物理化学学报 >> 2001, Vol. 17 >> Issue (08): 728-732.doi: 10.3866/PKU.WHXB20010812

研究论文 上一篇    下一篇

四种钌(Ⅱ)配合物的中心离子电化学行为的比较

李红;巢晖;蒋雄;计亮年   

  1. 中山大学化学与化学工程学院,广州 510275;华南师范大学化学系,广州 510631
  • 收稿日期:2001-01-18 修回日期:2001-04-10 发布日期:2001-08-15
  • 通讯作者: 计亮年 E-mail:cesjln@zsu.edu.cn

Comparative Study of the Electrochemical Behavior of the Central Ions of Four Ruthenium (Ⅱ) Complexes

Li Hong;Chao Hui;Jiang Xiong;Ji Liang-Nian   

  1. School of Chemistry and Chemical Engineering,Zhongshan University,Guangzhou 510275;Department of Chemistry,South China Normal University,Guangzhou 510631
  • Received:2001-01-18 Revised:2001-04-10 Published:2001-08-15
  • Contact: Ji Liang-Nian E-mail:cesjln@zsu.edu.cn

摘要: 应用循环伏安、循环交流伏安和微分电容技术等电化学方法研究了由Ru(Ⅱ)与2,2′-联吡啶(bpy)、1,10-邻菲咯啉(phen)和桥联配体1,4-二[2-咪唑并[4,5-f]邻菲咯啉]苯(DIPB)配位而成的四种配合物[Ru1:Ru(bpy)2DIPB(ClO4) 2、Ru2:(bpy)2Ru(DIPB)Ru(bpy)2(ClO4)4、Ru3:Ru(phen)2DIPB(ClO4)2和Ru4:(phen)2 Ru(DIPB)Ru(phen)2(ClO4)4]在铂电极上的电化学行为及金属间的相互作用.研究结果表明,在高氯酸四丁基铵(TBAP)的乙腈溶液中,单、双核中心离子在循环伏安图上分别呈现1对可逆的1电子和2电子的氧化还原波,单核对应的配位阳离子的扩散系数较双核的大,辅助配体为bpy的配位阳离子的扩散系数较phen的大.应用循环交流伏安法和微分电容技术研究则发现,双核中心离子的氧化还原过程表现为2个连续单电子过程的重叠,金属间的相互作用较弱.

关键词: 钌(Ⅱ)配合物, 铂电极, 中心离子, 电化学行为, 循环伏安法, 交流伏安法

Abstract: The electrochemical behavior of mononuclear and symmetrical binuclear ruthenium(Ⅱ) complexes [Ru1:Ru(bpy)2DIPB(ClO4)2,Ru2:(bpy)2 Ru(DIPB)Ru(bpy)2(ClO4)4,Ru3:Ru(phen)2DIPB(ClO4)2 and Ru4:(phen)2 Ru(DIPB)Ru (phen)2(ClO4)4] containing binuclear ligand 2,2′-bipyridine(bpy),1,10-phenanthroline(phen) and bridging ligand 1,4-di-[2-imidazo[4,5-f][1,10] phenanthroine benzene(DIPB) on a platinum electrode and the intermetallic interaction of binuclear complexes have been investigated using cyclic voltammetry,cyclic ac voltammetry and differential capacitance techniques,etc.In acetonitrile solution with a concentration of 0.1 mol穌m-3 TBAP,the central ions in four complexes all display single 1e and 2e reversible oxidation- reduction waves on the cyclic voltammograms,with apparent diffusion coefficients of the mononuclear complexed cations being larger than that of the binuclear ones.The apparent diffusion coefficients for complexed cations with auxiliary ligands bpy are also found to be larger than that with ligands phen.It appears that the overlapping of two continuous single-electron processes by cyclic ac voltammetry and differential capacitance techniques occurs during the redox processes of the central ions binuclear complexes.The results show that a weak electronic interaction exits between the two central ruthenium ions in binuclear complexes.

Key words: Ruthenium(Ⅱ) complex, Platinum electrode, Central ion, Electrochemial behavior, Cyclic voltammetry, Alternating current voltammetry