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

Journal Article · · Nature Chemistry
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
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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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
DOE Contract Number:
AC02–05CH11231
OSTI ID:
1529926
Journal Information:
Nature Chemistry, Vol. 11, Issue 4; ISSN 1755-4330
Country of Publication:
United States
Language:
English

References (53)

Adsorption of bifunctional organic disulfides on gold surfaces journal June 1983
Molecular-Level Control over Surface Order in Self-Assembled Monolayer Films of Thiols on Gold journal April 1988
Self-Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology journal April 2005
The gold–sulfur interface at the nanoscale journal May 2012
Comparison of self-assembled monolayers on gold: coadsorption of thiols and disulfides journal May 1989
X-ray Diffraction and Computation Yield the Structure of Alkanethiols on Gold(111) journal August 2008
Electrochemical and X-ray photoelectron spectroscopic evidence for differences in the binding sites of alkanethiolate monolayers chemisorbed at gold journal October 1995
The Self-Assembly Mechanism of Alkanethiols on Au(111) journal May 1996
Fundamental studies of the chemisorption of organosulfur compounds on gold(111). Implications for molecular self-assembly on gold surfaces journal February 1987
Self-assembled monolayers of thiols and dithiols on gold: new challenges for a well-known system journal January 2010
The Chemistry of the Sulfur–Gold Interface: In Search of a Unified Model journal March 2012
Competition of van der Waals and chemical forces on gold–sulfur surfaces and nanoparticles journal February 2017
Structure of a Thiol Monolayer-Protected Gold Nanoparticle at 1.1 A Resolution journal October 2007
Measurement of Single-Molecule Resistance by Repeated Formation of Molecular Junctions journal August 2003
Conductance of a Molecular Junction journal October 1997
Redox State Dependence of Single Molecule Conductivity journal December 2003
Charge Transport in Single Au | Alkanedithiol | Au Junctions:  Coordination Geometries and Conformational Degrees of Freedom journal January 2008
New Insights into Single-Molecule Junctions Using a Robust, Unsupervised Approach to Data Collection and Analysis journal July 2015
Anomalous length and voltage dependence of single molecule conductance journal January 2009
Dependence of single-molecule junction conductance on molecular conformation journal August 2006
Reversible on-surface wiring of resistive circuits journal January 2017
Electronically Transparent Au–N Bonds for Molecular Junctions journal October 2017
Contact Chemistry and Single-Molecule Conductance:  A Comparison of Phosphines, Methyl Sulfides, and Amines journal December 2007
In situ formation of highly conducting covalent Au–C contacts for single-molecule junctions journal May 2011
Structure–Property Relationships in Atomic-Scale Junctions: Histograms and Beyond journal February 2016
Amine−Gold Linked Single-Molecule Circuits:  Experiment and Theory journal November 2007
Conductance of Alkanedithiol Single-Molecule Junctions: A Molecular Dynamics Study journal January 2009
Stretching-Induced Conductance Variations as Fingerprints of Contact Configurations in Single-Molecule Junctions journal June 2017
Binding configurations and intramolecular strain in single-molecule devices journal February 2015
Flicker Noise as a Probe of Electronic Interaction at Metal–Single Molecule Interfaces journal May 2015
Density-functional method for nonequilibrium electron transport journal March 2002
Zero-bias molecular electronics: Exchange-correlation corrections to Landauer's formula journal March 2006
Length Dependence of Conductance in Aromatic Single-Molecule Junctions journal November 2009
Amine-linked single-molecule circuits: systematic trends across molecular families journal August 2008
The electrochemical desorption of n-alkanethiol monolayers from polycrystalline Au and Ag electrodes journal July 1991
Chemisorbed Monolayers of Corannulene Penta-Thioethers on Gold journal February 2013
Self-assembly of thioether functionalized fullerenes on gold and their activity in electropolymerization of styrene journal January 2015
High-Resolution STM and XPS Studies of Thiophene Self-Assembled Monolayers on Au(111) journal July 2002
Organosulfur Monolayers at Gold Surfaces:  Reexamination of the Case for Sulfide Adsorption and Implications to the Formation of Monolayers from Thiols and Disulfides journal December 1998
Measuring single molecule conductance with break junctions journal January 2006
Impact of Junction Formation Method and Surface Roughness on Single Molecule Conductance journal March 2009
Conductance of Single Alkanedithiols:  Conduction Mechanism and Effect of Molecule−Electrode Contacts journal February 2006
Properties of the gold–sulphur interface: from self-assembled monolayers to clusters journal January 2015
The Fate of Sulfur-Bound Hydrogen on Formation of Self-Assembled Thiol Monolayers on Gold:  1 H NMR Spectroscopic Evidence from Solutions of Gold Clusters journal February 2002
Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold journal March 2014
Physisorption and Chemisorption of Alkanethiols and Alkyl Sulfides on Au(111) journal April 1998
Experimental and Theoretical Analysis of Nanotransport in Oligophenylene Dithiol Junctions as a Function of Molecular Length and Contact Work Function journal July 2015
Extreme Conductance Suppression in Molecular Siloxanes journal July 2017
Electric Field Breakdown in Single Molecule Junctions journal February 2015
A Mild and Environmentally Benign Oxidation of Thiols to Disulfides journal November 2007
Luminescence Studies of Gold(I) Thiolate Complexes journal December 1995
Different emissive properties in dithiolate gold(i) complexes as a function of the presence of phenylene spacers journal January 2014
The SIESTA method for ab initio order- N materials simulation journal March 2002

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