Ab initio and DFT study of the electronic structures and spectroscopic properties of pyrene ligands and their cyclometalated complexes |
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| Authors: | Bao‐Zhu Yang Xin Zhou Tao Liu Fu‐Quan Bai Hong‐Xing Zhang |
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| Institution: | State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China |
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| Abstract: | Two ligands 1‐diphenylphosphinopyrene (1‐PyP) ( L 1 ), 1,6‐bis(diphenylphosphino)‐pyrene (1,6‐PyP) ( L 2 ) and their cyclometalated complexes Pt(dppm)(1‐PyP‐H)]+ ( 1 ), Pt2(dppm)2(1,6‐PyP‐H2)]2+ (dppm = bis(diphenylphosphino)methane ( 2 ), and Pd(dppe)(1‐PyP‐H)+ (dppe = bis(diphenylphosphino)ethane) ( 3 ) are investigated theoretically to explore their electronic structures and spectroscopic properties. The ground‐ and excited‐state structures are optimized by the density functional theory (DFT) and single‐excitation configuration interaction method, respectively. At the time‐dependent DFT (TDDFT) and B3LYP level, the absorption and emission spectra in solution are obtained. As revealed from the calculations, the lowest‐energy absorptions of 1 and 3 are attributed to the mixing ligand‐to‐metal charge transfer (CT)/intraligand (IL)/ligand‐to‐ligand CT transitions, while that of 2 is attributed to the IL transition. The lowest‐energy phosphorescent emissions of the cyclometalated complexes are attributed to coming from the 3ILCT transitions. With the increase of the spin‐orbit coupling effect, the phosphorescence intensities and the emissions wavelength are correspondingly increased. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 |
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| Keywords: | spin‐orbit coupling effect pyrenyl rings ab initio calculations DFT calculations luminescence |
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