应用循环伏安、循环交流伏安和微分电容测定等电化学方法研究了由 2 ,2一联吡啶(bpy)和桥联配体 1,4_二 [2_咪唑并 [4 ,5_f]邻菲咯啉 ]苯 (DIPB)或 1,4_二 [2_脱氢咪唑并 [4,5_f]邻菲咯啉 ]苯 (DIPB_2H)所形成的对称双核钌配合物 (Ru2 :(bpy) 2 Ru(DIPB)Ru(bpy) 2 (ClO4 ) 4 和Ru2_2H :(bpy) 2 Ru(DIPB_2H)Ru(bpy) 2 (ClO4 ) 2 )在铂电极上的电化学性质以及金属间的相互作用 .研究结果表明 ,在 0 .1mol/L高氯酸四丁基铵 (TBAP)的乙腈溶液中 ,中心离子在循环伏安图上均呈现 1对可逆的 2电子氧化还原波 ,电位也几乎不变 ,其所对应的配位阳离子的扩散系数分别为 3.50×10 - 6 cm2 /s和 3.94× 10 - 6 cm2 /s.循环交流伏安和微分电容测定研究发现 ,桥联配体去质子化后 ,中心离子间的电子相互作用增强
The electrochemical characteristics and intermetallic interaction of symmetrical binuclear ruthenium(Ⅱ) complexes [Ru2:(bpy) 2Ru(DIPB)Ru(bpy) 2(ClO 4) 4 and Ru2_2H:(bpy) 2Ru(DIPB-2H)Ru(bpy) 2(ClO 4) 2 ]containing dinuclear ligand 2,2_bipyridine(bpy) and bridging ligand 1,4_di[2_imidazo[4,5_f][1,10] phenanthroine]benzene(DIPB) or 1,4_di[2_dehydrogen_imidazo[4,5_f][1,10] phenanthroine]benzene(DIPB_2H) on a platinum electrode have been investigated using cyclic voltammetry,cyclic ac voltammetry and differential capacitance techniques,etc.In acetonitrile solutions with a concentration of 0.1 mol/L TBAP,the central ruthenium ions in Ru2 and Ru2_2H complexes have shown a single 2e reversible oxidation_reduction wave on the cyclic voltammograms with basically the same formal potentials of Ru2_2H and Ru2 and a slightly larger apparent diffusion coefficient of the Ru2_2H complex cation than that of Ru2,i.e.,3.94×10 -6 cm 2/s and 3.50 ×10 -6 cm 2/s respectively.It appears that an enhanced electronic interaction exists between the two central ruthenium ions in the deprotonation of the bridging ligand(DIPB).
[1] JurisA ,BalzaniV ,BarigellettiF ,CampagnaS ,BelserP ,ZelewskyAV .Ru(Ⅱ )polypyridinecomplexes:pho tophysics,photochemistry ,electrochemistry ,andchemiluminescence[J].Coord .Chem .Rev .,1988,84 :85～2 77.
[2 ] DeSilvaAP ,GunaratneHQN ,GunnlaugassonT ,etal.Signalingrecognitioneventswithfluorescentsensorsandswitches[J].Chem .Rev .,1997,97:1515～ 156 6 .
[3] BalzaniV ,JurisA ,VenturiM ,CampagnaS ,etal.LuminescentandRedox_ActivePolynucleartransitionmetalcomplexes[J].Chem .Rev .,1996 ,96 :759～ 833.
[4 ] AliMM ,SatoH ,MizukawaT ,etal.SelectiveformationofHCO2 - andC2 O4 2 - inelectrochemicalreductionofCO2 catalyzedbymono_andbi_nuclearrutheniumcomplexes[J].Chem .Commun .,1998,2 4 9～ 2 50 .
[5] HagaM ,AnoT ,KanoK ,etal.Proton_inducedswitchingofmetal_metalinteractionsinbinuclearrutheniumandosmiumcomplexesbridgedby 2 ,2_bis(2_pyridyl)bibenzimidazole[J].Inorg .Chem .,1991,30 :384 3～ 349.
[6 ] HagaM ,AliMM ,KosekiS ,etal.Proton_inducedtuningofelectrochemicalandphotophysicalpropertiesinmononuclearandbinuclearrutheniumcomplexescontaining 2 ,2_bis(benzimidazol_2_yl)_4 ,4_bipyridine :syn thesis ,molecularstructure ,andmixed_valencestateandexcited_stateproperties[J].Inorg .Chem .,1996 ,35:3335～ 3347.
[7] OtsukiJ,TsujinoM ,Iizaki,etal.Redox_responsivemolecularswitchforintra -molecularenergytransfer[J].J.Am .Chem .Soc .,1997,119:7895～ 7896 .
[8] BeerPD .AnionSelectiveRecognitionandOptical/ElectrochemicalSensingbyNovelTransition_MetalRecep torsystems[J].Chem .Commun .,1996 ,6 89～ 6 96 .
[9] ChaoH ,LiRH ,YeBHetal.Synthesis,characterizationandthirdordernon_linearopticalpropertiesoftheruthenium(Ⅱ )complexescontaining 2_phenylimidazo
[4,5_f]
[1,10 ]phenanthrolinederivatives[J].J .Chem .Soc .,DaltonTrans.,1999,3711～ 3717.
[10 ] BardAJ ,FaulknerLR .ElectrochemicalMethods[M ].NewYork :JohnWiley&Sons,1980 ,330～ 540 .
[11] WangYX ,PerezWJ,ZhengGY ,RillemaDP ,HuberCL .Preparationpurification ,andcharacterizationofbinuclearruthenium(Ⅱ )Complexes :bridgingligandsbasedondiazafluorenes[J].Inorg .Chem .,1998,37:22 2 7～ 2 2 34.
[12 ] YinYe_Gao ,CheungKung_Kai,WongWing_Tak .Electrochemicalstudiesontheintermetallicinteractioninpolynuclearcomplexes[J].Chem .J .ofChineseUniv .(inChinese) ,1998,19:136 9～ 1374 .
[13] LiHong ,JiangXiong ,ChaoHui,etal.Electrochemicalbehaviorofmononuclearandsymmetricalbinuclearruthenium(Ⅱ )Complexesonaplatinumelectrode[J].ActaChimicaSinica(inChinese) ,2 0 0 0 ,58:82 5～830
