Electrochemical gating of single osmium molecules tethered to Au surfaces
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- 作者：Santiago Herrera ; Catherine Adam…
- 关键词：Self ; assembled monolayer ; Osmium complex ; Electronic transfer ; Electrochemical scanning tunneling spectroscopy ; gating
- 刊名：Journal of Solid State Electrochemistry
- 出版年：2016
- 出版时间：April 2016
- 年：2016
- 卷：20
- 期：4
- 页码：957-967
- 全文大小：865 KB
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Catherine Adam (1)
Alejandra Ricci (1) (2)
Ernesto J. Calvo (1)
1. INQUIMAE. Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2, Ciudad Universitaria, AR-1419, Buenos Aires, Argentina
2. Aluar, Puerto Madryn, Chubut, U1200IA, Argentina - 刊物类别：Chemistry and Materials Science
- 刊物主题：Chemistry
Physical Chemistry
Analytical Chemistry
Industrial Chemistry and Chemical Engineering
Characterization and Evaluation Materials
Condensed Matter
Electronic and Computer Engineering - 出版者：Springer Berlin / Heidelberg
- ISSN：1433-0768
文摘
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 k ET 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, E ref − E s, and the tip-substrate bias potential, E bias. 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 bias. 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 ET 0.