Substituent Effect on the Luminescent Properties of a Series of Deep Blue Emitting Mixed Ligand Ir(III) Complexes

The syntheses of the bright deep blue emitting mixed ligand Ir(III) complexes comprising two cyclometalating,
one phosphine and one cyano, ligands are reported. In this study, a firm connection between the nature of the
excited states and the physicochemical behavior of the complexes with different ligand systems is elucidated
by correlating the observed crystal structures, spectroscopic properties, and electrochemical properties with
the theoretical results obtained by the density functional theory (DFT) methods. The cyclometalating ligands
used here are the anions of 2-(4‘,6‘-difluorophenyl)-pyridine (F2ppy), 2-(4‘,6‘-difluorophenyl)-4-methyl pyridine
(F2ppyM), and 4-amino-2-(4‘,6‘-difluorophenyl)-pyridine (DMAF2ppy). The phosphine ligands are PhP(O−(CH2CH2O)3−CH3)2 and Ph2P(O−(CH2CH2O)n−CH3), where Ph = phenyl and n = 1 (P1), 3 (P3), or 8
(P350). The thermal stabilities of the complexes were enhanced upon increasing the “n” value. The crystal
structures of the complexes, [(DMAF2ppy)2Ir(P1)CN], (P1)DMA, and [(F2ppyM)2Ir(P3)CN], (P3)F2M, show
the cyano and phosphine groups being in a cis configuration to each other and in a trans configuration to the
coordinating Cring atoms. The long Ir−Cring bond lengths are ascribed to the trans effect of the strong phosphine
and cyano ligands. DFT calculations indicate that the highest occupied molecular orbital (HOMO) is mainly
contributed from the d-orbitals of the iridium atom and the π-orbitals of cyclometalating and cyano ligands,
whereas the lowest unoccupied molecular orbital (LUMO) spreads over only one of the cyclometalating ligands,
with no contribution from phosphine ligands to both frontier orbitals. Dimethylamino substitution increases
the energy of the emitting state that has more metal-to-ligand-charge-transfer (MLCT) character evidenced
by the smaller vibronic progressions, smaller difference in the 1MLCT and 3MLCT absorption wavelengths,
and higher extinction coefficients (ε) than the F2ppy and F2ppyM complexes. However, the increase in the
basicity of the dimethylamino group in the DMAF2ppy complexes in the excited states leads to distortions
and consequent nonradiative depopulation of the excited states, decreasing their lower photoluminescence
(PL) efficiency. The effect of the substituents in the phosphine ligand is more pronounced in the
electroluminescence (EL) than in the PL properties. Multilayer organic light emitting devices (OLEDs) are
fabricated by doping the Ir(III) complexes in a blend of mCP (m-bis(N-carbazolyl benzene)) and polystyrene,
and their device characteristics are studied. The (P3)F2M complex shows a maximum external quantum
efficiency (ηex) of 2%, a maximum luminance efficiency (ηL) of 4.13 cd/A at 0.04 mA/cm2, and a maximum
brightness of 7200 cd/m2 with a shift of the Commission Internationale de L'Eclairage (CIE) coordinates
from (0.14, 0.15) in film PL to (0.19, 0.34) in EL.