Excited-State Modification of Phenylimidazole-Based Cyclometalated Ir(III) Complexes through Secondary Bulky Aryl Substitution and Inductive Modification Enhances the Blue Emission Efficiency in Phosphorescent OLEDs.

To elucidate the key parameters governing the emission properties of phenylimidazole (pim)-based Ir(III) emitters, including their electronic structure and the bulky aryl substitution effect, a series of pim-based iridium(III) complexes (Ir(Rpim-X)3, Rpim-X = 1-R-2-(X-phenyl)-1H-imidazole) bearing secondary pendants of increasing bulkiness [R = methyl (Me), phenyl (Ph), terphenyl (TPh), or 4-isopropyl terphenyl (ITPh)] and three different primary pim ligands (X = F, F2, and CN) were designed and synthesized. Based on photophysical and electrochemical analyses, it was found that the excited state properties are highly dependent on the bulkiness of the secondary substituent and the inductive nature of the primary pim ligand. The incorporation of bulky TPh/ITPh substituents in the second coordination sphere significantly enhanced the emission efficiencies in the solid state (ΦPL = 72.1-84.9%) compared to those of the methyl- or phenyl-substituted Ir(III) complexes (ΦPL = 30.4% for Ir(Mepim)3 and 63.7% for Ir(Phpim)3). Further modification of the secondary aryl substituent (Ir(TPhpim)3 → Ir(ITPhpim)3) through the incorporation of an isopropyl group and F substitution on the primary pim ligand (Ir(TPh/ITPhpim)3 → Ir(TPh/ITPhpim-F/F2)3) resulted in a slight decrease in the LUMO and a significant decrease in the HOMO energy levels, respectively; these energy level adjustments consequently amplified emission blue shifts, thereby enabling efficient blue electroluminescence in phosphorescent organic light-emitting diodes. Theoretical calculations revealed that the excited-state properties of pim-based Ir(III) complexes can be modulated by the nature of the peripheral substituent and the presence of an EWG substituent. Among the fabricated blue-emitting TPh/ITPh-substituted Ir(III) complexes, Ir(ITPhpim-F)3, Ir(TPhpim-F2)3, and Ir(ITPhpim-F2)3 were tested as blue-emitting dopants for blue phosphorescent OLEDs owing to their high solid radiative quantum yields (ΦPL = 75.9-84.9%). The Ir(ITPhpim-F)3-doped multilayer device displayed the best performance with a maximum external quantum efficiency of 21.0%, a maximum current efficiency of 43.6 cd/A, and CIE coordinates of 0.18 and 0.31.

Photophysical properties of structural isomers of homoleptic Ir-complexes derived from xylenyl-substituted N-heterocyclic carbene ligands.

The phosphorescence properties of fac-Ir(pmp)3, mer-Ir(pmp)3, fac-Ir(dmpmp)3 and mer-Ir(dmpmp)3 (where pmp = 3-methyl-1-phenyl-2,3-dihydro-1H-imidazo[4,5-b]pyridine and dmpmp = 1-(2',6'-dimethylbiphenyl-2-yl)-3-methyl-2,3-dihydro-1H-imidazo[4,5-b]pyridine) in CH2Cl2 were investigated. At 77 K, the fac-isomers showed blue emission with a vibronic structure, while the mer-isomers showed less structured emissions. At 300 K, all complexes showed broad and markedly red-shifted emission spectra compared to those at 77 K. The quantum yields of the Ir(dmpmp)3 isomers were very low, and their emission lifetimes were very short compared to those of Ir(pmp)3. In order to understand the large differences between the photodynamic properties of Ir(pmp)3 and Ir(dmpmp)3, we performed femtosecond time-resolved transient absorption (TA) spectroscopic measurements. The TA spectra of Ir(dmpmp)3 were almost the same as those of Ir(pmp)3 at a short delay time. However, Ir(dmpmp)3 showed a new broad TA band at around 720 nm with increasing delay time. The rise time of this band was ca. 10 ps for both isomers, and this may be attributed to the geometrical change in the excited state, which is associated with the steric hindrance of the bulky dimethylphenyl substituent. Actually, Ir(dmpmp)3 showed a strong rigidochromic shift in the emission spectra with varying temperature. To understand the molecular orbitals and the energy levels, theoretical calculations were performed using density functional theory. As a result, structural displacement takes place accompanied by the fast migration of localization of excited states via intraligand charge transfer.

Photoinduced electron and hole transfers in carbazole dendrimers with heteroleptic Ir-complex cores.

We synthesised carbazole (Cz) dendrimers with heteroleptic Ir-complex cores. Upon excitation of the carbazole (Cz) dendrons, the phosphorescence of the core Ir(iii) complex was quenched due to the photoinduced electron transfer (PET) process. The PET dynamics of the excited Cz-dendrons were investigated using the femtosecond time-resolved transient absorption technique. A broad transient absorption (TA) band attributed to the S1-Sn transition of the 1Cz*-dendron was observed at around 630 nm in the first generation Cz-dendrimer (G1). This TA band in the second-generation dendrimer (G2) decayed with a longer lifetime of 55.5 ps compared to that of G1 (9.8 ps), because G2 has a larger distance between the Cz-dendron and Ir-complex core than that of G1. The decay time of the free 1Cz*-dendron was 6.3 ns, and thus, the reduced decay time in Gn corresponds to the PET dynamics. As a result of the PET process, the Cz cationic radical species (Cz˙+) was observed at around 780 nm. Interestingly, when the core Ir-complex in the dendrimer was excited with a 400 nm pulse selectively, the TA band of Cz˙+ was also detected at around 780 nm. This may be due to the photoinduced hole transfer (PHT) from the highest occupied molecular orbital (HOMO) energy state of Cz to the lowest singly occupied molecular orbital (LSOMO) energy state of the excited Ir-complex. The oxidation potential of Cz is lower than that of the Ir-complex, indicating that the HOMO of the Cz-dendron is located at a higher energy state than that of the Ir-complex. To investigate the relative order of the energy states and their orbital shapes, we performed theoretical calculations using density functional theory. The TA spectra were globally deconvoluted to generate the decay-associated spectra (DAS), from which the species-associated spectra (SAS) were calculated. The SAS can distinguish the individual intermediate species participating in the PET and PHT processes. The analysed rate constants of SAS were consistent with the results determined by the TA decays.

Tuning the Photophysical Properties of Homoleptic Tris-Cyclometalated Ir(III) Complexes by Facile Modification of the Imidazo-Phenanthridine and Their Application to Phosphorescent Organic Light-Emitting Diodes.

To explore the excited-state electronic structure of the blue-emitting Ir(dmp)3 dopant material (dmp = 3-(2,6-dimethylphenyl)-7-methylimidazo[1,2-f]phenanthridine), which is notable for durable blue phosphorescent organic light-emitting diode (PhOLED), a series of homoleptic dmp-based Ir(III) complexes (DMP-R, tris[3-(2,6-dimethylphenyl)-7-R-imidazo[1,2-f]phenanthridin-12-yl-κC 12,κN 1]iridium, R = H, CH3, F, and CF3) were prepared by introducing an electron-donating group (EDG; -CH3) or an electron-withdrawing group (EWG; -F and -CF3) at the 7-position of the imidazo-phenanthridine ligand. The photophysical analysis demonstrated that the alteration from EDG to EWGs led to redshifted structureless emission profiles, which were correlated with variations in the 3MLCT/3ILCT ratio in the T1 excited state. From electrochemical studies and density functional theory calculations, it turned out that the excited-state nature of the dmp-based Ir(III) complexes was significantly affected by the inductive effect of the 7-substituent of the cyclometalating dmp ligand. As a result of the lowest unoccupied molecular orbital energy stabilization by the EWGs that suppressed the non-radiative pathway from the emissive triplet excited state to the 3 d-d state, the F- and CF3-modified Ir(dmp)3 complexes (DMP-F and DMP-CF 3 ) showed quantum yields of 27-30% in the solution state, which were at least 4- or 5-fold higher than those shown by DMP-H and DMP-CH 3 . A PhOLED device based on DMP-CF 3 [CIE chromaticity (0.17, 0.39)], which demonstrated a distinct 3MLCT characteristic, exhibited better electroluminescent efficiencies with an external quantum efficiency of 13.5% than that based on DMP-CH 3 .

Outbreak of infections caused by Group A Streptococcus after modified radical mastectomy.

BACKGROUND: Eight infections occurred after modified radical mastectomies in a tertiary-care hospital. Group A streptococci (GAS) were isolated from three of the eight patients. METHODS: To control the outbreak, an epidemiologic investigation was conducted, and healthcare workers were screened for pathogens. Strains isolated from healthcare workers were compared with patient strains by emm typing. RESULTS: One surgeon attended one of the eight operations and observed the other seven. Streptococcus strains from the hands of this surgeon were identical to the patient strains. After the surgeon was suspended from duty and underwent eradication treatment, the outbreak was controlled. CONCLUSIONS: This outbreak of GAS infection is believed to have occurred by airborne transmission. Suspending patient care by healthcare workers who carry the causative GAS in a site(s) other than the respiratory tract for only the first 24 h they are receiving chemoprophylaxis may not be long enough. Sampling of the hands of healthcare workers during an investigation of nosocomial GAS infection is valuable.