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Synthesis, Characterization, and Photochemical and Computational Investigations of Ru(II) Heterocyclic Complexes Containing 2,6-dimethylphenylisocyanide (CNx) Ligand

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Department of Chemistry, Wichita State University, 1845 North Fairmount Street, Wichita, Kansas 67260-0051, Department of Chemistry, Bethany College, 421 North First Street, Lindsborg, Kansas 67456-1897, and Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012
Cite this: Inorg. Chem. 2004, 43, 20, 6383–6396
Publication Date (Web):September 8, 2004
Copyright © 2004 American Chemical Society

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    The isocyanide ligand forms complexes with ruthenium(II) bis-bipyridine of the type [Ru(bpy)2(CNx)Cl](CF3SO3) (1), [Ru(bpy)2(CNx)(py)](PF6)2 (2), and [Ru(bpy)2(CNx)2](PF6)2 (3) (bpy = 2,2‘-bipyridine, py = pyridine, and CNx = 2,6-dimethylphenylisocyanide). The redox potentials shift positively as the number of CNx ligands increases. The metal-to-ligand charge-transfer (MLCT) bands of the complexes are located at higher energy than 450 nm and blue shift in proportion to the number of CNx ligands. The complexes are not emissive at room temperature but exhibit intense structured emission bands at 77 K with emission lifetimes as high as 25 μs. Geometry optimization of the complexes in the singlet ground and lowest-lying triplet states performed using density functional theory (DFT) provides information about the orbital heritage and correlates with X-ray and electrochemical results. The lowest-lying triplet-state energies correlate well with the 77 K emission energies for the three complexes. Singlet excited states calculated in ethanol using time-dependent density functional theory (TDDFT) and the conductor-like polarizable continuum model (CPCM) provide information that correlates favorably with the experimental absorption spectra in ethanol.

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     Wichita State University.

     Bethany College.


     Texas A&M University.


     To whom correspondence should be addressed. E-mail:  paul.rillema@

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    Crystallographic data for complex 3 in CIF format, optimized geometries (Table S1), calculated singlet excited-state energies of 13 in ethanol (Table S2), and percent molecular orbital contributions of 13 (Table S3) in text format. This material is available free of charge via the Internet at

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