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研究生:柯金蓮
研究生(外文):chin-lien Ko
論文名稱:含2-苯基酮啶之混配基型銠(III)錯合物之放光特性及電化學研究
論文名稱(外文):Electrochemistry and Emission spectroscopy of 2-benzoylpyridine Rh(III) complex
指導教授:黃文亮黃文亮引用關係
指導教授(外文):Wen-Liang Huang
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:1999
畢業學年度:87
語文別:中文
論文頁數:75
中文關鍵詞:2-苯甲基酮啶電化學放光光譜
外文關鍵詞:2-benzoylpyridineelectrochemistryemission spectroscopy
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中文摘要
本研究合成混配基型錯合物 cis α-Rh(phen)(bzpy)Cl2,其中phen = 1, 10-phenanthroline,bzpy = ortho-C-deprotonated form of 2-benzoylpyridine,並以元素分析、質譜、IR、NMR圖譜鑑定其結構,判定其為 cis α 型之異構物。
在紫外-可見光吸收光譜,錯合物於 43.48 ~ 30.77 kK 之間有很強的吸收峰 ( ε > 104 ),在此範圍吸收推測主要是配位子 Hbzpy 與 phen 之 ππ* 過渡。在 28.9 kK 處發現有一吸收峰,ε = 7.16 ×103,推測是配位到銠金屬 bzpy 之羰基吸收,屬於 n → π* 過渡。在 22 ~ 25 kK 含有肩帶微弱吸收亦皆延伸到可見光區,此區域吸收有可能是電荷轉移或 dd* 躍遷,推測可能是dd* 躍遷吸收很微弱而被埋入裡面見不到其吸收肩帶微弱的吸收。激發極化光譜在 34.01 及 25.25 kK有轉折處,可知此處具有兩種或兩種以上之吸收型態。
在放光性質偵測上,錯合物在低溫 77 K 時,乙醇 / 甲醇 ( 體積比 1 / 9 ) 中性溶液中,在 17.24 ~ 12.66 kK 的能量範圍內,可偵測到寬廣、對稱且不具結構性之放光帶,其最大放光位置在 14.97 kK,半生期約 60 μs 左右,推斷屬於 dd* 型態放光。在放光極化光譜,此放光區間呈現一平坦、斜率趨近零之曲線,表示為單一型態的放光。
電化學方面,從 CV、NPV、CPE 之實驗結果,推斷錯合物第一還原峰含二個單電子轉移隨後各伴同氯離子脫離的化學反應,即 ECEC 機構。第三還原峰由電流比值、可逆性以及加入 phenol 後之現象,推論是發生在 bzpy 羰基 π* 軌域上的可逆單電子轉移過程。
綜合放光特性及電化學行為,此混配基錯合物屬於 3dd* 放光,且其最低激發態之能階為金屬 d* 為主的軌域。

英文摘要
In this research, the complex Rh(phen)(bzpy)Cl2 ( phen is 1,10-phenarthroline, bzpy is ortho-C-deprotonated form of 2-benzoylpyridine ) has been synthesized and characterized by MS, IR and NMR spectra. The structure of the complex is assigned as cis a form isomer. In IR spectrum, the carbonyl absorption of bzpy in this complex, about 1666 cm-1, indicates N-C- bonding form to metal Rh(III).
The pp* transitions in ligands of the complex exhibit strong absorption in the UV region; the band of 22~25 kK is assigned that dd* absorption of center metal is covered with the charge transfer signal. It's difficult to distinguish clearly between the two absorptions under the long tail. The magnitude of the polarization in the excitation polarization spectrum obtained from the complex indicates that emission chromophore behaves as a linear oscillator corresponding the symmetry lower than C2v of the complex.
No luminescence is found at room temperature, but at 77 K, the complex in EtOH/MeOH (1/9 volume) neutral solution exhibits a broad, symmetric, structureless red emission and the luminescence lifetime is about 60 ms. The maximum emission intensity is about 14.97 kK. The luminescence is assigned as dd* phosphorescence. The emission polarization spectrum of this complex in emission region is a linear curve whose slope is closed to zero,indicates a single emission.
The cyclic voltammograms of the complex shows two reduction waves between 0 ~ -1.8 V vs. SCE in 0.1 TEAP/Me2SO. The first peak is constituted by two electronic reduction steps followed by fast elemination of a chloride. In the addition of phenol, the second one is suggested to be a reductive process that one electron transfer to p* orbital at carbonyl of bzpy.

總目錄
頁次
表目錄……………………………………………………………i
圖目錄…………………………………………………………… iii
第一章 緒論………………………………………………… 1
1-1 光物理…………………………………………….. 1
1-2 電化學…………………………………………….. 5
第二章 實驗部份……………………………………………….. 9
2-1 試劑………………………………………………… 92-2 錯合物的製備………………………………………11
2-2-1 配位子的純化……………………………………11
2-2-2 K[Rh(phen)Cl4] 的合成………………………….11
2-2-3 cis a-Rh(phen)(bzpy)Cl2 的合成…………………11
2-2-4 溶劑Dimethyl Sulfoxide的純化方法……………12
2-3 物理性質測定及儀器裝置…………………………13
2-4 電化學原理…………………………………………19
2-4-1 Cyclic Voltammetry……………………………….19
2-4-2 Normal Pulse Voltammetry………………………..20
2-4-3 Controlled-Potential Electrolysis………………….20
第三章 結果與討論………………………………………………22
3-1 錯合物cis a-Rh(phen)(bzpy)Cl2的合成…………… 22
3-2 鑑定…………………………………………………25
3-2-1 錯合物色澤、熔點及元素析……………………25
3-2-2 質譜………………………………………………26
3-2-3 紅外線光譜………………………………………29
3-2-4 核磁共振光譜……………………………………39
3-3 光物理………………………………………………44
3-3-1 紫外?可見光吸收光譜及激發極化光譜………44
3-3-2 放光及放光極化光譜……………………………50
3-4 電化學性質…………………………………………58
3-4-1 Hbzpy 之電化學性質………………………………58
3-4-2 cis a-Rh(phen)(bzpy)Cl2 之電化學性質…………61
第四章 結論………………………………………………………70
參考文獻……………………………………………………………72

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