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In Situ Gap-Mode Raman Spectroscopy on Single-Crystal Au(100) Electrodes : Tuning the Torsion Angle of 4,4'-Biphenyldithiols by an Electrochemical Gate Field

Cui, Li and Liu, Bo and Vonlanthen, David and Mayor, Marcel and Fu, Yongchun and Li, Jian-Feng and Wandlowski, Thomas. (2011) In Situ Gap-Mode Raman Spectroscopy on Single-Crystal Au(100) Electrodes : Tuning the Torsion Angle of 4,4'-Biphenyldithiols by an Electrochemical Gate Field. Journal of the American Chemical Society, 133 (19). pp. 7332-7335.

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Official URL: http://edoc.unibas.ch/dok/A5843760

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Abstract

In situ gap-mode Raman spectra were acquired in an electrochemical environment on a single-crystal gold electrode employing a Au(100)|4,4′-biphenyldithiol (BPDT)|Au-NP(55 nm) sandwich assembly. This geometry enabled an investigation of the influence of an applied electrochemical gate field on the conformational changes in nanojunctions, such as the torsion angle (φ) of molecules. A linear correlation between the intensity ratio IC═C/ICring–S and cos2 φ in 4,4′-BPDT-type molecular junctions was established and subsequently utilized to estimate the potential dependence of the torsion angle of the “flexible” molecule M1 at different potentials. The latter decreases as the potential (charge) becomes more negative, resulting in better π–π coupling, which correlates with enhanced junction conductance. The demonstrated spectroelectrochemical strategy and the direct correlation of the spectroscopic results with (single) molecular conductance studies may guide the selection and elucidation of functional molecules for potential applications in novel nanodevices.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Molecular Devices and Materials (Mayor)
UniBasel Contributors:Mayor, Marcel and Vonlanthen, David
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:0002-7863
e-ISSN:1520-5126
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:05 Apr 2017 12:01
Deposited On:14 Sep 2012 07:01

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