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Self-Assembly of Phenylene Ethynylene Diazonium Salts on Metal Surfaces as Potential Molecular Wires

  • Dmitry V. Kosynkin (a1), Jiping Yang (a1) and James M. Tour (a1)


A series of substituted phenylene ethynylene diazonium salts were prepared from the corresponding anilines by the action of nitrosonium tetrafluoroborate in sulfolane-acetonitrile solvent. Formation of self-assembled layers of the diazonium salts in acetonitrile solution was demonstrated on Au, Cu and Pt surfaces. The self-assembly rate of the diazonium salts was found to be markedly dependent on the electron withdrawing character of the substituents attached to the aromatic rings.



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8. To maximize the solubility of the starting amines, a mixture of sulfolane with only 10- 25% acetonitrile was used for their dissolution, while the nitrosonium tetrafluoroborate was suspended in a lower freezing mixture of sulfolane with 75-90% acetonitrile.
9. (a) Kosynkin, D., Bockman, T. M., Kochi, J. K., J. Chem. Soc., Perkin Trans. 2 2003 (1997) (b) D. Kosynkin, T. M. Bockman, J. K. Kochi, J. Am. Chem. Soc. 119, 4846 (1997). Commercial samples of NOBF4 give more by-products.
10. CAUTION! All dry diazonium salts reported in this study displayed considerable DSC exotherms above 100-120°C and should be handled as potentially explosive materials. Oligo(phenylene ethynylene)diazonium tetrafluoroborates are moderately light sensitive and should be stored in a freezer in the dark to avoid decomposition.
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