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    Rights statement: This is the peer reviewed version of the following article: H. Ozawa, M. Baghernejad, O. A. Al-Owaedi, V. Kaliginedi, T. Nagashima, J. Ferrer, T. Wandlowski, V. M. García-Suárez, P. Broekmann, C. J. Lambert, M.-a. Haga, Chem. Eur. J. 2016, 22, 12732 which has been published in final form at https://onlinelibrary.wiley.com/doi/full/10.1002/chem.201600616abstract This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving.

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Synthesis and Single-Molecule Conductance Study of Redox-Active Ruthenium Complexes with Pyridyl and Dihydrobenzo[b]thiophene Anchoring Groups

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<mark>Journal publication date</mark>26/08/2016
<mark>Journal</mark>Chemistry - A European Journal
Issue number36
Volume22
Number of pages9
Pages (from-to)12732-12740
Publication StatusPublished
Early online date29/07/16
<mark>Original language</mark>English

Abstract

The ancillary ligands 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine and 4′-(2,3-dihydrobenzo[b]thiophene)-2,2′-6′,2“-terpyridine were used to synthesize two series of mono- and dinuclear ruthenium complexes differing in their lengths and anchoring groups. The electrochemical and single-molecular conductance properties of these two series of ruthenium complexes were studied experimentally by means of cyclic voltammetry and the scanning tunneling microscopy-break junction technique (STM-BJ) and theoretically by means of density functional theory (DFT). Cyclic voltammetry data showed clear redox peaks corresponding to both the metal- and ligand-related redox reactions. Single-molecular conductance demonstrated an exponential decay of the molecular conductance with the increase in molecular length for both the series of ruthenium complexes, with decay constants of βPY=2.07±0.1 nm−1 and βBT=2.16±0.1 nm−1, respectively. The contact resistance of complexes with 2,3-dihydrobenzo[b]thiophene (BT) anchoring groups is found to be smaller than the contact resistance of ruthenium complexes with pyridine (PY) anchors. DFT calculations support the experimental results and provided additional information on the electronic structure and charge transport properties in those metal|ruthenium complex|metal junctions.

Bibliographic note

This is the peer reviewed version of the following article: H. Ozawa, M. Baghernejad, O. A. Al-Owaedi, V. Kaliginedi, T. Nagashima, J. Ferrer, T. Wandlowski, V. M. García-Suárez, P. Broekmann, C. J. Lambert, M.-a. Haga, Chem. Eur. J. 2016, 22, 12732 which has been published in final form at https://onlinelibrary.wiley.com/doi/full/10.1002/chem.201600616abstract This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving.