紅位移並且使紫質之還原電位大幅度地往正電位位移。在實驗中，我們發現在某些以 N-methyl-2、4-pyridylethynyl 為取代基的雙取代紫質中發現其還原之電致色變 (electrochromism) 可以在近紅外光區 (near-IR region) 具有強烈的吸收。
另一方面，在這些寡電子紫質的電化學實驗中，可觀測到電化學圖譜之電流密度有顯著的增加，由此可知有大量的紫質停留在電極表面。在紫外線－可見光光譜及傅立葉近紅外光光譜之實驗中，可以得知這些在電極表面之寡電子紫質化合物為電化學聚合方式聚合在電極表面而非以電沉積之方式聚合在電極表面。據我們了解，這是文獻上第一次出現以 N-methyl-pyridinium 官能基進行電聚合反應的例子。

關鍵字

電化學 ； 光譜電化學 ； 電致色變 ； 紫外線-可見光光譜 ； 傅立葉近紅外光光譜 ； 電聚合

並列摘要

We have previously studied a series of novel electron-deficient free-base porphyrins by attaching one or two N-methyl-2, 3, or 4-pyridylethynyl group to the 10 and / or 20-meso positions of free-base 5, 15-biphenyl porphine. In this thesis, we study by their electrochemical and spectro-electrochemical further.
Because N-methyl-pyridylethynes are powerful electron-withdrawing substituents, resulting in significant red-shifts of the porphyrin UV-Visible absorptions and large positive-shifts in porphyrin reduction potentials. We found porphyrins bearing N-methyl-2, 4-pyridylethynyl substituting group have strong electrochromism absorption in the near-IR region upon reduction reactions.
On the other hand, the current density of electro-chemical diagram have remarkably increased in electro-chemical experiment of these electron-deficient porphyrins. It suggests that a lot of porphyrins have rest onto surface of the electrode. In the UV-Vis spectra and FT-IR spectra, the electron-deficient porphyrin compounds on the electrode were eleectro-polymerizated onto the electrode rather than electro-deposited onto the electrode. To our knowledge, the thing which N-methyl-pyridinium group undergo electro- polymerization is the first time.

並列關鍵字

electrochemistry ； spectro-electrochemistry ； electrochromism ； UV-Vis ； FT-IR ； electro-polymerization

參考文獻

1.K. M. Kadish and E. V. Caemelbecke, J Solid State Electrochem., 2003, 7, 254-258.

2.(a) V. Balzani, P. Ceroni, A. Juris, M. Venturi, S. Campagna, F. Puntoriero and S. Serroni, Coord. Chem. Rev., 2001, 219-221, 545-572. (b) H. E. Toma and K. Araki, Coord. Chem. Rev., 2000, 196, 307-329. (c) H. Eichhorn, J. Porphyrins Phthalocyanines, 2000, 4, 88-102. (d) T. B. Amor and G. Jori, Insect Biochem. Mol. Biol., 2000, 30, 915-925. (e) P. Lugo-Ponce and D. R. McMillin, Coord. Chem. Rev., 2000, 208, 169-191.

3.(a) T. D. Mody, J. L. Sessler, and L. Jonathan, Perspect. Superamol. Chem., 1999, 4, 245-294. (b) R. Purrello, S. Gurrieri, and R. Lauceri, Coord. Chem. Rev., 1999, 190-192, 683-706. (c) L. S. Latos-Grazynski, K. Rachlewicz, and J. Wojaczynski, Coord. Chem. Rev., 1999, 190-192, 109-125. (d) S. Belanger, M. H. Keefe, J. L. Welch, and J. T. Hupp, Coord. Chem. Rev., 1999, 190-192, 29-45.

4.(a) J. L. Sessler, N. A. Tvermoes, J. Davis, P. Anzenbacher Jr., K. Jursikov, W. Sato, D. Seidel, V. Lynch, C. B. Black, A. Try, B. Andrioletti, G. Hemmi, T. D. Mody, D. J. Magda, and V. Kral, Pure Appl. Chem., 1999, 71, 2009-2018. (b) B. Jiang, S. W. Yang, S. L. Bailey, L. G. Hermans, R. A. Niver, M. A. Bolcar, and W. E. Jones Jr., Coord. Chem. Rev., 1998, 171, 365-386. (c) G. knor, Coord. Chem. Rev., 1998, 171, 61-70.

5.(a) P. C. Ford, J. Bourassa, B. Lee, I. Lorkovic, K. Miranda, and L. Laverman, Coord. Chem. Rev., 1998, 171, 185-202. (b) F. Bedioui, Coord. Chem. Rev., 1995, 144, 39-68. (c) Z. Bao, and L. Yu, Trends Polym. Sci., 1995, 3, 159-164.