dc.contributor.author | Stoyanov, Stanislav R. | |
dc.contributor.author | Villegas, John M. | |
dc.contributor.author | Cruz, Arvin John Filoteo | |
dc.contributor.author | Lockyear, Loranelle L. | |
dc.contributor.author | Reibenspies, Joseph H. | |
dc.contributor.author | Rillema, D. Paul | |
dc.date.accessioned | 2013-07-10T16:23:55Z | |
dc.date.available | 2013-07-10T16:23:55Z | |
dc.date.issued | 2005-01 | |
dc.identifier.citation | Stoyanov, 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.95-106 | en_US |
dc.identifier.uri | http://dx.doi.org/10.1021/ct049956g | |
dc.identifier.uri | http://hdl.handle.net/10057/5897 | |
dc.description | Click on the DOI link to access the article (may not be free). | en_US |
dc.description.abstract | Density 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.iso | en_US | en_US |
dc.publisher | American Chemical Society | en_US |
dc.relation.ispartofseries | Journal of Chemical Theory and Computation;v.1 no.1 | |
dc.title | Computational and spectroscopic studies of Re(I) bipyridyl complexes containing 2,6-dimethylphenylisocyanide (CNx) ligand | en_US |
dc.type | Article | en_US |
dc.description.version | Peer reviewed | |
dc.rights.holder | Copyright © 2005 American Chemical Society | |