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dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorVillegas, John M.en_US
dc.contributor.authorStoyanov, Stanislav R.en_US
dc.contributor.authorHuang, Weien_US
dc.contributor.authorRillema, D. Paulen_US
dc.identifier.citationDalton transactions (Cambridge, England : 2003). 2005 Mar 21; (6): 1042-51.en_US
dc.descriptionClick on the DOI link below to access the article.en_US
dc.description.abstract[Re(CO)3(CNx)(L)]+, where CNx = 2,6-dimethylphenylisocyanide, forms complexes with L = 1,10-phenanthroline (1), 4-methyl-1,10-phenanthroline (2), 4,7-dimethyl-1,10-phenanthroline (3), 3,4,7,8-tetramethyl-1,10-phenanthroline (4), 2,9-dimethyl-1,10-phenanthroline (5) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (6). The metal-ligand-to-ligand charge transfer transition (MLLCT) absorption bands follow the series: (27800 cm(-1)) > 1, 2, 4 and 5(27500 cm(-1)) > 6 (26600 cm(-1)). Density functional theory (DFT) geometry optimizations reveal elongated Re-N (L) distances of 2.28 and 2.27 A for 5 and 6, respectively, compared to 2.23 A for 1-4. The reversible reduction potentials (E(1/2(red))) of 1-4 are linearly dependent on the B3LYP calculated LUMO energies. Time-dependent (TD) DFT and conductor-like polarizable continuum model (CPCM) calculated singlet excited states deviate by 700 cm(-1) or less from the experimental absorption maxima and aid in the spectral assignments. The (3)MLLCT emitting state energies are within 900 cm(-1) of the experimental 77 K emission energies for 1-6. The 77 K emission energies, E(1/2(red)), and the room temperature emission quantum yields (phi(LUMO)(em)) decrease in the order 1 > 2 > 3 > 4 whereas E(LUMO) and the room temperature emission energies follow the opposite trend. The emission lifetimes (tau(em)) decrease in the order 3 > 4 > 2 > 1 > 5 with 3 having the highest emission lifetime values of 26.9 micros at room temperature and 384 micros at 77 K and complex 5 having the lowest emission lifetimes of 4.6 micros at room temperature and 61 micros and 77 K.en_US
dc.publisherRoyal Society of Chemistryen_US
dc.relation.ispartofseriesDalton transactions (Cambridge, England : 2003)en_US
dc.relation.ispartofseriesDalton Transen_US
dc.titleA spectroscopic and computational study on the effects of methyl and phenyl substituted phenanthroline ligands on the electronic structure of Re(I) tricarbonyl complexes containing 2,6-dimethylphenylisocyanideen_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © The Royal Society of Chemistry 2005en_US

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