Macrocycles Bearing Ferrocenyl Pendants and their Electrochemical Properties upon Binding to Divalent Transition Metal Cations
作者:Zhanghua Zeng、Matthew J. Belousoff、Leone Spiccia、Alan M. Bond、Angel A. J. Torriero
DOI:10.1002/cplu.201700550
日期:2018.7
process if 1 and 2 are complexed with Cd2+ , Cu2+ , Zn2+ , Ni2+ , or Co2+ . Binding of these metal ions produces a significant shift in the reversible midpoint potential (Em ). Except for Ni2+ , Em is linearly proportional to the charge density of the transition metal ion, demonstrating that 1 and 2 may undergo redox switching. The diffusion coefficients of Fc, DmFc, 1 and 2, and their metal ion complexes
与配体[Fc(cycln)](1)和[Fc(cycln)2](2)形成的Cu2 +,Co2 +,Cd2 +,Zn2 +和Ni2 +的金属配合物(Fc =二茂铁,cycln = 1、4、7,合成并表征了10-四氮杂环十二烷)。报告了2的Fc([Cu(cycln)(CH3 CN)] 2(ClO4)4的Cu2 +络合物的X射线结构,结果表明两个带正电的Cu2 +-环素单元的配位数为5 ,采用扭曲的三角-双锥体构型,相对于Fc基团,Cu2 +-环素单元呈反型排列,可能是为了最大程度地减少静电排斥力; CH2 Cl2 //中游离配体1和2的伏安氧化。 CH3 CN(1:4)溶剂混合物产生两个紧密间隔的氧化过程,两个电子转移步骤均与二茂铁基部分相关,暗示环氮原子和二茂铁基之间的强连通。相反,如果1和2与Cd2 +,Cu2 +,Zn2 +,Ni2 +或Co2 +络合,则循环伏安图仅显示简单的可逆单电子过