具Meso-五元環取代基紫質的光譜與電化學研究

Spectral and Electrochemical Studies of Phorphyrins with Meso-substituted Five-membered Heterocyclic Rings

張晏儒(Yan-Ru Chang)

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(2014年)

https://doi.org/10.6837/NCNU.2014.00054

摘要

本論文研究一系列含氮、氧、硫五元環取代基之紫質化合物，首先，我們使用TBAP做為電解質進行循環伏安法實驗，由於電解質TBAP有較強配位性質，而使其無法有效穩定氧化態下的紫質陽離子。後續我們進一步使用有較弱配位性質的電解質TBAPF6，實驗結果發現，在含有TBAPF6的CH2Cl2溶液中，可測得可逆的氧化電位，其中H2T(2，-furyl)P與H2T(2，-pyrrolyl)P的氧化電位為單次轉移兩個電子的氧化波。而後，我們再以WCA (weak coordination anion)的電解質NaBArF24，其可觀察到個別單電子轉移的兩個氧化波。在X-ray晶體結構分析中，化合物H2T(2’-furyl)P與H2T(5’-thiazolyl)P，?位的氫原子會與側枝五元環上的氧、硫原子，形成分子內氫鍵作用力，且與紫質環平面有較小的dihedral angle。

關鍵字

紫質 ； 循環伏安法 ； 氫鍵 ； 光譜電化學

並列摘要

This thesis studies a series of nitrogen-, oxygen-, and sulfur-substituted five-membered ring compound group of porphyrin. First of all, we used TBAP, a strong coordinated electrolyte, in cyclic voltammetry experiments. However, TBAP cannot effectively stabilize the oxidation state of porphyrin cation due to its properties. Accordingly, we choose electrolyte TBAPF6 with much weaker coordinated properties. Experimental results shows that, the reversible oxidation potential in CH2Cl2 which containing TBAPF6 can be measured. Furthermore, H2T (2’-furyl)P and H2T (2’-pyrrolyl)P oxidation potential is the oxidation waves of one single transfer for two electrons. Then, we had replaced TBAPF6 by WCA (weak coordination anion) electrolyte NaBArF24. After that, it can be observed two oxidation wave generated in one individual single-electron transfer. For the compound, H2T (2’-furyl)P and H2T (5’-thiazolyl)P, we found that in the X-ray crystal structure analysis, the hydrogen with ? position, together with the atom of oxygen or sulfur on five-membered ring respectively, it can finally formed the intermolecular hydrogen bonds. Hence, because of these bonds, the dihedral angle between porphyrin ring and substituted group plane becomes much smaller, which means, it has an excellent ?-conjugated system.

並列關鍵字

porphyrins ； cyclic voltammetry ； spectroelectrochemically ； hydrogen bonding

參考文獻

1. Kadish, K. M.; Smith, K. M.; Guilard, R., In The Porphyrin Handbook., 2000; Vol. 1.

2. Kadish, K. M.; Smith, K. M.; Guilard, R., In The Porphyrin Handbook., 2000; Vol. 7.

3. Kadish, K. M.; Smith, K. M.; Guilard, R., In The Porphyrin Handbook., 2003; Vol. 11.

4. Chou, J.-H.; Nalwa, H. S.; Kosal, M. E.; Rakow, N. A.; Suslick, K. S., The Porphyrin Handbook. 2000, 6, 43-132.

5. Bessho, T.; Zakeeruddin, S. M.; Yeh, C.-Y.; Diau, E. W.-G.; Gratzel, M., Angew. Chem. Int. Ed. 2010, 49, 6646-6649.