TY - JOUR
T1 - Self-assembled monolayers of oligophenylenecarboxylic acids on silver formed at the liquid-solid interface
AU - Aitchison, Hannah
AU - Lu, Hao
AU - Hogan, Simon W. L.
AU - Früchtl, Herbert
AU - Cebula, Izabela
AU - Zharnikov, Michael
AU - Buck, Manfred
N1 - This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Langmuir, copyright © American Chemical Society after peer review. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.langmuir.6b01773
PY - 2016/9/2
Y1 - 2016/9/2
N2 - A series of para-oligophenylene mono- and dicarboxylic acids (R-(C6H4)nCOOH, n=1-3, R=H,COOH) was studied. Adsorbed on Au(111)/mica modified by an underpotential deposited bilayer of Ag, the self-assembled monolayers (SAMs) were analysed by near edge X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy and scanning tunneling microscopy. In all cases SAMs are formed with molecules adopting an upright orientation and anchored to the substrate by a carboxylate. Except benzoic acid, all SAMs could be imaged at molecular resolution, which revealed highly crystalline layers with a dense molecular packing. The structures of the SAMs are described by a rectangular (5×√3) unit cell for the prevailing phase of the monocarboxylic acids and an oblique (√93×√133) unit cell for the dicarboxylic acids, thus, evidencing a pronounced influence of the second COOH moiety on the SAM structure. Density functional theory calculations suggest that hydrogen bonding between the SAM terminating COOH moieties accounts for the difference. Contrasting other classes of SAMs, the systems studied here are determined by intermolecular interactions whereas molecule-substrate interactions play a secondary role. Thus, eliminating problems arising from the mismatch between the molecular and substrate lattices, coordinatively bonded carboxylic acids on silver should provide considerable flexibility in the design of SAM structures.
AB - A series of para-oligophenylene mono- and dicarboxylic acids (R-(C6H4)nCOOH, n=1-3, R=H,COOH) was studied. Adsorbed on Au(111)/mica modified by an underpotential deposited bilayer of Ag, the self-assembled monolayers (SAMs) were analysed by near edge X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy and scanning tunneling microscopy. In all cases SAMs are formed with molecules adopting an upright orientation and anchored to the substrate by a carboxylate. Except benzoic acid, all SAMs could be imaged at molecular resolution, which revealed highly crystalline layers with a dense molecular packing. The structures of the SAMs are described by a rectangular (5×√3) unit cell for the prevailing phase of the monocarboxylic acids and an oblique (√93×√133) unit cell for the dicarboxylic acids, thus, evidencing a pronounced influence of the second COOH moiety on the SAM structure. Density functional theory calculations suggest that hydrogen bonding between the SAM terminating COOH moieties accounts for the difference. Contrasting other classes of SAMs, the systems studied here are determined by intermolecular interactions whereas molecule-substrate interactions play a secondary role. Thus, eliminating problems arising from the mismatch between the molecular and substrate lattices, coordinatively bonded carboxylic acids on silver should provide considerable flexibility in the design of SAM structures.
KW - carboxylic acids
KW - metal-organic coordination bonding
KW - molecular self-assembly
KW - liquid-solid interface
KW - underpotential deposition
KW - oligophenylenecarboxylic acids
KW - silver
UR - http://pubs.acs.org/journal/langd5
U2 - 10.1021/acs.langmuir.6b01773
DO - 10.1021/acs.langmuir.6b01773
M3 - Article
JO - Langmuir
JF - Langmuir
SN - 0743-7463
ER -