Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111)

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The electronic structure of aromatic and aliphatic thiols on Au(111) has been extensively studied in relation to possible applications in molecular electronics. In this work, the effect on the electronic structure of an additional anchor to the S-Au bond using 6-mercaptopurine as a model system has...

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Autores principales: Fernández, C.C., Pensa, E., Carro, P., Salvarezza, R., Williams, F.J.
Formato: JOUR
Materias:
Electronic structure
Interfaces (materials)
Molecules
Self assembled monolayers
Self assembly
6-Mercaptopurine
Aliphatic thiols
Molecular dipole
Molecular domains
Molecular state
Negative charge
Positive charges
Rectangular lattices
Substrates
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_07437463_v34_n20_p5696_Fernandez
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_07437463_v34_n20_p5696_Fernandez
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spelling todo:paper_07437463_v34_n20_p5696_Fernandez2023-10-03T15:38:50Z Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111) Fernández, C.C. Pensa, E. Carro, P. Salvarezza, R. Williams, F.J. Electronic structure Interfaces (materials) Molecules Self assembled monolayers Self assembly 6-Mercaptopurine Aliphatic thiols Molecular dipole Molecular domains Molecular state Negative charge Positive charges Rectangular lattices Substrates The electronic structure of aromatic and aliphatic thiols on Au(111) has been extensively studied in relation to possible applications in molecular electronics. In this work, the effect on the electronic structure of an additional anchor to the S-Au bond using 6-mercaptopurine as a model system has been investigated. Results from X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and density functional theory (DFT) confirm that this molecule adsorbs on Au(111) with S-Au and iminic N-Au bonds. Combined ultraviolet photoelectron spectroscopy and DFT data reveal that formation of the 6MP self-assembled monolayer generates a molecular dipole perpendicular to the surface, with negative charges residing at the metal/monolayer interface and positive charges at the monolayer/vacuum interface, which lowers the substrate work function. Scanning tunneling microscopy shows two surface molecular domains: a well-ordered rectangular lattice where molecules are tilted on average 30° with respect to the substrate and aligned 6MP islands where molecules are standing upright. Finally, we found a new electronic state located at -1.7 eV with respect to the Fermi level that corresponds to a localized π molecular state, while the state corresponding to the N-Au bond is hybridized with Au d electrons and stabilized at much lower energies (-3 eV). Copyright © 2018 American Chemical Society. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_07437463_v34_n20_p5696_Fernandez
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Electronic structure
Interfaces (materials)
Molecules
Self assembled monolayers
Self assembly
6-Mercaptopurine
Aliphatic thiols
Molecular dipole
Molecular domains
Molecular state
Negative charge
Positive charges
Rectangular lattices
Substrates
spellingShingle Electronic structure
Interfaces (materials)
Molecules
Self assembled monolayers
Self assembly
6-Mercaptopurine
Aliphatic thiols
Molecular dipole
Molecular domains
Molecular state
Negative charge
Positive charges
Rectangular lattices
Substrates
Fernández, C.C.
Pensa, E.
Carro, P.
Salvarezza, R.
Williams, F.J.
Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111)
topic_facet Electronic structure
Interfaces (materials)
Molecules
Self assembled monolayers
Self assembly
6-Mercaptopurine
Aliphatic thiols
Molecular dipole
Molecular domains
Molecular state
Negative charge
Positive charges
Rectangular lattices
Substrates
description The electronic structure of aromatic and aliphatic thiols on Au(111) has been extensively studied in relation to possible applications in molecular electronics. In this work, the effect on the electronic structure of an additional anchor to the S-Au bond using 6-mercaptopurine as a model system has been investigated. Results from X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and density functional theory (DFT) confirm that this molecule adsorbs on Au(111) with S-Au and iminic N-Au bonds. Combined ultraviolet photoelectron spectroscopy and DFT data reveal that formation of the 6MP self-assembled monolayer generates a molecular dipole perpendicular to the surface, with negative charges residing at the metal/monolayer interface and positive charges at the monolayer/vacuum interface, which lowers the substrate work function. Scanning tunneling microscopy shows two surface molecular domains: a well-ordered rectangular lattice where molecules are tilted on average 30° with respect to the substrate and aligned 6MP islands where molecules are standing upright. Finally, we found a new electronic state located at -1.7 eV with respect to the Fermi level that corresponds to a localized π molecular state, while the state corresponding to the N-Au bond is hybridized with Au d electrons and stabilized at much lower energies (-3 eV). Copyright © 2018 American Chemical Society.
format JOUR
author Fernández, C.C.
Pensa, E.
Carro, P.
Salvarezza, R.
Williams, F.J.
author_facet Fernández, C.C.
Pensa, E.
Carro, P.
Salvarezza, R.
Williams, F.J.
author_sort Fernández, C.C.
title Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111)
title_short Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111)
title_full Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111)
title_fullStr Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111)
title_full_unstemmed Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111)
title_sort electronic structure of a self-assembled monolayer with two surface anchors: 6-mercaptopurine on au(111)
url http://hdl.handle.net/20.500.12110/paper_07437463_v34_n20_p5696_Fernandez
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AT pensae electronicstructureofaselfassembledmonolayerwithtwosurfaceanchors6mercaptopurineonau111
AT carrop electronicstructureofaselfassembledmonolayerwithtwosurfaceanchors6mercaptopurineonau111
AT salvarezzar electronicstructureofaselfassembledmonolayerwithtwosurfaceanchors6mercaptopurineonau111
AT williamsfj electronicstructureofaselfassembledmonolayerwithtwosurfaceanchors6mercaptopurineonau111
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