To elucidate the nature of low-lying triplet states and the effect of ligand modifica- tions on the excited-state properties of functional cationic iridium complexes, the solvent- dependent excited-state dynamics of t...To elucidate the nature of low-lying triplet states and the effect of ligand modifica- tions on the excited-state properties of functional cationic iridium complexes, the solvent- dependent excited-state dynamics of two phosphorescent cationic iridium(Ⅲ) complexes, namely [Ir(dph-oxd)2(bpy)]PF6 (1) and [Ir(dph-oxd)2(pzpy)]Pf6 (2), were investigated by femtosecond and nanosecond transient absorption spectroscopy. Upon photoexcitation to the metal-to-ligand charge-transfer (MLCT) states, the excited-state dynamics shows a rapid process (τ-=0.7-3 ps) for the formation of solvent stabilized 3MLCT states, which significantly depends on the solvent polarity for both 1 and 2. Sequentially, a relatively slow process assigned to the vibrational cooling/geometrical relaxation and a long-lived phospho- rescent emissive state is identified. Due to the different excited-state electronic structures regulated by ancillary ligands, the solvation-induced stabilization of the 3MLCT state in 1 is faster than that in 2. The present results provide a better sight of excited-state relaxation dynamics of ligand-related iridium(Ⅲ) complexes and solvation effects on triplet manifolds.展开更多
A new cyclometalated iridium(IlI) complex Ir(DPP)3 (DPP=2,3-diphenylpyrazine) was prepared by reaction of DPP with iridium trichloride hydrate under microwave irradiation. The structure of the complex was confir...A new cyclometalated iridium(IlI) complex Ir(DPP)3 (DPP=2,3-diphenylpyrazine) was prepared by reaction of DPP with iridium trichloride hydrate under microwave irradiation. The structure of the complex was confirmed by elemental analysis, ^1H NMR, and mass spectroscopy. The UV-Vis absorption and photoluminescent properties of the complex were investigated. The complex shows strong ^1MLCT (singlet metal to ligand charge-transfer) and aMLCT (triplet metal to ligand charge-transfer) absorption at 382 and 504 nm, respectively. The complex also shows strong photoluminescence at 573 nm at room temperature. These results suggest the complex to be a promising phosphorescent material.展开更多
A new cyclometalated iridium(Ⅲ) complex [Ir(2-pq)2(HPIP)]C1 (lrl, 2-pq=3-phenylisoquinoline, HPIP= 2-(2-hydroxyphenyl)imidazo[4,5-f] 1,10-phenanthroline) was synthesized and applied to image mitochondria in...A new cyclometalated iridium(Ⅲ) complex [Ir(2-pq)2(HPIP)]C1 (lrl, 2-pq=3-phenylisoquinoline, HPIP= 2-(2-hydroxyphenyl)imidazo[4,5-f] 1,10-phenanthroline) was synthesized and applied to image mitochondria in living cells. Irl displayed excellent ability to selectively accumulate in mitochondria of live cells with no requirement of replacement of the culture medium. Due to Irl exhibiting better photostability than the commercially available mitochondrial trackers, this complex could be applicable for the imaging and tracking of the mitochondrial mor- phological changes over long periods of time. In addition, in vitro cytotoxicity investigation revealed that it! showed negligible cytotoxicity at the concentrations employed. Based on these, Irl is suitable for organelle-selective imaging in living cells.展开更多
The solid-state ECL behavior of a water-insoluble bis-cyclometalated (pq)2Ir(N-phMA) complex is presented, in which pq is a 2-phenylquinoline anion and N-phMA is N-phenyl methacrylamide, a monoanionic bidentate li...The solid-state ECL behavior of a water-insoluble bis-cyclometalated (pq)2Ir(N-phMA) complex is presented, in which pq is a 2-phenylquinoline anion and N-phMA is N-phenyl methacrylamide, a monoanionic bidentate ligand. The MWNTs/(pq)2Ir(N-phMA) film, MWNTs/Ru(bpy)3^2+ film and (pq)2Ir(N-phMA) directly modified glassy carbon electrode were fabricated; only the MWNTs/(pq)2Ir(N-phMA) film can produce steady ECL in the presence of tri-n-propylamine as a coreactant.展开更多
An iridium (Ⅲ) bis[(4,6-difluorophenyl)pyridinato-N, C^2][6-(6'-(4"-( 5"-phenyl- 1", 3", 4"-oxadiazole-2"-yl) phenoxy) hexyloxy picolinate) was synthesized and characterized by IH NMR and elementary ...An iridium (Ⅲ) bis[(4,6-difluorophenyl)pyridinato-N, C^2][6-(6'-(4"-( 5"-phenyl- 1", 3", 4"-oxadiazole-2"-yl) phenoxy) hexyloxy picolinate) was synthesized and characterized by IH NMR and elementary analysis in order to study the effect of ancillary ligand of the oxadiazole-based picolinic acid derivative on optophysical properties of its iridium complex, and further to obtain an iridium complex with highly-efficient blue emission. The thermal stability, UV absorption and photoluminescent properties of this iridium complex were investigated. Compared with iridium (Ⅲ) bis[(4,6-difluorophenyl)pyridinato-N, C^2](picolinate) reported as a highly-efficient blue electroluminescent material, this iridium complex bearing an oxadiazole-based picolinic acid derivative presents higher thermal stability, more intense UV absorption at 291 nm and similar photoluminescent spectrum peaked at 469 nm. This indicates that tuning ancillary ligand of picolinic acid with an oxadiazole unit can improve the optophysical properties of its iridium complex.展开更多
A cyclometalated greenish-yellow emitter 2,3-diphenylimidazo[1,2-a]pyridine iridium(Ill) complex is successfully synthesized and used to fabricate phosphorescent organic light-emitting diodes. The optimized device e...A cyclometalated greenish-yellow emitter 2,3-diphenylimidazo[1,2-a]pyridine iridium(Ill) complex is successfully synthesized and used to fabricate phosphorescent organic light-emitting diodes. The optimized device exhibits a greenish-yellow emission with the peak at 523nm and a strong shoulder at 557nm, corresponding to Commission Internationale de l'Eclairage coordinates of (0.38, 0.68). The full width at half maximum of the device is 93 nm, which is broader than the fac-tris(2-phenylpyridine)iridium [Ir(ppy)3] based reference device of 78 nm. Meanwhile, a maximum current efficiency of 62.6 cd/A (47.51m/W) is obtained. This result is higher than a maximum current efficiency of 54.8 cd/A (431m/W) of the Ir(ppy)a based device. The results indicate that this new iridium complex may have potential applications in fabricating high color rendering index white organic light emitting diodes.展开更多
Organic light-emitting diodes(OLEDs)have important applications in the field of next-generation displays and lighting,and phosphorescent iridium complexes are an important class of electroluminescent phosphorescent ma...Organic light-emitting diodes(OLEDs)have important applications in the field of next-generation displays and lighting,and phosphorescent iridium complexes are an important class of electroluminescent phosphorescent materials.In this paper,Ir(bmppy)_(3),tris(4-methyl-2,5-diphenylpyridine)iridium,was synthesized and elvaluted for photo-physical characteristics.Single crystals suitale for X-ray diffraction(XRD)were grown from a mixture solvent of dichloromethane and absolute ethanol.The composition and structur of Ir(bmppy)_(3)were determined by element analysis,NMR spectra and XRD.The complex crystallizes in the monoclinic symmetry with the space group P21/c with a slightly distorted octahedral configuration.As measured by UV-Visible and photoluminescence spectra,Ir(bmppy)_(3) displays a maximum emission at at 527 nm at ambient temperature,a typical green-emitting profile.The complex has potential for application in the OLED industry.展开更多
Two cationic iridium(Ⅲ) complexes, [(pqcm)2Ir(pybz)](PF6) (Ir1) and [(pqcm)2Ir(apybz)](PF6) (Ir2) (pqcmH = 2-phenyl-quinoline-4-carboxylic acid methyl ester, pybz = 2-pyridyl-benzimidazole, apybz =...Two cationic iridium(Ⅲ) complexes, [(pqcm)2Ir(pybz)](PF6) (Ir1) and [(pqcm)2Ir(apybz)](PF6) (Ir2) (pqcmH = 2-phenyl-quinoline-4-carboxylic acid methyl ester, pybz = 2-pyridyl-benzimidazole, apybz = 1-allyl-2-pyridyl-benzimidazole), were readily synthesized from the reaction of IrⅢ-μ-chloro-bridged dimer [Ir(pqcm)2(Cl)]2 and corresponding ancillary ligands, and characterized by NMR and mass spectroscopies. The structure of It2 was also confirmed by single-crystal X-ray diffraction. The photophysical properties of the two complexes were also investigated. Irl shows deep red emission peaked at around 652 nm with the phosphorescence quantum yield of ca. 0.29 and the emission lifetime of 233 ns, while Ir2 shows red emission peaked at around 615 nm with the phosphorescence quantum yield of ca. 0.13 and the emission lifetime of 430 ns. The active hydrogen on pybz ligand is believed to have a great influence on the photophysical properties of Ir1.展开更多
文摘To elucidate the nature of low-lying triplet states and the effect of ligand modifica- tions on the excited-state properties of functional cationic iridium complexes, the solvent- dependent excited-state dynamics of two phosphorescent cationic iridium(Ⅲ) complexes, namely [Ir(dph-oxd)2(bpy)]PF6 (1) and [Ir(dph-oxd)2(pzpy)]Pf6 (2), were investigated by femtosecond and nanosecond transient absorption spectroscopy. Upon photoexcitation to the metal-to-ligand charge-transfer (MLCT) states, the excited-state dynamics shows a rapid process (τ-=0.7-3 ps) for the formation of solvent stabilized 3MLCT states, which significantly depends on the solvent polarity for both 1 and 2. Sequentially, a relatively slow process assigned to the vibrational cooling/geometrical relaxation and a long-lived phospho- rescent emissive state is identified. Due to the different excited-state electronic structures regulated by ancillary ligands, the solvation-induced stabilization of the 3MLCT state in 1 is faster than that in 2. The present results provide a better sight of excited-state relaxation dynamics of ligand-related iridium(Ⅲ) complexes and solvation effects on triplet manifolds.
文摘A new cyclometalated iridium(IlI) complex Ir(DPP)3 (DPP=2,3-diphenylpyrazine) was prepared by reaction of DPP with iridium trichloride hydrate under microwave irradiation. The structure of the complex was confirmed by elemental analysis, ^1H NMR, and mass spectroscopy. The UV-Vis absorption and photoluminescent properties of the complex were investigated. The complex shows strong ^1MLCT (singlet metal to ligand charge-transfer) and aMLCT (triplet metal to ligand charge-transfer) absorption at 382 and 504 nm, respectively. The complex also shows strong photoluminescence at 573 nm at room temperature. These results suggest the complex to be a promising phosphorescent material.
文摘A new cyclometalated iridium(Ⅲ) complex [Ir(2-pq)2(HPIP)]C1 (lrl, 2-pq=3-phenylisoquinoline, HPIP= 2-(2-hydroxyphenyl)imidazo[4,5-f] 1,10-phenanthroline) was synthesized and applied to image mitochondria in living cells. Irl displayed excellent ability to selectively accumulate in mitochondria of live cells with no requirement of replacement of the culture medium. Due to Irl exhibiting better photostability than the commercially available mitochondrial trackers, this complex could be applicable for the imaging and tracking of the mitochondrial mor- phological changes over long periods of time. In addition, in vitro cytotoxicity investigation revealed that it! showed negligible cytotoxicity at the concentrations employed. Based on these, Irl is suitable for organelle-selective imaging in living cells.
基金supported by the National Natural Science Foundation of China (No.20571033).
文摘The solid-state ECL behavior of a water-insoluble bis-cyclometalated (pq)2Ir(N-phMA) complex is presented, in which pq is a 2-phenylquinoline anion and N-phMA is N-phenyl methacrylamide, a monoanionic bidentate ligand. The MWNTs/(pq)2Ir(N-phMA) film, MWNTs/Ru(bpy)3^2+ film and (pq)2Ir(N-phMA) directly modified glassy carbon electrode were fabricated; only the MWNTs/(pq)2Ir(N-phMA) film can produce steady ECL in the presence of tri-n-propylamine as a coreactant.
基金Projects(20772101,50473046) supported by the National Natural Science Foundation of ChinaProject(2007FJ3017) supported by the Hunan Provincial Science Foundation, ChinaProject(07C764) supported by the Science Foundation of the Education Department of Hunan Province,China
文摘An iridium (Ⅲ) bis[(4,6-difluorophenyl)pyridinato-N, C^2][6-(6'-(4"-( 5"-phenyl- 1", 3", 4"-oxadiazole-2"-yl) phenoxy) hexyloxy picolinate) was synthesized and characterized by IH NMR and elementary analysis in order to study the effect of ancillary ligand of the oxadiazole-based picolinic acid derivative on optophysical properties of its iridium complex, and further to obtain an iridium complex with highly-efficient blue emission. The thermal stability, UV absorption and photoluminescent properties of this iridium complex were investigated. Compared with iridium (Ⅲ) bis[(4,6-difluorophenyl)pyridinato-N, C^2](picolinate) reported as a highly-efficient blue electroluminescent material, this iridium complex bearing an oxadiazole-based picolinic acid derivative presents higher thermal stability, more intense UV absorption at 291 nm and similar photoluminescent spectrum peaked at 469 nm. This indicates that tuning ancillary ligand of picolinic acid with an oxadiazole unit can improve the optophysical properties of its iridium complex.
文摘A cyclometalated greenish-yellow emitter 2,3-diphenylimidazo[1,2-a]pyridine iridium(Ill) complex is successfully synthesized and used to fabricate phosphorescent organic light-emitting diodes. The optimized device exhibits a greenish-yellow emission with the peak at 523nm and a strong shoulder at 557nm, corresponding to Commission Internationale de l'Eclairage coordinates of (0.38, 0.68). The full width at half maximum of the device is 93 nm, which is broader than the fac-tris(2-phenylpyridine)iridium [Ir(ppy)3] based reference device of 78 nm. Meanwhile, a maximum current efficiency of 62.6 cd/A (47.51m/W) is obtained. This result is higher than a maximum current efficiency of 54.8 cd/A (431m/W) of the Ir(ppy)a based device. The results indicate that this new iridium complex may have potential applications in fabricating high color rendering index white organic light emitting diodes.
文摘Organic light-emitting diodes(OLEDs)have important applications in the field of next-generation displays and lighting,and phosphorescent iridium complexes are an important class of electroluminescent phosphorescent materials.In this paper,Ir(bmppy)_(3),tris(4-methyl-2,5-diphenylpyridine)iridium,was synthesized and elvaluted for photo-physical characteristics.Single crystals suitale for X-ray diffraction(XRD)were grown from a mixture solvent of dichloromethane and absolute ethanol.The composition and structur of Ir(bmppy)_(3)were determined by element analysis,NMR spectra and XRD.The complex crystallizes in the monoclinic symmetry with the space group P21/c with a slightly distorted octahedral configuration.As measured by UV-Visible and photoluminescence spectra,Ir(bmppy)_(3) displays a maximum emission at at 527 nm at ambient temperature,a typical green-emitting profile.The complex has potential for application in the OLED industry.
基金financially supported by the National Natural Science Foundation of China (No. 50903001)the Guangxi Department of Education research project (200911MS281, 200911MS282)
文摘Two cationic iridium(Ⅲ) complexes, [(pqcm)2Ir(pybz)](PF6) (Ir1) and [(pqcm)2Ir(apybz)](PF6) (Ir2) (pqcmH = 2-phenyl-quinoline-4-carboxylic acid methyl ester, pybz = 2-pyridyl-benzimidazole, apybz = 1-allyl-2-pyridyl-benzimidazole), were readily synthesized from the reaction of IrⅢ-μ-chloro-bridged dimer [Ir(pqcm)2(Cl)]2 and corresponding ancillary ligands, and characterized by NMR and mass spectroscopies. The structure of It2 was also confirmed by single-crystal X-ray diffraction. The photophysical properties of the two complexes were also investigated. Irl shows deep red emission peaked at around 652 nm with the phosphorescence quantum yield of ca. 0.29 and the emission lifetime of 233 ns, while Ir2 shows red emission peaked at around 615 nm with the phosphorescence quantum yield of ca. 0.13 and the emission lifetime of 430 ns. The active hydrogen on pybz ligand is believed to have a great influence on the photophysical properties of Ir1.