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dc.contributor.authorRillema, D. Paul
dc.contributor.authorStoyanov, Stanislav R.
dc.contributor.authorCruz, Arvin John Filoteo
dc.contributor.authorHuy, Nguyen
dc.contributor.authorMoore, Curtis E.
dc.contributor.authorHuang, Wei
dc.contributor.authorSiam, Khamis
dc.contributor.authorJehan, Ali S.
dc.contributor.authorKomreddy, Venugopal R.
dc.identifier.citationRillema, D. Paul; Stoyanov, Stanislav R.; Cruz, Arvin John Filoteo; Huy Nguyen; Moore, Curtis E.; Huang, Wei; Siam, Khamis; Jehan, Ali S.; Komreddy, Venugopal. 2015. HOMO-LUMO energy gap control in platinum(II) biphenyl complexes containing 2,2 '-bipyridine ligands. Dalton Transactions, vol. 44:no. 39:pp 17075-17090en_US
dc.descriptionClick on the DOI link to access the article (may not be free).en_US
dc.description.abstractA series of platinum(II) biphenyl 2,2'-bipyridine complexes containing electron-donating and electron-withdrawing moieties on the 4 and 4' positions of the bipyridine ligand exhibit emission from excited states in the 600 nm region of the spectrum upon excitation in the metal-to-ligand charge transfer transition located near 450 nm. These complexes are distorted from planarity based on both single crystal structure determinations and density functional theory (DFT) calculations of isolated molecules in acetonitrile. The DFT also reveals the geometry of the lowest-lying triplet state (LLTS) of each complex that is important for emission behavior. The LLTS are assigned based on the electron spin density distributions and correlated with the singlet excited states to understand the mechanism of electronic excitation and relaxation. Time-dependent DFT calculations are performed to compute the singlet excited state energies of these complexes so as to help interpret their UV-Vis absorption spectra. Computational and experimental results, including absorption and emission energy maxima, electrochemical reduction potentials, LLTS, singlet excited states, and LUMO and HOMO energies, exhibit linear correlations with the Hammett constants for para-substituents sigma(p). These correlations are employed to screen complexes that have not yet been synthesized. The correlation analysis indicates that the electronic structure and the HOMO-LUMO energy gap in Pt(II) complexes can be effectively controlled using electron-donating and electron-withdrawing moieties covalently bonded to the ligands. The information presented in this paper provides a better understanding of the fundamental electronic and thermodynamic behavior of these complexes and could be used to design systems with specific applications.en_US
dc.description.sponsorshipWichita State University High Performance Computing Center, the Wichita State University Office of Research Administration, Kansas-NSF EPSCoR and the Department of Energy for support. S. R. Stoyanov acknowledges the support of the National Institute for Nanotechnology (NINT), a joint initiative of the National Research Council of Canada, the University of Alberta, the Government of Alberta, and the Government of Canada. S. R. Stoyanov thanks Dr John M. Villegas for the helpful comments on the presentation of the results. The computations were partially performed at the Compute/Calcul Canada's Western Canada Research Grid WestGrid as part of the allocation of Dr Andriy Kovalenko, Senior Research Officer at the National Institute for Nanotechnology and Adjunct Professor at the Department of Mechanical Engineering, University of Alberta, Edmonton, Alberta, Canada.en_US
dc.publisherRoyal Society of Chemistryen_US
dc.relation.ispartofseriesDalton Transactions;v.44:no.39
dc.subjectDensity-functional theoryen_US
dc.subjectExcited-state propertiesen_US
dc.subjectGeneralized gradient approximationen_US
dc.subjectResolved infrared-spectroscopyen_US
dc.subjectPhotophysical propertiesen_US
dc.subjectDicarbonyl complexen_US
dc.subjectRedox propertiesen_US
dc.subjectResonance ramanen_US
dc.titleHOMO-LUMO energy gap control in platinum(II) biphenyl complexes containing 2,2 '-bipyridine ligandsen_US
dc.rights.holder© Royal Society of Chemistry 2015en_US

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