Sciences Chimiques de Rennes (Equipe MaCSE), CNRS, UMR 6226, Université de Rennes 1, Campus de Beaulieu, Bat 10C, 35042 Rennes Cedex, France.
J Am Chem Soc. 2010 Oct 13;132(40):14039-41. doi: 10.1021/ja106971x.
A global strategy to prepare a versatile and robust reactive platform for immobilizing molecules on carbon substrates with controlled morphology and high selectivity is presented. The procedure is based on the electroreduction of a selected triisopropylsilyl (TIPS)-protected ethynyl aryldiazonium salt. It avoids the formation of multilayers and efficiently protects the functional group during the electrografting step. After TIPS deprotection, a dense reactive ethynyl aryl monolayer is obtained which presents a very low barrier to charge transfer between molecules in solution and the surface. As a test functionalization, azidomethylferrocene was coupled by "click" chemistry with the modified surface. Analysis of the redox activity highlights a surface concentration close to the maximum possible attachment considering the steric hindrance of a ferrocenyl group.
提出了一种在具有受控形态和高选择性的碳基底上固定分子的通用且稳健的反应性平台的全球策略。该方法基于三异丙基硅基（TIPS）保护的乙炔基芳基重氮盐的电化学还原。它避免了多层的形成，并在电接枝步骤中有效地保护了官能团。TIPS 脱保护后，得到致密的反应性乙炔基芳基单层，其在溶液中的分子和表面之间的电荷转移具有非常低的势垒。作为测试功能化，叠氮甲基二茂铁通过“点击”化学与修饰后的表面偶联。对氧化还原活性的分析突出表明，考虑到二茂铁基团的空间位阻，表面浓度接近最大可能的附着。
