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Abstract:

The electrochemical study of electron transport between Au electrodes and the redox molecule Os[(bpy)2(PyCH2 NH2CO-]ClO4 tethered to molecular linkers of different length (1.3 to 2.9 nm) to Au surfaces has shown an exponential decay of the rate constant kET 0 with a slope β = 0.53 consistent with through bond tunneling to the redox center. Electrochemical gating of single osmium molecules in an asymmetric tunneling nano-gap between a Au(111) substrate electrode modified with the redox molecules and a Pt-Ir tip of a scanning tunneling microscope was achieved by independent control of the reference electrode potential in the electrolyte, Eref − Es, and the tip-substrate bias potential, Ebias. Enhanced tunneling current at the osmium complex redox potential was observed as compared to the off resonance set point tunneling current with a linear dependence of the overpotential at maximum current vs. the Ebias. This corresponds to a sequential two-step electron transfer with partial vibration relaxation from the substrate Au(111) to the redox molecule in the nano-gap and from this redox state to the Pt-Ir tip according to the model of Kuznetsov and Ulstrup (J Phys Chem A 104: 11531, 2000). Comparison of short and long linkers of the osmium complex has shown the same two-step ET (electron transfer) behavior due to the long time scale in the complete reduction-oxidation cycle in the electrochemical tunneling spectroscopy (EC-STS) experiment as compared to the time constants for electron transfer for all linker distances, kET 0. © 2015, Springer-Verlag Berlin Heidelberg.

Registro:

Documento: Artículo
Título:Electrochemical gating of single osmium molecules tethered to Au surfaces
Autor:Herrera, S.; Adam, C.; Ricci, A.; Calvo, E.J.
Filiación:INQUIMAE. Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2, Ciudad Universitaria, Buenos Aires, AR-1419, Argentina
Aluar, Puerto Madryn, Chubut U1200IA, Argentina
Palabras clave:Electrochemical scanning tunneling spectroscopy-gating; Electronic transfer; Osmium complex; Self-assembled monolayer; Binary alloys; Chlorine compounds; Electrochemical electrodes; Electrolytes; Electron transitions; Electron transport properties; Electron tunneling; Gold; Iridium alloys; Molecules; Nanostructures; Nitrogen compounds; Osmium compounds; Platinum alloys; Rate constants; Redox reactions; Scanning tunneling microscopy; Self assembled monolayers; Spectroscopy; Substrates; Au (111) substrates; Electrochemical gating; Electrochemical studies; Electronic transfers; Osmium complexes; Reference electrode potentials; Scanning tunneling spectroscopy; Tunneling spectroscopy; Phosphorus compounds
Año:2016
Volumen:20
Número:4
Página de inicio:957
Página de fin:967
DOI: http://dx.doi.org/10.1007/s10008-015-2983-8
Título revista:Journal of Solid State Electrochemistry
Título revista abreviado:J. Solid State Electrochem.
ISSN:14328488
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14328488_v20_n4_p957_Herrera

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Citas:

---------- APA ----------
Herrera, S., Adam, C., Ricci, A. & Calvo, E.J. (2016) . Electrochemical gating of single osmium molecules tethered to Au surfaces. Journal of Solid State Electrochemistry, 20(4), 957-967.
http://dx.doi.org/10.1007/s10008-015-2983-8
---------- CHICAGO ----------
Herrera, S., Adam, C., Ricci, A., Calvo, E.J. "Electrochemical gating of single osmium molecules tethered to Au surfaces" . Journal of Solid State Electrochemistry 20, no. 4 (2016) : 957-967.
http://dx.doi.org/10.1007/s10008-015-2983-8
---------- MLA ----------
Herrera, S., Adam, C., Ricci, A., Calvo, E.J. "Electrochemical gating of single osmium molecules tethered to Au surfaces" . Journal of Solid State Electrochemistry, vol. 20, no. 4, 2016, pp. 957-967.
http://dx.doi.org/10.1007/s10008-015-2983-8
---------- VANCOUVER ----------
Herrera, S., Adam, C., Ricci, A., Calvo, E.J. Electrochemical gating of single osmium molecules tethered to Au surfaces. J. Solid State Electrochem. 2016;20(4):957-967.
http://dx.doi.org/10.1007/s10008-015-2983-8