机构地区: 中山大学化学与化学工程学院
出 处: 《物理化学学报》 2001年第8期728-732,共5页
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[Rul: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。 The electrochemical behavior of mononuclear and symmetrical binuclear ruthenium(Ⅱ) complexes [Rul: 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· dm -3 TBAP, the central ions in four complexes all display single le 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 sin- gle-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.