Accessibility navigation


Diruthenium complexes with bridging diethynyl polyaromatic ligands: synthesis, spectroelectrochemistry, and theoretical calculations

Zhang, J., Zhang, M.-X., Sun, C.-F., Xu, M., Hartl, F., Yin, J., Yu, G. A., Rao, L. and Liu, S. H. (2015) Diruthenium complexes with bridging diethynyl polyaromatic ligands: synthesis, spectroelectrochemistry, and theoretical calculations. Organometallics, 34 (16). pp. 3967-3978. ISSN 1520-6041

Full text not archived in this repository.

It is advisable to refer to the publisher's version if you intend to cite from this work. See Guidance on citing.

To link to this item DOI: 10.1021/acs.organomet.5b00276

Abstract/Summary

This work describes syntheses and electrochemical, spectroscopic, and bonding properties in a new series of dinuclear ruthenium(II) complexes bridged by polyaromatic (biphenyl, fluorene, phenanthrene, and pyrene) alkynyl ligands. Longitudinal expansion of the π-conjugated polyaromatic core of the bridging ligands caused a reduced potential difference between the anodic steps and reinforced their bridge-localized nature, as evidenced by UV/vis/near-IR and IR spectroelectrochemical data combined with DFT and TDDFT calculations. Importantly, the intricate multiple IR ν(CC) absorption bands for the singly oxidized states imply a thermal population of a range of conformers (rotamers) with distinct electronic character. This behavior was demonstrated with more accurate DFT calculations of selected nontruncated 1e− oxidized complexes in three different conformations. The combined experimental and theoretical data reveal that thermally populated rotamers featuring various mutual orientations of the ligated metal termini and the bridging diethynyl polyaromatic moieties have a significant impact on the electronic absorption and ν(CC) wavenumbers of the singly oxidized systems.

Item Type:Article
Refereed:Yes
Divisions:Interdisciplinary centres and themes > Chemical Analysis Facility (CAF)
Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:46521
Publisher:American Chemical Society

University Staff: Request a correction | Centaur Editors: Update this record

Page navigation