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

Ozawa, Hiroaki; Baghernejad, Masoud; Al-Owaedi, Oday A.; Kaliginedi, Veera Bhadra Rao; Nagashima, Takumi; Ferrer, Jaime; Wandlowski, Thomas; García-Suárez, Víctor M.; Broekmann, Peter; Lambert, Colin J.; 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. Wiley-VCH 10.1002/chem.201600616

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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 (Original Article)

Division/Institute:

08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Baghernejad, Masoud; Kaliginedi, Veera Bhadra Rao; Wandlowski, Thomas and Broekmann, Peter

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry
500 Science

ISSN:

0947-6539

Publisher:

Wiley-VCH

Language:

English

Submitter:

Beatrice Niederhauser

Date Deposited:

24 Jan 2017 10:40

Last Modified:

24 Jan 2017 10:40

Publisher DOI:

10.1002/chem.201600616

PubMed ID:

27472889

BORIS DOI:

10.7892/boris.92719

URI:

https://boris.unibe.ch/id/eprint/92719

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