Ferrocenylalkylthiolates as a probe of heterogeneity in binary self-assembled monolayers on gold

Yoon Suk Lee; Todd C. Sutherland; Simona Rucareanu; R. Brace Lennox

doi:10.1021/la053317r

Ferrocenylalkylthiolates as a probe of heterogeneity in binary self-assembled monolayers on gold

Yoon Suk Lee, Todd C. Sutherland, Simona Rucareanu, R. Brace Lennox

Research output: Journal article publication › Journal article › Academic research › peer-review

146 Citations (Scopus)

Abstract

The oft-cited complexity of tethered ferrocene electrochemistry in single component (FcRS-) or binary (FcRS-/ CH3R′S-) self-assembled monolayers (SAMs) on gold has been investigated. The complex voltammetry is shown to be linked to local electrostatics caused by the formation of the ferrocenium ion. This conclusion is reached by studying model effects in binary SAMs, where a cationic alkylthiolate (H3N+C11S-Au) is mixed with FcC12S-Au. A fitting procedure involving both a Gaussian and a Lorentzian distribution is used for deconvolution of the two peaks which are consistently observed in the SAMs when χFcsurf≥0.2. The lower-potential (Eo′ = 250 mV) and higherpotential (Eo′ = 350 mV) voltammetric peaks are assigned to Fc moieties in "isolated" and "clustered" states, respectively. Use of this method to better understand SAM structure is demonstrated by distinguishing the degree of homogeneity in two binary SAMs of similar composition.

Original language	English
Pages (from-to)	4438-4444
Number of pages	7
Journal	Langmuir
Volume	22
Issue number	9
DOIs	https://doi.org/10.1021/la053317r
Publication status	Published - 25 Apr 2006
Externally published	Yes

ASJC Scopus subject areas

Materials Science(all)
Condensed Matter Physics
Surfaces and Interfaces
Spectroscopy
Electrochemistry

More information

10.1021/la053317r

Cite this

@article{0072975a76a745ceb3712772030f9892,

title = "Ferrocenylalkylthiolates as a probe of heterogeneity in binary self-assembled monolayers on gold",

abstract = "The oft-cited complexity of tethered ferrocene electrochemistry in single component (FcRS-) or binary (FcRS-/ CH3R′S-) self-assembled monolayers (SAMs) on gold has been investigated. The complex voltammetry is shown to be linked to local electrostatics caused by the formation of the ferrocenium ion. This conclusion is reached by studying model effects in binary SAMs, where a cationic alkylthiolate (H3N+C11S-Au) is mixed with FcC12S-Au. A fitting procedure involving both a Gaussian and a Lorentzian distribution is used for deconvolution of the two peaks which are consistently observed in the SAMs when χFcsurf≥0.2. The lower-potential (Eo′ = 250 mV) and higherpotential (Eo′ = 350 mV) voltammetric peaks are assigned to Fc moieties in {"}isolated{"} and {"}clustered{"} states, respectively. Use of this method to better understand SAM structure is demonstrated by distinguishing the degree of homogeneity in two binary SAMs of similar composition.",

author = "Lee, {Yoon Suk} and Sutherland, {Todd C.} and Simona Rucareanu and Lennox, {R. Brace}",

year = "2006",

month = apr,

day = "25",

doi = "10.1021/la053317r",

language = "English",

volume = "22",

pages = "4438--4444",

journal = "Langmuir",

issn = "0743-7463",

publisher = "American Chemical Society",

number = "9",

}

TY - JOUR

T1 - Ferrocenylalkylthiolates as a probe of heterogeneity in binary self-assembled monolayers on gold

AU - Lee, Yoon Suk

AU - Sutherland, Todd C.

AU - Rucareanu, Simona

AU - Lennox, R. Brace

PY - 2006/4/25

Y1 - 2006/4/25

N2 - The oft-cited complexity of tethered ferrocene electrochemistry in single component (FcRS-) or binary (FcRS-/ CH3R′S-) self-assembled monolayers (SAMs) on gold has been investigated. The complex voltammetry is shown to be linked to local electrostatics caused by the formation of the ferrocenium ion. This conclusion is reached by studying model effects in binary SAMs, where a cationic alkylthiolate (H3N+C11S-Au) is mixed with FcC12S-Au. A fitting procedure involving both a Gaussian and a Lorentzian distribution is used for deconvolution of the two peaks which are consistently observed in the SAMs when χFcsurf≥0.2. The lower-potential (Eo′ = 250 mV) and higherpotential (Eo′ = 350 mV) voltammetric peaks are assigned to Fc moieties in "isolated" and "clustered" states, respectively. Use of this method to better understand SAM structure is demonstrated by distinguishing the degree of homogeneity in two binary SAMs of similar composition.

AB - The oft-cited complexity of tethered ferrocene electrochemistry in single component (FcRS-) or binary (FcRS-/ CH3R′S-) self-assembled monolayers (SAMs) on gold has been investigated. The complex voltammetry is shown to be linked to local electrostatics caused by the formation of the ferrocenium ion. This conclusion is reached by studying model effects in binary SAMs, where a cationic alkylthiolate (H3N+C11S-Au) is mixed with FcC12S-Au. A fitting procedure involving both a Gaussian and a Lorentzian distribution is used for deconvolution of the two peaks which are consistently observed in the SAMs when χFcsurf≥0.2. The lower-potential (Eo′ = 250 mV) and higherpotential (Eo′ = 350 mV) voltammetric peaks are assigned to Fc moieties in "isolated" and "clustered" states, respectively. Use of this method to better understand SAM structure is demonstrated by distinguishing the degree of homogeneity in two binary SAMs of similar composition.

UR - http://www.scopus.com/inward/record.url?scp=33646431710&partnerID=8YFLogxK

U2 - 10.1021/la053317r

DO - 10.1021/la053317r

M3 - Journal article

SN - 0743-7463

VL - 22

SP - 4438

EP - 4444

JO - Langmuir

JF - Langmuir

IS - 9

ER -

Ferrocenylalkylthiolates as a probe of heterogeneity in binary self-assembled monolayers on gold

Abstract

ASJC Scopus subject areas

More information

Other files and links

Fingerprint

Cite this