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Abstract:

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.

Registro:

Documento: Artículo
Título:Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111)
Autor:Fernández, C.C.; Pensa, E.; Carro, P.; Salvarezza, R.; Williams, F.J.
Filiación:Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, INQUIMAE-CONICET, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, Buenos Aires, C1428EHA, Argentina
Facultad de Ciencias Exactas, Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Universidad Nacional de la Plata, CONICET, La Plata, 1900, Argentina
Área de Química Física, Departamento de Química, Facultad de Ciencias, Universidad de la Laguna, Instituto de Materiales y Nanotecnología, Avda. Francisco Sánchez, s/n, La Laguna, Tenerife, 38200, Spain
Palabras clave: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
Año:2018
Volumen:34
Número:20
Página de inicio:5696
Página de fin:5702
DOI: http://dx.doi.org/10.1021/acs.langmuir.8b00807
Título revista:Langmuir
Título revista abreviado:Langmuir
ISSN:07437463
CODEN:LANGD
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_07437463_v34_n20_p5696_Fernandez

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Citas:

---------- APA ----------
Fernández, C.C., Pensa, E., Carro, P., Salvarezza, R. & Williams, F.J. (2018) . Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111). Langmuir, 34(20), 5696-5702.
http://dx.doi.org/10.1021/acs.langmuir.8b00807
---------- CHICAGO ----------
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)" . Langmuir 34, no. 20 (2018) : 5696-5702.
http://dx.doi.org/10.1021/acs.langmuir.8b00807
---------- MLA ----------
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)" . Langmuir, vol. 34, no. 20, 2018, pp. 5696-5702.
http://dx.doi.org/10.1021/acs.langmuir.8b00807
---------- VANCOUVER ----------
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). Langmuir. 2018;34(20):5696-5702.
http://dx.doi.org/10.1021/acs.langmuir.8b00807