Self-assembly, characterization, and chemical stability of isocyanide-bound molecular wire monolayers on gold and palladium surfaces

Joshua James Stapleton, Thomas A. Daniel, Sundarajan Uppili, Orlando M. Cabarcos, Jawad Naciri, Ranganathan Shashidhar, David L. Allara

Research output: Contribution to journalArticle

66 Citations (Scopus)

Abstract

Self-assembled monolayers (SAMs) of the isocyano derivative of 4,4′-di(phenylene-ethynylene)benzene (1), a member of the "OPE" family of "molecular wires" of current interest in molecular electronics, have been prepared on smooth, {111} textured films of Au and Pd. For assembly in oxygen-free environments with freshly deposited metal surfaces, infrared reflection spectroscopy (IRS) indicates the molecules assume a tilted structure with average tilt angles of 18-24° from the surface normal. The combination of IRS, X-ray photoelectron spectroscopy, and density functional theory calculations all support a single σ-type bond of the -NC group to the Au surface and a σ/π-type of bond to the Pd surface. Both SAMs show significant chemical instability when exposed to typical ambient conditions. In the case of the Au SAM, even a few hours storage in air results in significant oxidation of the -NC moieties to -NCO (isocyanate) with an accompanying decrease in surface chemical bonding, as evidenced by a significant increase in instability toward dissolution in solvent. In the case of the Pd SAM, similar air exposure does not result in incorporation of oxygen or loss of solvent resistance but rather results in a chemically altered interface which is attributed to polymerization of the -NC moieties to quasi-2D poly(imine) structures. Conductance probe atomic force microscope measurements show the conductance of the degraded Pd SAMs can diminish by ∼2 orders of magnitude, an indication that the SAM-Pd electrical contact has severely degraded. These results underscore the importance of careful control of the assembly procedures for aromatic isocyanide SAMs, particularly for applications in molecular electronics where the molecule-electrode junction is critical to the operational characteristics of the device.

Original languageEnglish (US)
Pages (from-to)11061-11070
Number of pages10
JournalLangmuir
Volume21
Issue number24
DOIs
StatePublished - Nov 22 2005

Fingerprint

Chemical stability
Palladium
Cyanides
Self assembled monolayers
Gold
Self assembly
self assembly
palladium
Monolayers
wire
Wire
gold
molecular electronics
infrared reflection
assembly
Molecular electronics
isocyanates
air
oxygen
imines

All Science Journal Classification (ASJC) codes

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

Cite this

Stapleton, Joshua James ; Daniel, Thomas A. ; Uppili, Sundarajan ; Cabarcos, Orlando M. ; Naciri, Jawad ; Shashidhar, Ranganathan ; Allara, David L. / Self-assembly, characterization, and chemical stability of isocyanide-bound molecular wire monolayers on gold and palladium surfaces. In: Langmuir. 2005 ; Vol. 21, No. 24. pp. 11061-11070.
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abstract = "Self-assembled monolayers (SAMs) of the isocyano derivative of 4,4′-di(phenylene-ethynylene)benzene (1), a member of the {"}OPE{"} family of {"}molecular wires{"} of current interest in molecular electronics, have been prepared on smooth, {111} textured films of Au and Pd. For assembly in oxygen-free environments with freshly deposited metal surfaces, infrared reflection spectroscopy (IRS) indicates the molecules assume a tilted structure with average tilt angles of 18-24° from the surface normal. The combination of IRS, X-ray photoelectron spectroscopy, and density functional theory calculations all support a single σ-type bond of the -NC group to the Au surface and a σ/π-type of bond to the Pd surface. Both SAMs show significant chemical instability when exposed to typical ambient conditions. In the case of the Au SAM, even a few hours storage in air results in significant oxidation of the -NC moieties to -NCO (isocyanate) with an accompanying decrease in surface chemical bonding, as evidenced by a significant increase in instability toward dissolution in solvent. In the case of the Pd SAM, similar air exposure does not result in incorporation of oxygen or loss of solvent resistance but rather results in a chemically altered interface which is attributed to polymerization of the -NC moieties to quasi-2D poly(imine) structures. Conductance probe atomic force microscope measurements show the conductance of the degraded Pd SAMs can diminish by ∼2 orders of magnitude, an indication that the SAM-Pd electrical contact has severely degraded. These results underscore the importance of careful control of the assembly procedures for aromatic isocyanide SAMs, particularly for applications in molecular electronics where the molecule-electrode junction is critical to the operational characteristics of the device.",
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Self-assembly, characterization, and chemical stability of isocyanide-bound molecular wire monolayers on gold and palladium surfaces. / Stapleton, Joshua James; Daniel, Thomas A.; Uppili, Sundarajan; Cabarcos, Orlando M.; Naciri, Jawad; Shashidhar, Ranganathan; Allara, David L.

In: Langmuir, Vol. 21, No. 24, 22.11.2005, p. 11061-11070.

Research output: Contribution to journalArticle

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T1 - Self-assembly, characterization, and chemical stability of isocyanide-bound molecular wire monolayers on gold and palladium surfaces

AU - Stapleton, Joshua James

AU - Daniel, Thomas A.

AU - Uppili, Sundarajan

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N2 - Self-assembled monolayers (SAMs) of the isocyano derivative of 4,4′-di(phenylene-ethynylene)benzene (1), a member of the "OPE" family of "molecular wires" of current interest in molecular electronics, have been prepared on smooth, {111} textured films of Au and Pd. For assembly in oxygen-free environments with freshly deposited metal surfaces, infrared reflection spectroscopy (IRS) indicates the molecules assume a tilted structure with average tilt angles of 18-24° from the surface normal. The combination of IRS, X-ray photoelectron spectroscopy, and density functional theory calculations all support a single σ-type bond of the -NC group to the Au surface and a σ/π-type of bond to the Pd surface. Both SAMs show significant chemical instability when exposed to typical ambient conditions. In the case of the Au SAM, even a few hours storage in air results in significant oxidation of the -NC moieties to -NCO (isocyanate) with an accompanying decrease in surface chemical bonding, as evidenced by a significant increase in instability toward dissolution in solvent. In the case of the Pd SAM, similar air exposure does not result in incorporation of oxygen or loss of solvent resistance but rather results in a chemically altered interface which is attributed to polymerization of the -NC moieties to quasi-2D poly(imine) structures. Conductance probe atomic force microscope measurements show the conductance of the degraded Pd SAMs can diminish by ∼2 orders of magnitude, an indication that the SAM-Pd electrical contact has severely degraded. These results underscore the importance of careful control of the assembly procedures for aromatic isocyanide SAMs, particularly for applications in molecular electronics where the molecule-electrode junction is critical to the operational characteristics of the device.

AB - Self-assembled monolayers (SAMs) of the isocyano derivative of 4,4′-di(phenylene-ethynylene)benzene (1), a member of the "OPE" family of "molecular wires" of current interest in molecular electronics, have been prepared on smooth, {111} textured films of Au and Pd. For assembly in oxygen-free environments with freshly deposited metal surfaces, infrared reflection spectroscopy (IRS) indicates the molecules assume a tilted structure with average tilt angles of 18-24° from the surface normal. The combination of IRS, X-ray photoelectron spectroscopy, and density functional theory calculations all support a single σ-type bond of the -NC group to the Au surface and a σ/π-type of bond to the Pd surface. Both SAMs show significant chemical instability when exposed to typical ambient conditions. In the case of the Au SAM, even a few hours storage in air results in significant oxidation of the -NC moieties to -NCO (isocyanate) with an accompanying decrease in surface chemical bonding, as evidenced by a significant increase in instability toward dissolution in solvent. In the case of the Pd SAM, similar air exposure does not result in incorporation of oxygen or loss of solvent resistance but rather results in a chemically altered interface which is attributed to polymerization of the -NC moieties to quasi-2D poly(imine) structures. Conductance probe atomic force microscope measurements show the conductance of the degraded Pd SAMs can diminish by ∼2 orders of magnitude, an indication that the SAM-Pd electrical contact has severely degraded. These results underscore the importance of careful control of the assembly procedures for aromatic isocyanide SAMs, particularly for applications in molecular electronics where the molecule-electrode junction is critical to the operational characteristics of the device.

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