Electroactive self-assembled monolayers of unique geometric structures by using rigid norbornylogous bridges

Nadim Darwish, Paul K. Eggers, Paulo Dasilva, Yi Zhang, Yujin Tong, Shen Ye, J. Justin Gooding, Michael N. Paddon-Row

Research output: Contribution to journalArticlepeer-review

12 Citations (Scopus)

Abstract

Herein, we describe the synthesis of straight (S) and L-shaped (L) norbornylogous bridges (NBs) with an anthraquinone moiety at the distal end as the redox-active head group and two thiol feet at the proximal end, by which the molecules assemble on gold surfaces. The NB molecules were shown to form self-assembled monolayers (SAMs) with a well-behaved surface redox process. The SAMs were characterized by using in situ IR spectroscopy, cyclic voltammetry, scanning tunnelling microscopy and electrochemical impedance spectroscopy. The surface selection rules associated with the IR band intensities allowed the estimation of the position of the anthraquinone moiety with respect to the surface and the tilt of the bridge with respect to the surface normal, both in pure and diluted monolayers. It is shown that the S-and L-NBs hold the plane of the anthraquinone moiety close to the surface normal or the surface tangent, respectively. Neither NB molecule changes its orientation if spaced by diluents on the surface. The difference in the structure of the S-and L-NB SAMs provides a suitable framework for the investigation of factors that govern electron transfer of anthraquinone moieties across self-assembled monolayers with limited structural ambiguity, as compared with the commonly used structurally flexible alkanethiol monolayers.

Original languageEnglish
Pages (from-to)283-292
Number of pages10
JournalChemistry - A European Journal
Volume18
Issue number1
DOIs
Publication statusPublished - 2012 Jan 2
Externally publishedYes

Keywords

  • IR spectroscopy
  • anthraquinones
  • bridging ligands
  • electrochemistry
  • monolayers

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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