Computational and spectroscopic studies of Re(I) bipyridyl complexes containing 2,6-dimethylphenylisocyanide (CNx) ligand
Stoyanov, Stanislav R. Villegas, John M. Cruz, Arvin John Filoteo Lockyear, Loranelle L. Reibenspies, Joseph H. Rillema, D. Paul
Stoyanov, Stanislav R.
Villegas, John M.
Cruz, Arvin John Filoteo
Lockyear, Loranelle L.
Reibenspies, Joseph H.
Rillema, D. Paul
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2005-01
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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
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.
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American Chemical Society
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Journal of Chemical Theory and Computation;v.1 no.1