View in EDS

Electrochemical gating of single osmium molecules tethered to Au surfaces.

Saved in:
Bibliographic Details
Title: Electrochemical gating of single osmium molecules tethered to Au surfaces.
Authors: Herrera, Santiago1, Adam, Catherine1, Ricci, Alejandra, Calvo, Ernesto1 calvo@qi.fcen.uba.ar
Source: Journal of Solid State Electrochemistry. Apr2016, Vol. 20 Issue 4, p957-967. 11p.
Subjects: Osmium, Gold, Electrochemical analysis, Electron transport, Electrodes
Abstract: The electrochemical study of electron transport between Au electrodes and the redox molecule Os[(bpy)(PyCH NHCO-]ClO 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 k 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, E − E, and the tip-substrate bias potential, E. 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 E. 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, k. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Solid State Electrochemistry is the property of Springer Nature and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
FullText Text:
  Availability: 0
Header DbId: egs
DbLabel: Engineering Source
An: 113929545
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
IllustrationInfo
Items – Name: Title
  Label: Title
  Group: Ti
  Data: Electrochemical gating of single osmium molecules tethered to Au surfaces.
– Name: Author
  Label: Authors
  Group: Au
  Data: <searchLink fieldCode="AR" term="%22Herrera%2C+Santiago%22">Herrera, Santiago</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Adam%2C+Catherine%22">Adam, Catherine</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Ricci%2C+Alejandra%22">Ricci, Alejandra</searchLink><br /><searchLink fieldCode="AR" term="%22Calvo%2C+Ernesto%22">Calvo, Ernesto</searchLink><relatesTo>1</relatesTo><i> calvo@qi.fcen.uba.ar</i>
– Name: TitleSource
  Label: Source
  Group: Src
  Data: <searchLink fieldCode="JN" term="%22Journal+of+Solid+State+Electrochemistry%22">Journal of Solid State Electrochemistry</searchLink>. Apr2016, Vol. 20 Issue 4, p957-967. 11p.
– Name: Subject
  Label: Subjects
  Group: Su
  Data: <searchLink fieldCode="DE" term="%22Osmium%22">Osmium</searchLink><br /><searchLink fieldCode="DE" term="%22Gold%22">Gold</searchLink><br /><searchLink fieldCode="DE" term="%22Electrochemical+analysis%22">Electrochemical analysis</searchLink><br /><searchLink fieldCode="DE" term="%22Electron+transport%22">Electron transport</searchLink><br /><searchLink fieldCode="DE" term="%22Electrodes%22">Electrodes</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: The electrochemical study of electron transport between Au electrodes and the redox molecule Os[(bpy)(PyCH NHCO-]ClO 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 k 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, E − E, and the tip-substrate bias potential, E. 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 E. 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, k. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of Solid State Electrochemistry is the property of Springer Nature and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
PLink https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=113929545
RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1007/s10008-015-2983-8
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 11
        StartPage: 957
    Subjects:
      – SubjectFull: Osmium
        Type: general
      – SubjectFull: Gold
        Type: general
      – SubjectFull: Electrochemical analysis
        Type: general
      – SubjectFull: Electron transport
        Type: general
      – SubjectFull: Electrodes
        Type: general
    Titles:
      – TitleFull: Electrochemical gating of single osmium molecules tethered to Au surfaces.
        Type: main
  BibRelationships:
    HasContributorRelationships:
      – PersonEntity:
          Name:
            NameFull: Herrera, Santiago
      – PersonEntity:
          Name:
            NameFull: Adam, Catherine
      – PersonEntity:
          Name:
            NameFull: Ricci, Alejandra
      – PersonEntity:
          Name:
            NameFull: Calvo, Ernesto
    IsPartOfRelationships:
      – BibEntity:
          Dates:
            – D: 01
              M: 04
              Text: Apr2016
              Type: published
              Y: 2016
          Identifiers:
            – Type: issn-print
              Value: 14328488
          Numbering:
            – Type: volume
              Value: 20
            – Type: issue
              Value: 4
          Titles:
            – TitleFull: Journal of Solid State Electrochemistry
              Type: main
ResultId 1