Self-assembling bipyridinium multilayers

Robert J. Alvarado, Jhindan Mukherjee, Eden J. Pacsial, Daniel Alexander, Francisco Raymo

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

The identification of strategies to assemble nanostructured films with engineered properties on solid supports can lead to the development of innovative functional materials. In particular, the self-assembly of electroactive multilayers from simple molecular building blocks on metallic electrodes can offer the opportunity to regulate the exchange of electrons between the underlying substrate and solution species. In this context, we designed an experimental protocol to prepare electroactive films from bipyridinium bisthiols. Specifically, we found that a compound incorporating two bipyridinium dications at its core and terminal thiol groups self-assembles into remarkably stable multilayers on polycrystalline gold. The surface coverage of the resulting films can be regulated by adjusting the exposure time of the gold substrate to the bipyridinium solution. Control experiments with appropriate model compounds demonstrate that both bipyridinium dications as well as both thiol groups must be present in the molecular skeleton to encourage multilayer growth. The resulting films transport electrons efficiently from the electrode surface to the film/solution interface. Indeed, they mediate the reduction of Ru(NH 3) 6 3+ in the electrolyte solution but prevent the back oxidation of the resulting Ru(NH 3) 6 2+. Furthermore, these polycationic bipyridinium films capture electrostatically Fe(CN) 6 4- tetraanions, which can also be exploited to transport electrons across the interfacial assembly. In fact, electrons can travel through the bipyridnium 2-/1+ couples to redox probes in solution and then back to the electrode through the Fe(CN) 6 4/3- couples. Thus, our original approach to self-assembling multilayers can produce stable electroactive films with unique electron transport properties, which can be regulated with a careful choice of the anionic components.

Original languageEnglish
Pages (from-to)6164-6173
Number of pages10
JournalJournal of Physical Chemistry B
Volume109
Issue number13
DOIs
StatePublished - Apr 7 2005

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assembling
Multilayers
electrons
Sulfhydryl Compounds
thiols
Gold
Electrodes
electrodes
gold
Electron transport properties
Functional materials
Electrons
Substrates
musculoskeletal system
Self assembly
Electrolytes
travel
self assembly
Ion exchange
assembly

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Alvarado, R. J., Mukherjee, J., Pacsial, E. J., Alexander, D., & Raymo, F. (2005). Self-assembling bipyridinium multilayers. Journal of Physical Chemistry B, 109(13), 6164-6173. https://doi.org/10.1021/jp044797i

Self-assembling bipyridinium multilayers. / Alvarado, Robert J.; Mukherjee, Jhindan; Pacsial, Eden J.; Alexander, Daniel; Raymo, Francisco.

In: Journal of Physical Chemistry B, Vol. 109, No. 13, 07.04.2005, p. 6164-6173.

Research output: Contribution to journalArticle

Alvarado, RJ, Mukherjee, J, Pacsial, EJ, Alexander, D & Raymo, F 2005, 'Self-assembling bipyridinium multilayers', Journal of Physical Chemistry B, vol. 109, no. 13, pp. 6164-6173. https://doi.org/10.1021/jp044797i
Alvarado RJ, Mukherjee J, Pacsial EJ, Alexander D, Raymo F. Self-assembling bipyridinium multilayers. Journal of Physical Chemistry B. 2005 Apr 7;109(13):6164-6173. https://doi.org/10.1021/jp044797i
Alvarado, Robert J. ; Mukherjee, Jhindan ; Pacsial, Eden J. ; Alexander, Daniel ; Raymo, Francisco. / Self-assembling bipyridinium multilayers. In: Journal of Physical Chemistry B. 2005 ; Vol. 109, No. 13. pp. 6164-6173.
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