English  |  正體中文  |  简体中文  |  Items with full text/Total items : 64191/96979 (66%)
Visitors : 8132265      Online Users : 9853
RC Version 7.0 © Powered By DSPACE, MIT. Enhanced by NTU Library & TKU Library IR team.
Scope Tips:
  • please add "double quotation mark" for query phrases to get precise results
  • please goto advance search for comprehansive author search
  • Adv. Search
    HomeLoginUploadHelpAboutAdminister Goto mobile version
    Please use this identifier to cite or link to this item: https://tkuir.lib.tku.edu.tw/dspace/handle/987654321/32720


    Title: 雙苯咪唑取代聯吡啶錯合物之合成與性質
    Other Titles: Syntheses and characterizations of ru complexes with 4,4'-dibenzimidazole-2,2'-bipyridine
    Authors: 黃建益;Huang, Chien-yi
    Contributors: 淡江大學化學學系碩士班
    王文竹;Wang, Wen-jwu
    Keywords: ;苯咪唑;聯吡啶;Ruthenium;benzimidazole;bipyridine
    Date: 2005
    Issue Date: 2010-01-11 02:37:15 (UTC+8)
    Abstract: 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.
    Appears in Collections:[化學學系暨研究所] 學位論文

    Files in This Item:

    File SizeFormat
    0KbUnknown315View/Open

    All items in 機構典藏 are protected by copyright, with all rights reserved.


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