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

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...

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Main Authors: Darwish, Nadim, Eggers, P., Dasilva, P., Zhang, Y., Tong, Y., Ye, S., Gooding, J., Paddon-Row, M.
Format: Journal Article
Published: Wiley - V C H Verlag GmbH & Co. KGaA 2012
Online Access:http://hdl.handle.net/20.500.11937/9401
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author Darwish, Nadim
Eggers, P.
Dasilva, P.
Zhang, Y.
Tong, Y.
Ye, S.
Gooding, J.
Paddon-Row, M.
author_facet Darwish, Nadim
Eggers, P.
Dasilva, P.
Zhang, Y.
Tong, Y.
Ye, S.
Gooding, J.
Paddon-Row, M.
author_sort Darwish, Nadim
building Curtin Institutional Repository
collection Online Access
description 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.
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spelling curtin-20.500.11937-94012017-09-13T14:51:28Z Electroactive self-assembled monolayers of unique geometric structures by using rigid norbornylogous bridges Darwish, Nadim Eggers, P. Dasilva, P. Zhang, Y. Tong, Y. Ye, S. Gooding, J. Paddon-Row, M. 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. 2012 Journal Article http://hdl.handle.net/20.500.11937/9401 10.1002/chem.201101588 Wiley - V C H Verlag GmbH & Co. KGaA restricted
spellingShingle Darwish, Nadim
Eggers, P.
Dasilva, P.
Zhang, Y.
Tong, Y.
Ye, S.
Gooding, J.
Paddon-Row, M.
Electroactive self-assembled monolayers of unique geometric structures by using rigid norbornylogous bridges
title Electroactive self-assembled monolayers of unique geometric structures by using rigid norbornylogous bridges
title_full Electroactive self-assembled monolayers of unique geometric structures by using rigid norbornylogous bridges
title_fullStr Electroactive self-assembled monolayers of unique geometric structures by using rigid norbornylogous bridges
title_full_unstemmed Electroactive self-assembled monolayers of unique geometric structures by using rigid norbornylogous bridges
title_short Electroactive self-assembled monolayers of unique geometric structures by using rigid norbornylogous bridges
title_sort electroactive self-assembled monolayers of unique geometric structures by using rigid norbornylogous bridges
url http://hdl.handle.net/20.500.11937/9401