具鄰位取代紫質的合成與電化學研究

Synthesis and electrochemical studies of ortho-substituted porphyrins

鍾秀卿(Shew-ching Chung)

指導教授 ： 蘇玉龍

國立暨南國際大學/科技學院/應用化學系/碩士(2009年)

摘要

本研究包含合成meso 位置上以nitrophenyl, aniline, 1,3-diphenylurea, nicotinanilide 取代的紫質，利用電化學和光譜電化學方法，瞭解不同鄰位取代基 和數目對紫質還原電位和其光譜變化的影響。
以循環伏安法及光譜電化學的觀察結果，可推斷aniline(推電子基) 的取代會使紫質環較難還原；nitrophenyl, 1,3-diphenylurea, nicotinanilide (拉電子基) 的取代會使紫質環較易還原。而隨著單取代變便為雙取代紫質時，電位移動的現象
也變的較為明顯。
並進一步以循環伏安法的研究結果，觀察還原H2(o-APurea)2(mesityl)2P 和 H2(o-APnic)2(mesityl)P 時，分子內氫鍵對紫質環節結構的影響。

關鍵字

紫質 ； 循環伏安法 ； 透光薄層電化學法

並列摘要

We have synthesized free-base porphyrins with nitrophenyl, aniline,1,3-diphenylurea, and nicotinanilide on the meso-position successfully. The cyclic voltammetry and spectroelectrochemical studies have also been investigated.
By cyclic voltammetry and spectroelectrochemistry studies, the electron-donatinggroup (aniline) would make the reduction potential of the porphyrin ring negatively.
Oppositely, the electron-withdrawing group (nitrophenyl, 1,3-diphenylurea,nicotinanilide) made the reduction of the porphyrin positively. With the increasing ofthe meso-substituents, the substituent effect was obvious easily.
The effect of internal hydrogen binding on the structure of free-base porphyrins(H2(o-APurea)2(mesityl)2P, H2(o-APnic)2(mesityl)P) also could be observed by Cyclic voltammetry.

並列關鍵字

porphyrin ； Cyclic voltammetry ； optically transparent thin-layer electrode(OTTLE)

參考文獻

1. 陳錦地, Chemistry (The Chinese Chem Soc.,Taipei) . 2000, 58, 447-448.

2. Kalyanasundaram, K. Photochemistry of Polypyridine and Porphyrin

Complexs, Academic Press:London, 1992.

3. (a) Khorasani-Motlagh, M.; Noroozifar, M.; Ghaemi, A.; Safari, N. J. Electroanal. Chem. 2004, 565, 115-120

(b) Hendrickson, D. K.; Kinnaird, M. G.; Suslick, K. S. J. Am. Chem. Soc. 1987, 109, 1244-1245