Electrochemical gating of single osmium molecules tethered to Au surfaces

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 th...

Descripción completa

Guardado en:

Detalles Bibliográficos
Autores principales:	Herrera, S., Adam, C., Ricci, A., Calvo, E.J.
Formato:	JOUR
Materias:	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
Acceso en línea:	http://hdl.handle.net/20.500.12110/paper_14328488_v20_n4_p957_Herrera
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	todo:paper_14328488_v20_n4_p957_Herrera
record_format	dspace
spelling	todo:paper_14328488_v20_n4_p957_Herrera2023-10-03T16:14:00Z Electrochemical gating of single osmium molecules tethered to Au surfaces Herrera, S. Adam, C. Ricci, A. Calvo, E.J. 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 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. Fil:Ricci, A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Calvo, E.J. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_14328488_v20_n4_p957_Herrera
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	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
spellingShingle	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 Herrera, S. Adam, C. Ricci, A. Calvo, E.J. Electrochemical gating of single osmium molecules tethered to Au surfaces
topic_facet	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
description	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.
format	JOUR
author	Herrera, S. Adam, C. Ricci, A. Calvo, E.J.
author_facet	Herrera, S. Adam, C. Ricci, A. Calvo, E.J.
author_sort	Herrera, S.
title	Electrochemical gating of single osmium molecules tethered to Au surfaces
title_short	Electrochemical gating of single osmium molecules tethered to Au surfaces
title_full	Electrochemical gating of single osmium molecules tethered to Au surfaces
title_fullStr	Electrochemical gating of single osmium molecules tethered to Au surfaces
title_full_unstemmed	Electrochemical gating of single osmium molecules tethered to Au surfaces
title_sort	electrochemical gating of single osmium molecules tethered to au surfaces
url	http://hdl.handle.net/20.500.12110/paper_14328488_v20_n4_p957_Herrera
work_keys_str_mv	AT herreras electrochemicalgatingofsingleosmiummoleculestetheredtoausurfaces AT adamc electrochemicalgatingofsingleosmiummoleculestetheredtoausurfaces AT riccia electrochemicalgatingofsingleosmiummoleculestetheredtoausurfaces AT calvoej electrochemicalgatingofsingleosmiummoleculestetheredtoausurfaces
_version_	1807321751015653376

Electrochemical gating of single osmium molecules tethered to Au surfaces

Ejemplares similares