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Theoretical investigation on the spectroscopic properties of cyclometallated iridium (III) complexes and the deprotonation influence on them in solution
Author(s) -
Wang Jian,
Xia BaoHui,
Bai FuQuan,
Sun Lei,
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.22948
Subject(s) - deprotonation , iridium , chemistry , excited state , density functional theory , absorption (acoustics) , ground state , absorption spectroscopy , ligand (biochemistry) , bipyridine , electronic structure , solvent , photochemistry , crystallography , computational chemistry , atomic physics , materials science , catalysis , crystal structure , organic chemistry , ion , physics , biochemistry , receptor , quantum mechanics , composite material
Electronic structures and spectroscopic properties of mixed‐ligand cyclometallated iridium complexes with general formula [Ir(NˆC) 2 (NˆN)] + (NˆC = 2‐phenylpyridine, NˆN = Hcmbpy = 4‐carboxyl‐4 ′ ‐methyl‐2,2 ′ ‐bipyridine, 1 ; H 2 dcbpy = 4,4 ′ ‐dicarboxyl‐2,2 ′ ‐bipyridine, 2 ) were studied theoretically. The geometries of the complexes in ground and excited state were optimized at B3LYP and CIS levels, respectively. The absorption and emission of the complexes in CH 3 CN solutions were calculated by time‐dependent density functional theory (TD‐DFT) with the PCM solvent model. The calculated absorptions and emissions of the complexes are in good agreement with the measured results. The deprotonation influence on the electronic structure and the optical properties of 2 was also investigated. The results indicate that the deprotonation which occurs on the COOH groups influences the geometries of the complexes in ground and excited state slightly but leads to significant blue‐shifts in low energy absorption and emission maximum. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010