鈥楥lick鈥?Synthesis and Redox Properties of Triazolyl Cobalticinium Dendrimers

详细信息    查看全文

• 作者：Amalia Rapakousiou ; Yanlan Wang ; Colette Belin ; No毛l Pinaud ; Jaime Ruiz ; Didier Astruc
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：June 3, 2013
• 年：2013
• 卷：52
• 期：11
• 页码：6685-6693
• 全文大小：544K
• 年卷期：v.52,no.11(June 3, 2013)
• ISSN：1520-510X

文摘

The derivatization of macromolecules with redox-stable groups is a challenge for molecular electronics applications. The large majority of redox-derivatized macromolecules involve ferrocenes, and there are only a few reports with cobalticinium. We report here the first click derivatization of macromolecules with the cobalticinium redox group using ethynylcobalticinium hexafluorophosphate, 1. Cu^I catalysis was used for these selective click metallodendrimer syntheses starting from 1 and providing the tripodal dendron 3 that contains three 1,2,3-triazolylcobalticinium termini and a phenol focal point and the dendrimers of generations 0, 1, and 2 containing 9, 27, and 81 triazolylcobalticinium units for the dendrimers 4, 5, and 6, respectively. Atomic force microscopy (AFM) statistical studies provided the progression of height upon increase of dendrimer generation. Cyclic voltammetry studies in MeCN and dimethylformamide (DMF) show the solvent-dependent reversibility of the Co^III/II wave (18e/19e) and generation dependent reversibility of the Co^II/I (19e/20e) wave in DMF. The H₂PO₄^{鈥?/sup> anion is only recognized by the largest metallodendrimer 6 by a significant cathodic shift of the CoIII/II wave.}