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Theoretical Analyses on Phosphorescent Processes in Pt(thpy)2 and Its Derivatives

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journal contribution
posted on 17.07.2014 by Shiro Koseki, Yuhki Kagita, Sachiko Matsumoto, Toshio Asada, Shigayuki Yagi, Hiroyuki Nakazumi, Takeshi Matsushita
Theoretical estimation of the peak wavelengths of phosphorescence was performed at the MCSCF+SOCI/SBKJC+p level of theory for several typical platinum complexes in the research field of organic-light-emitting-diodes (OLEDs), where MCSCF+SOCI is the abbreviation of multiconfiguration self-consistent field calculations followed by second-order configuration interaction calculations. The spin–orbit coupling (SOC) integrals among low-lying electronic states of different spin multiplicities were explicitly calculated within the Zeff approximation. By using these computational methods, the experimental results for peak wavelengths of phosphorescence were reasonably explained for cis-bis­[2-(2′-thienyl)­pyridinato-N,C3′]­platinum­(II) and its derivatives. The replacement of one of the 2-(2′-thienyl)­pyridinate (thpy) ligands by a 2,4-pentanedionate (acac) ligand causes a blue shift of the phosphorescent peak by about 10 nm. The use of a 1,3-bis­(phenyl)­propane-1,3-dionate (bpp), 1,3-bis­(n-methoxyphenyl)­propane-1,3-dionate (bmp), or 1,3-bis­(3,4-methoxyphenyl)­propane-1,3-dionate (bdmp) ligand, instead of an acac ligand, has almost no effect on the peak wavelength of phosphorescence. When a benzene ring is fused to a thpy ligand, the peak wavelength is estimated to be 613 or 651 nm for [2,2′-(4′,5′-benzo)­thienyl)­pyridinato-N,C3′]­[1,3-bis­(3,4-dibutoxyphenyl)­propane-1,3-dionato-O,O]­platinum­(II) [btpPt­(bdbp)] and [1-(2′-thienyl)­isoquinolyl-N,C3′]­[1,3-bis­(3,4-dibutoxyphenyl)­propane-1,3-dionato-O,O]­platinum­(II) [1tiqPt­(bdbp)], respectively, after correction of the present computational underestimation. These theoretical estimations are in good agreement with the corresponding observations.