Does thiol-functionalized viologen monolayer memorize anion present when forming the monolayer?

T. Sagara, H. Tsuruta, Naotoshi Nakashima

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

We investigated the effect of the presence of an additive anion while forming a self-assembled monolayer of a thiol-functionalized redox active species upon the behavior in aqueous solutions. A bromide salt was added in an acetonitrile solution of a thiol-functionalized viologen (viologen-thiol: N-pentyl-N′-(11-mercapto)undecyl-4,4′-bipyridinium bishexafluorophosphate) in which the self-assembled monolayer was formed on a polycrystalline Au electrode. We examined the structure and electrochemical behavior of the resulting monolayer-modified electrode in three different aqueous electrolyte solutions. The viologen-thiol monolayer prepared in the presence of Br- exhibited obviously different behavior in both KBr and KF electrolyte solutions from that prepared in the absence of Br-. On the other hand, the difference was minor in KPF6 solution. The difference of the electrochemical behavior was represented by the coverage of the viologen-thiol and the formal potential of viologen dication/radical cation redox couple. The memory that the viologen-thiol monolayer was formed in the presence of Br- was retained in KF and KBr solutions, though it was erased in the electrolyte solution containing PF6-, which is a softer anion than Br-. However, no definitive difference of the film structure was deduced from the electroreflectance study in regard to the monomer content and the average orientation of the viologen moiety.

Original languageEnglish
Pages (from-to)255-263
Number of pages9
JournalJournal of Electroanalytical Chemistry
Volume500
Issue number1-2
DOIs
Publication statusPublished - Mar 16 2001

Fingerprint

Viologens
Sulfhydryl Compounds
Anions
Monolayers
Negative ions
Electrolytes
Self assembled monolayers
Electrodes
Acetonitrile
Bromides
Cations
Salts
Monomers
Positive ions
Data storage equipment

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry
  • Chemical Engineering(all)
  • Electrochemistry

Cite this

Does thiol-functionalized viologen monolayer memorize anion present when forming the monolayer? / Sagara, T.; Tsuruta, H.; Nakashima, Naotoshi.

In: Journal of Electroanalytical Chemistry, Vol. 500, No. 1-2, 16.03.2001, p. 255-263.

Research output: Contribution to journalArticle

Sagara, T. ; Tsuruta, H. ; Nakashima, Naotoshi. / Does thiol-functionalized viologen monolayer memorize anion present when forming the monolayer?. In: Journal of Electroanalytical Chemistry. 2001 ; Vol. 500, No. 1-2. pp. 255-263.
@article{910d90868e4f49dcb85e4b619d96b548,
title = "Does thiol-functionalized viologen monolayer memorize anion present when forming the monolayer?",
abstract = "We investigated the effect of the presence of an additive anion while forming a self-assembled monolayer of a thiol-functionalized redox active species upon the behavior in aqueous solutions. A bromide salt was added in an acetonitrile solution of a thiol-functionalized viologen (viologen-thiol: N-pentyl-N′-(11-mercapto)undecyl-4,4′-bipyridinium bishexafluorophosphate) in which the self-assembled monolayer was formed on a polycrystalline Au electrode. We examined the structure and electrochemical behavior of the resulting monolayer-modified electrode in three different aqueous electrolyte solutions. The viologen-thiol monolayer prepared in the presence of Br- exhibited obviously different behavior in both KBr and KF electrolyte solutions from that prepared in the absence of Br-. On the other hand, the difference was minor in KPF6 solution. The difference of the electrochemical behavior was represented by the coverage of the viologen-thiol and the formal potential of viologen dication/radical cation redox couple. The memory that the viologen-thiol monolayer was formed in the presence of Br- was retained in KF and KBr solutions, though it was erased in the electrolyte solution containing PF6-, which is a softer anion than Br-. However, no definitive difference of the film structure was deduced from the electroreflectance study in regard to the monomer content and the average orientation of the viologen moiety.",
author = "T. Sagara and H. Tsuruta and Naotoshi Nakashima",
year = "2001",
month = "3",
day = "16",
doi = "10.1016/S0022-0728(00)00395-8",
language = "English",
volume = "500",
pages = "255--263",
journal = "Journal of Electroanalytical Chemistry",
issn = "0368-1874",
publisher = "Elsevier Sequoia",
number = "1-2",

}

TY - JOUR

T1 - Does thiol-functionalized viologen monolayer memorize anion present when forming the monolayer?

AU - Sagara, T.

AU - Tsuruta, H.

AU - Nakashima, Naotoshi

PY - 2001/3/16

Y1 - 2001/3/16

N2 - We investigated the effect of the presence of an additive anion while forming a self-assembled monolayer of a thiol-functionalized redox active species upon the behavior in aqueous solutions. A bromide salt was added in an acetonitrile solution of a thiol-functionalized viologen (viologen-thiol: N-pentyl-N′-(11-mercapto)undecyl-4,4′-bipyridinium bishexafluorophosphate) in which the self-assembled monolayer was formed on a polycrystalline Au electrode. We examined the structure and electrochemical behavior of the resulting monolayer-modified electrode in three different aqueous electrolyte solutions. The viologen-thiol monolayer prepared in the presence of Br- exhibited obviously different behavior in both KBr and KF electrolyte solutions from that prepared in the absence of Br-. On the other hand, the difference was minor in KPF6 solution. The difference of the electrochemical behavior was represented by the coverage of the viologen-thiol and the formal potential of viologen dication/radical cation redox couple. The memory that the viologen-thiol monolayer was formed in the presence of Br- was retained in KF and KBr solutions, though it was erased in the electrolyte solution containing PF6-, which is a softer anion than Br-. However, no definitive difference of the film structure was deduced from the electroreflectance study in regard to the monomer content and the average orientation of the viologen moiety.

AB - We investigated the effect of the presence of an additive anion while forming a self-assembled monolayer of a thiol-functionalized redox active species upon the behavior in aqueous solutions. A bromide salt was added in an acetonitrile solution of a thiol-functionalized viologen (viologen-thiol: N-pentyl-N′-(11-mercapto)undecyl-4,4′-bipyridinium bishexafluorophosphate) in which the self-assembled monolayer was formed on a polycrystalline Au electrode. We examined the structure and electrochemical behavior of the resulting monolayer-modified electrode in three different aqueous electrolyte solutions. The viologen-thiol monolayer prepared in the presence of Br- exhibited obviously different behavior in both KBr and KF electrolyte solutions from that prepared in the absence of Br-. On the other hand, the difference was minor in KPF6 solution. The difference of the electrochemical behavior was represented by the coverage of the viologen-thiol and the formal potential of viologen dication/radical cation redox couple. The memory that the viologen-thiol monolayer was formed in the presence of Br- was retained in KF and KBr solutions, though it was erased in the electrolyte solution containing PF6-, which is a softer anion than Br-. However, no definitive difference of the film structure was deduced from the electroreflectance study in regard to the monomer content and the average orientation of the viologen moiety.

UR - http://www.scopus.com/inward/record.url?scp=0035276115&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035276115&partnerID=8YFLogxK

U2 - 10.1016/S0022-0728(00)00395-8

DO - 10.1016/S0022-0728(00)00395-8

M3 - Article

AN - SCOPUS:0035276115

VL - 500

SP - 255

EP - 263

JO - Journal of Electroanalytical Chemistry

JF - Journal of Electroanalytical Chemistry

SN - 0368-1874

IS - 1-2

ER -