Gietter Amber A S, Pupillo Rachel C, Yap Glenn P A, Beebe Thomas P, Rosenthal Joel, Watson Donald A
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE, 19716 USA.
Chem Sci. 2013 Jan 1;4(1):437-443. doi: 10.1039/C2SC21413J.
Controlling the molecular topology of electrode-catalyst interfaces is a critical factor in engineering devices with specific electron transport kinetics and catalytic efficiencies. As such, the development of rational methods for the modular construction of tailorable electrode surfaces with robust molecular wires (MWs) exhibiting well-defined molecular topologies, conductivities and morphologies is critical to the evolution and implementation of electrochemical arrays for sensing and catalysis. In response to this need, we have established modular on-surface Sonogashira and Glaser cross-coupling processes to synthetically install arrays of ferrocene-capped MWs onto electrochemically functionalized surfaces. These methods are of comparable convenience and efficiency to more commonly employed Huisgen methods. Furthermore, unlike the Huisgen reaction, this new surface functionalization chemistry generates modified electrodes that do not contain unwanted ancillary metal binding sites, while allowing the bridge between the ferrocenyl moiety and electrode surface to be synthetically tailored. Electrochemical and surface analytical characterization of these platforms demonstrate that the linker topology and connectivity influences the ferrocene redox potential and the kinetics of charge transport at the interface.
控制电极 - 催化剂界面的分子拓扑结构是设计具有特定电子传输动力学和催化效率的器件的关键因素。因此，开发合理的方法以模块化方式构建具有明确分子拓扑结构、电导率和形态的坚固分子线（MWs）的可定制电极表面，对于电化学传感和催化阵列的发展与应用至关重要。为满足这一需求，我们建立了模块化的表面Sonogashira和Glaser交叉偶联过程，以将二茂铁封端的MWs阵列合成安装到电化学功能化表面上。这些方法与更常用的Huisgen方法具有相当的便利性和效率。此外，与Huisgen反应不同，这种新的表面功能化化学方法生成的修饰电极不包含不需要的辅助金属结合位点，同时允许二茂铁部分与电极表面之间的连接桥进行合成定制。对这些平台的电化学和表面分析表征表明，连接子拓扑结构和连接性会影响二茂铁的氧化还原电位以及界面处的电荷传输动力学。
