Chun‐Yuen Wong, L. Lai, P. Pat
Sep 16, 2009
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Organometallics
Abstract
Ruthenium(II)−acetylide complexes bearing 1,4,7-trithiacyclononane ([9]aneS3) and 1,10-phenanthroline (phen) have been prepared. The molecular structure of [([9]aneS3)(phen)Ru−C≡CPh]+ shows that the trans influence of the acetylide ligand is only slightly weaker than that of isocyanide and is stronger than that of chloride. The Ru(II/III) oxidation waves for the complexes are irreversible, with Epa = 0.30−0.39 V vs Cp2Fe+/0. The lowest-energy dipole-allowed absorptions for the complexes (λmax = 441−466 nm, emax = (4−5) × 103 dm3 mol−1 cm−1) are assigned as dπ(RuII) → π*(phen) metal-to-ligand charge transfer (MLCT) transitions. The complexes are emissive in glassy MeOH/EtOH at 77 K upon photoexcitation and give emission at λmax = 606−623 nm. Density functional theory (DFT) calculations and charge decomposition analysis (CDA) have been used to probe the Ru−C bonding interaction in these complexes, and the results are compared with their isocyanide congeners. The rotational barrier for the phenyl ring in [([...