Theoretical investigation of the vibronic phosphorescence spectra and quantum yields for iridium(III) complexes with 2-(2,5,2',3',4',5',6'-heptafluoro-biphenyl-4-yl)-pyridine as the primary ligand.

Abstract

Cyclometalated Ir(III) complexes are widely used as phosphorescent materials in organic light-emitting diodes. In this work, the vibrationally resolved phosphorescence spectra of an experimental reported and four novel designed Ir(III) complexes with 2-(2,5,2',3',4',5',6'-heptafluoro-biphenyl-4-yl)-pyridine (HFYP) as primary ligand are investigated by theoretical calculations. The ancillary ligands are 3-(pentafluorophenyl)-pyridin-2-yl-1,2,4-triazolate (exp3), 3-(trifluoromethyl)-pyridin-2-yl-1,2,4-triazolate (5), 5-methylsulfonyl-2-oxyphenyl-2-oxazole (6), 5-trifluoromethyl-2-oxyphenyl-2-oxazole (7), 2-(3-(trifluoromethyl)-1H-1,2-diazol-5-yl)pyridine (8), respectively. Phosphorescence spectra show that there are mainly two strong peaks, which can be ascribed as low-frequency vibrational modes such as the rotation of ligand plane, and benzene ring/pyridine ring in ligand HFYP1 skeleton vibration coupled with CH in pyridine ring in plane bending vibration. The phosphorescence quantum yields were quantitatively determined by evaluating radiative decay rate constant kr, intersystem crossing rate constatant kISC and temperature-dependent nonradiative decay rate constant knr(T). It shows that the quantum yields of compounds exp3, 5 and 8 are relative higher, while those of compounds 6 and 7 are much smaller. This is mainly caused by larger knr(T) of compounds 6 and 7. It is anticipated that in Ir(III) complex with HFYP primary ligand, pyridin-2-yl-1,2,4-triazolate, 1,2-diazol-5-yl-pyridine are good ancillary ligand, while 2'-oxyphenyl-2-oxazoline is not appropriate to be ancillary ligand.