Synthesis of Ferrocenethiols Containing Oligo(phenylenevinylene) Bridges and Their Characterization on Gold Electrodes
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- 作者：Stephen P. Dudek ; Hadley D. Sikes ; and Christopher E. D. Chidsey
- 刊名：Journal of the American Chemical Society
- 出版年：2001
- 出版时间：August 22, 2001
- 年：2001
- 卷：123
- 期：33
- 页码：8033 - 8038
- 全文大小：86K
- 年卷期：v.123,no.33(August 22, 2001)
- ISSN：1520-5126
文摘
Ferrocene-terminated oligo(phenylenevinylene) (OPV) methyl thiols have been prepared by orthogonalcoupling of phenylene monomers. Ethoxy substituents on the phenyl rings improve the solubility of OPV,enabling the synthesis of longer oligomers. Self-assembled monolayers containing a mixture of a ferroceneOPV methyl thiol and a diluent alkanethiol were deposited on gold. A cyclic voltammetric study of monolayerscontaining oligomers of the same length with and without ethoxy solubilizing groups reveals that both solubilizedand unsolubilized oligomers form well-packed self-assembled monolayers. Changing the position of thesolubilizing groups on an oligomer chain does not preclude packing of the oligomer in the monolayer.Conventional chronoamperometry, which can be used to measure rate constants up to ~104 s-1, is too slowto measure the electron-transfer rate through these oligomers over distances up to 35 Å. OPV bridges areexpected to be highly conjugated unlike oligo(phenyleneethynylene) bridges, which may be only partiallyconjugated because of rotation of the phenyl rings about the ethynylene bonds. Because of its high conjugation,OPV may prove useful as a molecular wire.