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

Ozawa, Hiroaki and Baghernejad, Masoud and Al-Owaedi, Oday and Kaliginedi, Veerabhadrarao and Nagashima, Takumi and Ferrer, Jamie and Wandlowski, Thomas and Garcia-Suarez, Victor Manuel and Broekmann, Peter and Lambert, Colin John and Haga, Masa-aki (2016) Synthesis and Single-Molecule Conductance Study of Redox-Active Ruthenium Complexes with Pyridyl and Dihydrobenzo[b]thiophene Anchoring Groups. Chemistry - A European Journal, 22 (36). pp. 12732-12740. ISSN 0947-6539

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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.

Item Type: Journal Article
Journal or Publication Title: Chemistry - A European Journal
Additional Information: 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.
Uncontrolled Keywords: /dk/atira/pure/subjectarea/asjc/1600
Subjects:
Departments: Faculty of Science and Technology > Physics
ID Code: 82145
Deposited By: ep_importer_pure
Deposited On: 05 Feb 2019 13:40
Refereed?: Yes
Published?: Published
Last Modified: 15 Nov 2019 02:54
URI: https://eprints.lancs.ac.uk/id/eprint/82145

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