LM Ballesteros
Controlling the Structural and Electrical Properties of Diacid Oligo(Phenylene Ethynylene) Langmuir-Blodgett Films
Ballesteros, LM; Martín, S; Cortes, J; Marqués-González, S; Higgins, SJ; Nichols, RJ; Low, PJ; Cea, P
Authors
S Martín
J Cortes
S Marqués-González
SJ Higgins
RJ Nichols
PJ Low
P Cea
Abstract
The preparation, characterization and electrical properties of Langmuir–Blodgett (LB) films composed of a symmetrically substituted oligomeric phenylene ethynylene derivative, namely, 4,4′-[1,4-phenylenebis(ethyne-2,1-diyl)]dibenzoic acid (OPE2A), are described. Analysis of the surface pressure versus area per molecule isotherms and Brewster angle microscopy reveal that good-quality Langmuir (L) films can be formed both on pure water and a basic subphase. Monolayer L films were transferred onto solid substrates with a transfer ratio of unity to obtain LB films. Both L and LB films prepared on or from a pure water subphase show a red shift in the UV/Vis spectrum of about 14 nm, in contrast to L and LB films prepared from a basic subphase, which show a hypsochromic shift of 15 nm. This result, together with X-ray photoelectron spectroscopic and quartz crystal microbalance experiments, conclusively demonstrate formation of one-layer LB films in which OPE2A molecules are chemisorbed onto gold substrates and consequently COOAu junctions are formed. In LB films prepared on a basic subphase the other terminal acid group is also deprotonated and associates with an Na+ counterion. In contrast, LB films prepared from a pure water subphase preserve the protonated acid group, and lateral H-bonds with neighbouring molecules give rise to a supramolecular structure. STM-based conductance studies revealed that films prepared from a basic subphase are more conductive than the analogous films prepared from pure water, and the electrical conductance of the deprotonated films also coincides more closely with single-molecule conductance measurements. This result was interpreted not only in terms of better electron transmission in COOAu molecular junctions, but also in terms of the presence of lateral H-bonds in the films formed from pure water, which lead to reduced conductance of the molecular junctions.
Citation
Ballesteros, L., Martín, S., Cortes, J., Marqués-González, S., Higgins, S., Nichols, R., …Cea, P. (2013). Controlling the Structural and Electrical Properties of Diacid Oligo(Phenylene Ethynylene) Langmuir-Blodgett Films. Chemistry - A European Journal, 19(17), 5352-5363. https://doi.org/10.1002/chem.201203261
Journal Article Type | Article |
---|---|
Publication Date | Apr 22, 2013 |
Deposit Date | Aug 13, 2013 |
Publicly Available Date | Jan 18, 2019 |
Journal | Chemistry - A European Journal |
Print ISSN | 0947-6539 |
Electronic ISSN | 1521-3765 |
Publisher | Wiley |
Peer Reviewed | Peer Reviewed |
Volume | 19 |
Issue | 17 |
Pages | 5352-5363 |
DOI | https://doi.org/10.1002/chem.201203261 |
Keywords | Carboxylic acids, Conducting materials, Langmuir–Blodgett films, Oligo(phenylene ethynylene)s, Scanning probe microscopy. |
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Copyright Statement
This is the accepted version of the following article: Ballesteros, L M, Martín, S, Cortes, J, Marqués-González, S, Higgins, S J, Nichols, R J, Low, P J & Cea, P (2013). Controlling the Structural and Electrical Properties of Diacid Oligo(Phenylene Ethynylene) Langmuir-Blodgett Films. Chemistry - A European Journal 19(17): 5352-5363 which has been published in final form at http://dx.doi.org/10.1002/chem.201203261. This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving.
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