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dc.contributor.authorStoyanov, Stanislav R.
dc.contributor.authorVillegas, John M.
dc.contributor.authorCruz, Arvin John Filoteo
dc.contributor.authorLockyear, Loranelle L.
dc.contributor.authorReibenspies, Joseph H.
dc.contributor.authorRillema, D. Paul
dc.date.accessioned2013-07-10T16:23:55Z
dc.date.available2013-07-10T16:23:55Z
dc.date.issued2005-01
dc.identifier.citationStoyanov, Stanislav R.; Villegas, John M.; Cruz, Arvin J.; Lockyear, Loranelle L.; Reibenspies, Joseph H.; Rillema, D. Paul. 2005. Computational and spectroscopic studies of Re(I) bipyridyl complexes containing 2,6-dimethylphenylisocyanide (CNx) ligand. Journal of Chemical Theory and Computation, v.1 no.1 pp.95-106en_US
dc.identifier.urihttp://dx.doi.org/10.1021/ct049956g
dc.identifier.urihttp://hdl.handle.net/10057/5897
dc.descriptionClick on the DOI link to access the article (may not be free).en_US
dc.description.abstractDensity Functional Theory (DFT) calculations produce optimized geometries of the complexes [Re(CO)3(bpy)Cl] (1), [Re(CO)3(bpy)(py)](CF3SO3) (2), [Re(CO)3(bpy)(CNx)](CF3SO3) (3), and [Re(CO)(bpy)(CNx)3](CF3SO3) (4), where bpy = 2,2‘-bipyridine, py = pyridine, and CNx = 2,6-dimethylphenylisocyanide in their ground and lowest-lying triplet states. The ground-state optimized geometry for the cation of [Re(CO)3(bpy)(CNx)](CF3SO3) (3) results in a Re−C (CNx) bond length of 2.10 Å, a Re−C (CO) bond length trans to CNx of 2.01 Å, and a Re−C (CO) bond length cis to CNx of 1.96 Å which compares favorably to the single-crystal analysis of a Re−C (CNx) bond length of 2.074(4) Å, a Re−C (CO) bond length trans to CNx of 1.971(4) Å, and Re−C (CO) bond length cis to CNx of 1.932(4) Å. The majority of the singlet excited-state energies calculated using Time-dependent Density Functional Theory (TDDFT) and Conductor-like Polarizable Continuum Model (CPCM) are metal-ligand-to-ligand charge transfer (MLLCT) states and are in good agreement with the UV−vis spectral energies for the complexes in ethanol. The complexes exhibit emission both at room temperature and at 77 K except 4 which is only emissive at 77 K. The 77 K emission lifetimes range from 3.9 μs for 1 to 8.8 μs for 3. The emissive lowest-lying triplet state is a 3MLLCT state for complexes 1−3 but a triplet ligand-to-metal charge transfer (3LMCT) state for complex 4. The electronic, electrochemical, thermodynamic, HOMO−LUMO, and emitting-state energy gaps as well as the emission lifetimes increase in the order 1 < 2 < 3. A 3d−d excited- state, which is located above the 3LMCT state, accounts for the loss of room-temperature emission for complex 4.en_US
dc.language.isoen_USen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofseriesJournal of Chemical Theory and Computation;v.1 no.1
dc.titleComputational and spectroscopic studies of Re(I) bipyridyl complexes containing 2,6-dimethylphenylisocyanide (CNx) liganden_US
dc.typeArticleen_US
dc.description.versionPeer reviewed
dc.rights.holderCopyright © 2005 American Chemical Society


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