| 研究生: |
羅偉中 Wei-Zhong Luo |
|---|---|
| 論文名稱: |
偶氮金屬配位化合物合成鑑定與性質探討 Synthesis and Property of Metal Azo Compounds |
| 指導教授: | 劉陵崗,賴重光 |
| 口試委員: | |
| 學位類別: |
碩士 Master |
| 系所名稱: |
理學院 - 化學學系 Department of Chemistry |
| 論文出版年: | 2016 |
| 畢業學年度: | 104 |
| 語文別: | 中文 |
| 論文頁數: | 152 |
| 中文關鍵詞: | 偶氮 、微流體 |
| 相關次數: | 點閱:8 下載:0 |
| 分享至: |
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閃化學(flash chemistry)的有機合成,是指不穩定的中間物質,僅能
短時間存活,反應過程只需要一秒或更短的時間,無法使用常規的批
次反應達成。但在微流體反應系統中,比表面積大幅增加,熱傳及質
傳快速,能使反應快速的進行,故閃化學反應在微流體反應器中卻非
常適合。簡單調整實驗參數,便可使有機合成反應在微流體反應器中
得到理想的效果。本論文中利用微流體反應之系統合成4個偶氮化合
物並使之金屬化。
4個偶氮化合物的UV-Vis光譜中,呈現出明顯的π→π*峯訊和n→π*
峯訊。而偶氮化合物金屬化後,UV-Vis光譜中發現π→π*躍遷兩個峯
訊僅有輕微的位移和峯訊強度的變化,其他大致相同,但n→π*峯訊
因為金屬與配體鍵結的關係,產生紅移現象。
鉻(Cr3+)金屬偶氮配體化合物的ESI質譜分析,發現其中心Cr3+離子
在ESI過程中會還原成Cr2+。Cr2+水溶液離子交換速率比Na+水溶液離
子交換速率大約快2倍,游離化過程中產生陽離子交換,在質譜圖中
看到M及M-25的峯訊。
A flash reaction in organic chemistry is a reaction, in which an
unstable intermediate is with very short life and the reaction is completed
in one second or less. Consequently it is very difficult to conduct such a
reaction in common batch type setups to successfully obtain the end
product. On the other hand, a microfluidic reactor system exhibits very
large specific area in setup and has very great mass transfer and heat
transfer property. A microfluidic reactor allows fast heating or cooling,
and thus is suitable for a flash reaction and in general favoring rapid
reactions. One could achieve very good results to run organic reactions in
microfluidic reactors by simple adjustment of experimental parameters.
In this thesis, the preparation of 4 azobenzene derivatives was
successfully demonstrated using the microfluidic reactor system. The
azobenzenes were used as chelates to coordinate to chromium and iron to
form metallic azo-dyes.
The 4 azobenzenes and 8 metallic azo-dyes were studied with the
UV-Vis spectroscopic method. As ligands, the azobenzenes show clear
π−π* and n−π* absorption bands, while the metallic azo-dyes show slight
shift/change on π−π* absorption bands yet pronounced red-shifts on n−π*
absorption bands.
The 4 azobenzenes and 8 metallic azo-dyes were all analyzed with
mass spectroscopic method using the electrospray ionization source. The
Cr+3 azo-dyes were interesting in that the central Cr+3 metal ions along the ESI process could be reduced to Cr+2 metal ions that led to exchange of
Cr+2 metal ions with the counter Na+ metal ions. The negative mass
spectra of Cr+3 azo-dyes revealed very strong peaks at m/e = [M] and
[M-25], where M is the molecular ion, agreeing to the facile water
exchange rates for Cr+2 and Na+ but inert water exchange for Cr+3. No
such exchange was observed for the analogous Fe+3 azo-dyes: slow water
exchange being known for both Fe+3 and Fe+2 metal ions.
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