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Title: Non-chemisorbed gold–sulfur binding prevails in self-assembled monolayers

Abstract

Gold–thiol contacts are ubiquitous across the physical and biological sciences in connecting organic molecules to surfaces. When thiols bind to gold in self-assembled monolayers (SAMs) the fate of the hydrogen remains a subject of profound debate—with implications for our understanding of their physical properties, spectroscopic features and formation mechanism(s). Exploiting measurements of the transmission through a molecular junction, which is highly sensitive to the nature of the molecule–electrode contact, we demonstrate here that the nature of the gold–sulfur bond in SAMs can be probed via single-molecule conductance measurements. Critically, we find that SAM measurements of dithiol-terminated molecular junctions yield a significantly lower conductance than solution measurements of the same molecule. Through numerous control experiments, conductance noise analysis and transport calculations based on density functional theory, we show that the gold–sulfur bond in SAMs prepared from the solution deposition of dithiols does not have chemisorbed character, which strongly suggests that under these widely used preparation conditions the hydrogen is retained.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [3];  [2]; ORCiD logo [4]
  1. Columbia Univ., New York, NY (United States). Dept. of Applied Physics
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics
  3. Columbia Univ., New York, NY (United States). Dept. of Chemistry
  4. Columbia Univ., New York, NY (United States). Dept. of Applied Physics; Columbia Univ., New York, NY (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1529926
DOE Contract Number:  
AC02–05CH11231
Resource Type:
Journal Article
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 11; Journal Issue: 4; Journal ID: ISSN 1755-4330
Country of Publication:
United States
Language:
English

Citation Formats

Inkpen, Michael S., Liu, Zhen–Fei, Li, Haixing, Campos, Luis M., Neaton, Jeffrey B., and Venkataraman, Latha. Non-chemisorbed gold–sulfur binding prevails in self-assembled monolayers. United States: N. p., 2019. Web. doi:10.1038/s41557-019-0216-y.
Inkpen, Michael S., Liu, Zhen–Fei, Li, Haixing, Campos, Luis M., Neaton, Jeffrey B., & Venkataraman, Latha. Non-chemisorbed gold–sulfur binding prevails in self-assembled monolayers. United States. doi:10.1038/s41557-019-0216-y.
Inkpen, Michael S., Liu, Zhen–Fei, Li, Haixing, Campos, Luis M., Neaton, Jeffrey B., and Venkataraman, Latha. Mon . "Non-chemisorbed gold–sulfur binding prevails in self-assembled monolayers". United States. doi:10.1038/s41557-019-0216-y.
@article{osti_1529926,
title = {Non-chemisorbed gold–sulfur binding prevails in self-assembled monolayers},
author = {Inkpen, Michael S. and Liu, Zhen–Fei and Li, Haixing and Campos, Luis M. and Neaton, Jeffrey B. and Venkataraman, Latha},
abstractNote = {Gold–thiol contacts are ubiquitous across the physical and biological sciences in connecting organic molecules to surfaces. When thiols bind to gold in self-assembled monolayers (SAMs) the fate of the hydrogen remains a subject of profound debate—with implications for our understanding of their physical properties, spectroscopic features and formation mechanism(s). Exploiting measurements of the transmission through a molecular junction, which is highly sensitive to the nature of the molecule–electrode contact, we demonstrate here that the nature of the gold–sulfur bond in SAMs can be probed via single-molecule conductance measurements. Critically, we find that SAM measurements of dithiol-terminated molecular junctions yield a significantly lower conductance than solution measurements of the same molecule. Through numerous control experiments, conductance noise analysis and transport calculations based on density functional theory, we show that the gold–sulfur bond in SAMs prepared from the solution deposition of dithiols does not have chemisorbed character, which strongly suggests that under these widely used preparation conditions the hydrogen is retained.},
doi = {10.1038/s41557-019-0216-y},
journal = {Nature Chemistry},
issn = {1755-4330},
number = 4,
volume = 11,
place = {United States},
year = {2019},
month = {3}
}

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