臺灣博碩士論文加值系統

本論文分為二個部分，第一部分研究釕紫質Ru(CO)TMP與不同的軸配位基（imidazole，N-methylimidazole，OH－）形成錯合物時的電化學及光譜性質。由FT-IR光譜圖中得知，Ru(CO)TMP與軸配位基形成錯合物時，會使得νco值減小，其νco值順序為：
Ru(CO)TMP＞(Im)Ru(CO)TMP≒(N-MeIm)Ru(CO)TMP＞[(OH)Ru(CO)TMP]－
電化學的實驗中可以得知，當Ru(CO)TMP與imidazoles形成錯合物時，會使得釕紫質的第一個氧化電位往負方向移動，表示更容易氧化，而第二個氧化電位則往正方向移動，表示較難氧化。當Ru(CO)TMP與OH－配位後，則使釕紫質較易氧化，由電位的偏移可以計算形成常數。
第二部分是研究NO2取代基對於紫質環及鋅紫質的電化學性質影響，在TPP system中，發現以NO2取代meso-phenyl group上的氫原子，在氧化部分會直接影響紫質環的氧化還原性質，使其更難氧化，在還原部分nitrophenyl與紫質環的氧化還原電位重疊，使得電化學行為變得較為複雜。

There are two subjects in the thesis. In chapter 1, a spectral and electrochemical study for the carbonylruthenium(II) complexes of meso-tetramesitylporphyrin dianion (TMP) in the presence of nitrogeneous and oxygeneous bases in CH2Cl2 solution were presented. Spectrophotometric titration of RuII(CO)TMP with imidazole (Im), N-methylimidazole (N-MeIm) and tetra-n-butylammonium hydroxide (TBAOH) using as the axial ligands for Ru(CO)TMP was monitored. The Soret band and Q band of the carbonylruthenium(II) porphyrins were red-shift in the presence of Im, N-MeIm and TBAOH. The formation constants( ) were calculated by the Benesi-Hildebrand method. Infrared spectra showed the weakening CO stretching vibration after the axial ligation. The complexation of imidazoles and hydroxide to the oxidized carbonylruthenium porphyrin was achieved by cyclic voltammetry. Spectroelectrochemical method were used to obtain the absorption spectra of the complexed carbonylruthenium porphyrin cation radicals.
In chapter 2, an electrochemical study of the substituent effects on porphyrin free base and zinc porphyrin were presented. The effects of meso-nitrophenyl group substituent on porphyrins cause the anodic shift of the oxidation potential. The cyclic voltammograms porphyrin and nitrophenyl group were overlapped in the reductive scan, therefore the electrochemical behaviors become complicated to resolve.

目 錄
中文摘要………………………………………………………………….i
Abstract…………………………………………………………………..ii
謝誌……………………………………………………………………...iii
目錄……………………………………………………………………...iv
圖表目錄………………………………………………………………...vi
第一章 釕紫質軸配位基效應的光譜及電化學研究
Abbreviation……………………………………………………………...2
金屬紫質結構圖…………………………………………………………3
A.簡介……………………………………………………………………5
B.實驗
( I ) 儀器…………………………………………………………...17
( II ) 藥品…………………………………………………………...19
( III ) 合成…………………………………………………………...20
( IV ) 形成常數的測定……………………………………………...27
C.結果與討論
( I ) 紫外光-可見光吸收光譜的研究…………………………….36
( II ) 傅立葉轉換紅外線光譜的研究………………………….…..38
( III ) 電化學性質的研究
i. RuII（CO）TMP…………………………………………39
ii. RuII（CO）TMP in the presence of imidazoles…………40
iii. RuII（CO）TMP in the presence of OH－………………..44
第二章 鋅紫質取代基效應的光譜及電化學研究
Abbreviation……………………………………………………..……...67
金屬紫質結構圖……………………………………………………..…68
D.簡介……………………………………………………………..……69
E.實驗
( I ) 藥品…………………………………………………………..72
( II ) 合成…………………………………………………………..72
F.結果與討論
電化學性質的研究
i. Free base porphyrin氧化部分的電化學研究………………….75
ii. Zinc porphyrin氧化部分的電化學研究……………………….77
iii. Free base porphyrin還原部分的電化學研究…………………78
iv. Zinc porphyrin還原部分的電化學研究………………………81
結論……………………………………………………………………..94
Appendix 1. ………………….……………………………………….96
參考文獻………………………………………………………………..97

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