研究生: |
曾俊峰 Chun Feng Tseng |
---|---|
論文名稱: |
聯吡啶釕錯合物的光物理性質研究 Photopysical Properties Of Ruthenium(Ⅱ) Polypyridyl Complexes |
指導教授: |
張ㄧ知
Chang, I-Jy |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2004 |
畢業學年度: | 92 |
語文別: | 中文 |
論文頁數: | 105 |
中文關鍵詞: | 釕錯合物 |
英文關鍵詞: | Ruthenium(Ⅱ) Polypyridyl Complexes |
論文種類: | 學術論文 |
相關次數: | 點閱:232 下載:0 |
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本論文中合成出不同官能基的聯吡啶和含酸基的聯吡啶與釕金屬結合為錯合物,主要在研究此類具有酸基錯合物的酸解離平衡常數。
並分析其基態與激發態的電子密度分佈,以及影響電子分佈的因素。
由錯合物在基態時 UV-vis 吸收光譜上 MLCT band 的吸收度對pH滴定曲線的變化,可求得基態的解離平衡常數,此即pKa;而以錯合物 Emission 光譜的強度對pH滴定曲線的變化,可得到其反折點,pKa*’,再測得錯合物在質子化與去質子化兩者的生命期加以校正,即可得到激發態的解離平衡常數,pKa*。錯合物的酸解離平衡常數在激發態與基態的差值 ΔpKa (pKa*-pKa) 越大代表錯合物在激發態時是比基態更具鹼性,也就是說,錯合物在激發態有較多的電子密度分布在含有酸基的聯吡啶上。越小代表錯合物在激發態有較少的電子密度分布在含有酸基的聯吡啶上。
實驗結果ΔpKa為[Ru(tmbpy)2(tmcbpy)] 2+, 1.77; [Ru(dmbpy)2(tmcbpy)] 2+, 0.79; [Ru(phen)2(tmcbpy)] 2+, 0.64; [Ru(dabpy)2(tmcbpy)] 2+, 0.62; [Ru(dpphen)2(tmcbpy)] 2+, -0.84。結果以[Ru(tmbpy)2(tmcbpy)] 2+的電子由釕金屬轉移到含酸基聯吡啶的效益最好。以[Ru(dpphen)2(tmcbpy)] 2+的電子由釕金屬轉移到含酸基聯吡啶的效益最差。
Ruthenium(II) tris(dipyridyl) complexes have been synthesized. By varying the electron-withdrawing and electron-donating abilities on each bipyridyl ligand, we have made six complexes that contain 4-carboxyl-3,3’4,’-trimethy,2’-bipyridine. These complexes are [Ru(tmbpy)2(tmcbpy)] 2+, [Ru(dmbpy)2(tmcbpy)] 2+, [Ru(phen)2(tmcbpy)] 2+, [Ru(dabpy)2(tmcbpy)] 2+, [Ru(dpphen)2(tmcbpy)] 2+, [Ru(phenNO2)2(tmcbpy)] 2+.
The ground-state acid dissociation constant (pKa) were obtained from the titration curve of absorption changes. The excited-state acid dissociation constant (pKa*) were obtained from the luminescence titration curve and lifetime calibration. A positive ΔpKa (ΔpKa = pKa* - pKa) indicates the electron density of the bipyridine that contains the carboxyl group has a higher electron density in the excited state than the ground state. A negative ΔpKa indicates the carboxyl containing bipyridine has less electron density in the excited state. From the acid dissociation constant studies, the electron density in the excited state of Ruthenium(II) tris(dipyridyl) complexes can be qualitatively mapped.
The experiment data forΔpKa are 1.77, 0.79, 0.64, 0.62, and -0.84 for [Ru(tmbpy)2(tmcbpy)] 2+, [Ru(dmbpy)2(tmcbpy)] 2+,[Ru(phen)2(tmcbpy)] 2+, [Ru(dabpy)2(tmcbpy)] 2+, [Ru(dpphen)2(tmcbpy)] 2+,respectively. The results indicate that if it is desired to have higher electron density in the excited state on the carboxyl containing bipyridine, [Ru(tmbpy)2(tmcbpy)] 2+ is the best choise. On the other hand, if carboxyl containing bipyridine is designated to have less electron density in the excited state , [Ru(dpphen)2(tmcbpy)] 2+ is the best candidate.
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