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Title: | 3-雙苯咪唑取代聯吡啶釕錯合物之合成及性質研究 |
Other Titles: | Synthesis and characterizations of Ru(II) complex with 3, 3-dibenzimidazole-2, 2'-bipyridine |
Authors: | 彭松崑;Peng, Sung-kun |
Contributors: | 淡江大學化學學系碩士班 王文竹;Wang, Wen-jwu |
Keywords: | 釕金屬;苯咪唑;聯吡啶;氟離子偵測;ruthenium;benzimidazole;bipyridine;F sensing |
Date: | 2009 |
Issue Date: | 2010-01-11 02:46:41 (UTC+8) |
Abstract: | 我們合成出在聯吡啶3,3’位置苯咪唑取代之配位子,並將配位子與RuII(bp)2Cl2反應,得到釕錯合物[Ru(3-dbimbp)(bpy)2](PF6)2,利用核磁共振光譜、質譜及X-ray晶體解析來鑑定化合物的結構,利用電子吸收光譜、發射光譜及電化學來探討其物理及化學性質。 [Ru(3-dbimbp)(bpy)2](PF6)2的單晶結構中,釕金屬與聯吡啶的氮原子形成六配位的八面體形狀,苯咪唑未參與配位,配位子以聯吡啶與金屬配位的方式,我們是第一個發現的。配位子3-dbimbp的發射光譜中,有屬於TICT的發光。釕錯合物的紫外光-可見光光譜中,有配位子、聯吡啶的π-π*電子躍遷及MLCT吸收峰。發射光譜中,660 nm有一放射峰,此為來自於MLCT激態的磷光。電化學實驗中,有一組RuII/RuIII氧化還原峰在1.54 V,在還原部份,有四組不可逆的氧化還原峰(-1.06 V、-1.35 V、-1.54 V、-1.78 V),分別來自於配位子及聯吡啶。 在氟離子滴定實驗中,配位子及錯合物在吸收光譜及發射光譜皆有顯著的變化,酸鹼滴定的實驗中,發現[OH-]與氟離子的表現相似,此結果顯示配位子與錯合物是受到了去質子化的影響。在其他陰離子(Cl-, Br-, I-, ClO4-, HSO4-, NO3-)滴定實驗中,並沒有偵測效果,故我們所合成出的配位子及錯合物對於氟離子有選擇性。 A new polypyridyl ruthenium complex, [Ru(3-dbimbp)(bpy)2](PF6)2 , containing two bipyridines and one bipyridine derivative ligand 3-dbimbp (3-dbimbp = 3,3''-dibenzimidazole-2,2''-bipyridine) was synthesized. Mass, NMR, UV-vis and Emission spectrometer are employed to study the structure of this complex. Single crystal x-ray diffraction structure of [Ru(3-dbimbp)(bpy)2](PF6)2 was obtained. Electronic absorption and emission spectra of this complex are measured to investigate the electronic structure of the complex. A strong absorption is assigned as intraligand π-π* transition and the strong absorption is attributed to an MLCT transition. However, emission spectra exhibit photoluminescence, which has been attributed to MLCT triplet emission. The cyclic voltammogram was measured, showing a metal-centered RuII/RuIII oxidation with potentials at 1.54V. The results of absorption and emission spectra revealed that the ligand and complex can be employed as a sensor for fluoride anion. Finally, a proposed deprotonation mechanism for sensing fluoride anion was discussed. |
Appears in Collections: | [化學學系暨研究所] 學位論文
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