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Chem Asian J. 2013 Sep;8(9):2023-32. doi: 10.1002/asia.201300419. Epub 2013 Jun 14.

Experimental and theoretical studies of charge delocalization in biruthenium-alkynyl complexes bridged by thiophenes.

Author information

  • 1Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China.

Abstract

A series of binuclear ruthenium-alkynyl complexes that are bridged by thiophene groups (thiophene, bithiophene, and terthiophene) have been synthesized. All of these complexes have been well-characterized by NMR spectroscopy, X-ray diffraction, and elemental analysis. The electronic properties of these complexes have been examined by using cyclic voltammetry, UV/Vis/NIR and IR spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and density functional theory (DFT) calculations. Electrochemical results showed that the potential difference (ΔE) and comproportionation constant (Kc) decreased with increasing size of the thiophene bridging unit. The UV/Vis/NIR spectra and TDDFT calculations of the monocations indicated that the NIR transitions displayed aromatic bridging character. EPR studies of the mono-oxidized radical species further demonstrated that the unpaired electron/hole was delocalized over both metals and the bridging ligand and established significant participation in the ligand oxidation.

Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

KEYWORDS:

bridging ligands; radicals; redox chemistry; ruthenium; thiophenes

PMID:
23775815
[PubMed - indexed for MEDLINE]
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