The effect of halogen substitution in self-assembled monolayers of 4-mercaptobiphenyls on noble metal substrates

A. Shaporenko, K. Heister, Abraham Ulman, M. Grunze, M. Zharnikov

Research output: Contribution to journalArticle

Abstract

Self-assembled monolayers (SAMs) formed from 4′-substituted 4-mercaptobiphenyls X-(C 6H 4) 2SH (X-BPT, with X = I, Cl, and F) on polycrystalline (111) gold and silver substrates have been characterized by synchrotron-based high-resolution X-ray photoelectron spectroscopy and angle-resolved near-edge X-ray absorption fine structure spectroscopy. The X-BPT molecules were found to form highly oriented and densely packed SAMs on both substrates, with a smaller molecular inclination in the case of Ag. The experimental data show clear evidence for the charge transfer between the 4′-substituent and biphenyl moieties with the direction and extent of the transfer depending on the electronegativity of the halogen substituent. At the same time, no direct evidence of the charge transfer between the 4′-substituent and the thiolate group was observed. However, the substitution of the 4′-hydrogen by a halogen atom seems to affect the detailed packing arrangements of the SAM constituents.

Original languageEnglish (US)
Pages (from-to)4096-4103
Number of pages8
JournalJournal of Physical Chemistry B
Volume109
Issue number9
DOIs
StatePublished - Mar 10 2005

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Halogens
Self assembled monolayers
Precious metals
noble metals
halogens
Substitution reactions
charge transfer
substitutes
Charge transfer
Substrates
X ray absorption near edge structure spectroscopy
inclination
Electronegativity
synchrotrons
x rays
fine structure
silver
photoelectron spectroscopy
gold
Synchrotrons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

The effect of halogen substitution in self-assembled monolayers of 4-mercaptobiphenyls on noble metal substrates. / Shaporenko, A.; Heister, K.; Ulman, Abraham; Grunze, M.; Zharnikov, M.

In: Journal of Physical Chemistry B, Vol. 109, No. 9, 10.03.2005, p. 4096-4103.

Research output: Contribution to journalArticle

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AU - Grunze, M.

AU - Zharnikov, M.

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N2 - Self-assembled monolayers (SAMs) formed from 4′-substituted 4-mercaptobiphenyls X-(C 6H 4) 2SH (X-BPT, with X = I, Cl, and F) on polycrystalline (111) gold and silver substrates have been characterized by synchrotron-based high-resolution X-ray photoelectron spectroscopy and angle-resolved near-edge X-ray absorption fine structure spectroscopy. The X-BPT molecules were found to form highly oriented and densely packed SAMs on both substrates, with a smaller molecular inclination in the case of Ag. The experimental data show clear evidence for the charge transfer between the 4′-substituent and biphenyl moieties with the direction and extent of the transfer depending on the electronegativity of the halogen substituent. At the same time, no direct evidence of the charge transfer between the 4′-substituent and the thiolate group was observed. However, the substitution of the 4′-hydrogen by a halogen atom seems to affect the detailed packing arrangements of the SAM constituents.

AB - Self-assembled monolayers (SAMs) formed from 4′-substituted 4-mercaptobiphenyls X-(C 6H 4) 2SH (X-BPT, with X = I, Cl, and F) on polycrystalline (111) gold and silver substrates have been characterized by synchrotron-based high-resolution X-ray photoelectron spectroscopy and angle-resolved near-edge X-ray absorption fine structure spectroscopy. The X-BPT molecules were found to form highly oriented and densely packed SAMs on both substrates, with a smaller molecular inclination in the case of Ag. The experimental data show clear evidence for the charge transfer between the 4′-substituent and biphenyl moieties with the direction and extent of the transfer depending on the electronegativity of the halogen substituent. At the same time, no direct evidence of the charge transfer between the 4′-substituent and the thiolate group was observed. However, the substitution of the 4′-hydrogen by a halogen atom seems to affect the detailed packing arrangements of the SAM constituents.

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