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Title: Ruthenium Bis-diimine Complexes with a Chelating Thioether Ligand: Delineating 1,10-Phenanthrolinyl and 2,2'-Bipyridyl Ligand Substituent Effects

A new series of ruthenium(II) bis-diimine complexes with a chelating thioether donor ligand has been prepared: Ru(diimine)2(dpte)2+ (diimine=1,10-phenanthroline (phen) (1); 5-CH3-phen (2), 5-Cl-phen (3); 5-Br-phen (4); 5-NO2-phen (5); 3,4,7,8-tetramethyl-phen (6); 4,7-diphenyl-phen (7); 5,5'-dimethyl-2,2'-bipyridine (8); 4,4'-di-tert-butyl-2,2'-bipyridine (9)). Crystal structures of 2, 5, 7 and 9 show that the complexes form 2 of the 12 possible conformational/configurational isomers, adopting compact C2-symmetric structures with short intramolecular transannular interactions between the diimine ligands and dpte phenyl groups; crystals of 2 and 5 contain non-statistical distributions of geometric isomers. In keeping with the π-acidity of the dpte, the Ru(III/II) couple, E°'(Ru3+/2+), occurs at relatively high potentials (1.4-1.7 V vs Ag/AgCl), and the lowest spin-allowed MLCT absorption band occurs near 400 nm. Surprisingly, the complexes also exhibit fluid-solution luminescence originating from a lowest MLCT excited state with lifetimes in the 140-750 ns time range; in acetonitrile, compound 8 undergoes photo-induced solvolysis. Variations in the MLCT energies and redox potentials are quantitatively described using a summative Hammett parameter (σT), as well as using Lever's electrochemical parameters (EL). Recommended parameterizations for 2,2'-bipyridyl and 1,10-phenanthrolinyl ligands were derived from analysis of correlations based on 199 measurements of E°'(Ru3+/2+) for 99 homo- and heteroleptic ruthenium(II) tris-diimine complexes. Variations in E°'(Ru3+/2+)more » due to substituents at the 4- and 4'-positions of bipyridyl ligands and 4- and 7-positions of phenanthrolinyl ligands are significantly more strongly correlated with σp+ than either σm or σp. Substituents at the 5- and 6-positions of phenanthrolinyl ligands are best described by σm and have effects comparable to those of substituents at the 3- and 8-positions. Correlations of EL with σT for 20 1,10-phenanthrolinyl ligands and for 35 2,2'-bipyridyl ligands show similar results, except that σp and σp+ are almost equally effective in describing the influence of substituents at the 4- and 4'-positions of bipyridyl ligands. For complexes 1-5 having an X-substituent at the 5-position of the phenanthrolinyl ligand, the MLCT absorption and emission energies, as well as the d5/d6-electron redox couple, are correlated with values for several other series of d6-electron metal complexes and give slopes that can be rationalized in terms of the relative number of diimine ligands and X-substituents.« less
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Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 0020-1669
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 53; Journal Issue: 1
American Chemical Society (ACS)
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
Sponsoring Org:
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Ruthenium complexes; 1,10-Phenanthroline derivatives; 2,2'-Bipyridine derivatives; Redox activity; Emission.