Premium
Ab initio and DFT study of the electronic structures and spectroscopic properties of pyrene ligands and their cyclometalated complexes
Author(s) -
Yang BaoZhu,
Zhou Xin,
Liu Tao,
Bai FuQuan,
Zhang HongXing
Publication year - 2011
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22546
Subject(s) - time dependent density functional theory , chemistry , phosphorescence , density functional theory , ab initio , excited state , ligand (biochemistry) , photochemistry , ground state , computational chemistry , fluorescence , atomic physics , organic chemistry , biochemistry , physics , receptor , quantum mechanics
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 ), [Pt 2 (dppm) 2 (1,6‐PyP‐H 2 )] 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 3 ILCT 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