淡江大學機構典藏:Item 987654321/32720
English  |  正體中文  |  简体中文  |  全文筆數/總筆數 : 64191/96979 (66%)
造訪人次 : 8221271      線上人數 : 7172
RC Version 7.0 © Powered By DSPACE, MIT. Enhanced by NTU Library & TKU Library IR team.
搜尋範圍 查詢小技巧：
  • 您可在西文檢索詞彙前後加上"雙引號"，以獲取較精準的檢索結果
  • 若欲以作者姓名搜尋，建議至進階搜尋限定作者欄位，可獲得較完整資料
    •  進階搜尋


    請使用永久網址來引用或連結此文件: https://tkuir.lib.tku.edu.tw/dspace/handle/987654321/32720


    題名: 雙苯咪唑取代聯吡啶錯合物之合成與性質
    其他題名: Syntheses and characterizations of ru complexes with 4,4'-dibenzimidazole-2,2'-bipyridine
    作者: 黃建益;Huang, Chien-yi
    貢獻者: 淡江大學化學學系碩士班
    王文竹;Wang, Wen-jwu
    關鍵詞: 釕;苯咪唑;聯吡啶;Ruthenium;benzimidazole;bipyridine
    日期: 2005
    上傳時間: 2010-01-11 02:37:15 (UTC+8)
    摘要: 由起始物4甲基吡啶(4-methyl,2-pyridine)成功合出雙苯咪唑取代聯吡啶(4,4''-dibenzimidazole-2,2''-bipyridine)，並以氫核磁光譜加以確定。並成功以雙苯咪唑取代聯吡啶與釕金屬形行成二價釕金屬錯合物[Ru(DBBP)(bpy)2](PF6)2。
    在吸收光譜中，二價釕金屬聯吡啶錯合物的MLCT吸收在480nm，另有一組從釕金屬到苯咪唑的MLCT再365nm；在冷光光譜中可用三個激發光源λex = 330nm、λex = 360nm和λex = 470nm，得到二個發光分別為 λem = 410nm和λem = 640nm。
    藉由鹼滴定可得到兩個pKa，pKa1 = 7.7 和pKa2 = 12.4是聯吡啶的兩個苯咪唑amine上的氫原子脫離的結果；在冷光光譜中pH小於10.37，兩組放光強度 (λem = 410nm和λem = 640nm)逐漸增強，pH>10.37兩組放光強度逐漸減弱；在激發態可捯到兩組pKa*，分別為pKa* = 6.3和pKa* = 12.6；並且在酸鹼滴定，放光具有再現性。在氧化滴定的電子吸收光譜中，釕金屬從二價氧化成三價，365nm和480nm位置的MLCT均消失；在冷光光譜中的二組放光也消失。
    另外在離子溶液的滴定中，冷光光譜λem = 410nm放光強度逐漸減弱，λem = 640nm放光強度逐漸增加，並可在λem = 410nm的放光強度得知苯咪唑取代聯吡啶釕金屬錯合物對離子溶液的靈敏度為Zn(ClO4)2、Hg(CH3COO)2>Cd(CH3COO)2、Eu(ClO4)3。在甲醇溶液中，汞離子與錯合物之間並不會有作用力的存在。
    4,4''-dibenzimidazole-2,2''-bipyridine (DBBP) was synthesized from 4-methyl- 2-pyridine and had been identify by H1-NMR. [Ru(DBBP)(bpy)2](PF6)2 was also obtained by reflux of 4,4''-dibenzimidazole-2,2''-bipyridine with [RuCl2(bpy)2]. Electronic absorption spectra and luminescence spectra were measured for [Ru(DBBP)(bpy)2](PF6)2 complex. MLCT bands of [Ru(DBBP)(bpy)2](PF6)2 at 480nm and 365nm were observed. The emission spectrum of title complex upon excited at λex = 330、360、470nm. Ru(DBBP)(bpy)2](PF6)2 exhibits emission at 410nm and 640nm. From pH titration experiment of electronic absorption and luminescence spectra of DBBP two pKa value of pKa1 11.36 and pKa2 12.45 for ground state. [Ru(DBBP)(bpy)2](PF6)2 has two pKa values at 7.72 and 12.48 was come from and pK*a1 = 6.3 and pK*a2 = 12.6 for excited state deprotonation on imidazole group. In oxidative titration of Ru complex the electronic spectrum showed MLCT bands at 365nm and 480nm was disappeared which was attributed as oxidization of RuII to RuIII. This phenomenon was also found in luminescent titration spectrum. Finally, [Ru(DBBP)(bpy)2](PF6)2 had ability to sensing Zn(ClO4)2、Hg(CH3COO)2、Cd(CH3COO)2 and Eu(ClO4)3, the same concentration but different kind of cation can effect the intensity of emission band at 410nm, which can provided an examination tool for sensing heavy metals in solvent. In methanol the complex has no interaction with mercury.
    顯示於類別:[化學學系暨研究所] 學位論文

    文件中的檔案:

    檔案 大小格式瀏覽次數
    0KbUnknown319檢視/開啟

    在機構典藏中所有的資料項目都受到原著作權保護.

    TAIR相關文章

    DSpace Software Copyright © 2002-2004  MIT &  Hewlett-Packard  /   Enhanced by   NTU Library & TKU Library IR teams. Copyright ©   - 回饋