A novel cyclometalated iridium complex with 1, 3, 4-oxadiazole moiety was synthesizedand characterized. Its UV and photoluminescent properties were studied. The strong UVabsorption intensity around 462 nm attributed t...A novel cyclometalated iridium complex with 1, 3, 4-oxadiazole moiety was synthesizedand characterized. Its UV and photoluminescent properties were studied. The strong UVabsorption intensity around 462 nm attributed to spin-forbidden triplet metal–ligand charge transferband and photoluminescence at 518 nm were observed. This indicated that achieved iridiumcomplex could be used as an efficient electrophosphorescent material.展开更多
An ionic iridium（Ⅲ） complex[Ir（F2dpyb）（bzdpp）2Cl][OTf]with 1,3-difluoro-4,6-di（2-pyridinyl） benzene（F2dpybH） terdentate ligand and benzyldiphenylphosphine（bzdpp）ligand was synthesized and characterized.Th...An ionic iridium（Ⅲ） complex[Ir（F2dpyb）（bzdpp）2Cl][OTf]with 1,3-difluoro-4,6-di（2-pyridinyl） benzene（F2dpybH） terdentate ligand and benzyldiphenylphosphine（bzdpp）ligand was synthesized and characterized.The structure of iridium complex was verified by single-crystal X-ray crystallography.It crystallizes in monoclinic,space group P21/n with a =14.3654（7）,b = 23.0026（10）,c = 15.7964（7） A°,β = 97.6029（11）,V= 5173.9（4） A°3,Z = 4,F（000） =2552,Dc = 1.645 Mg/m^3,Mr = 1281.49 and μ = 0.071 mm^-1.The UV-vis absorption and phosphorescence of the complex were discussed.The complex was ＇aggregation induced emission（AIE）＇ active.It exhibited no emission in CH2Cl2 solution but strong blue-green emission in solid state under ultraviolet light excitation.The complex emitted a strong phosphorescence centered at493 nm when doped in PMMA.Its lifetime is 0.755 μs and quantum yield is approximately 0.134.展开更多
A new functionalized heteroleptic iridium complex coordinated with 1-phenylisoquinoline （1-piq） and a functionalized fl-diketone （G1）, Ir（1-piq）2G1, was synthesized and characterized by 1H-NMR, mass spectrometry...A new functionalized heteroleptic iridium complex coordinated with 1-phenylisoquinoline （1-piq） and a functionalized fl-diketone （G1）, Ir（1-piq）2G1, was synthesized and characterized by 1H-NMR, mass spectrometry and elemental analysis. The larger conjugation of the replacement of acetylacetone （acac） by a functionalizedβ-diketonate ligand led to a significant decrease in the HOMO level toward vacuum level, while Ir（1-piq）2G1 and Ir（1-piq）2（acac） showed red phosphorescent emissions of about 620 nm in dichloromethane solution. The phosphorescent polymer light-emitting devices were achieved, with the complexes incorporated with polyfluorene （PFO） as a host polymer doped with 30% of 5-（4-biphenylyl）-2-（4-tert-butylphenyl）-1,3,4-oxadiazole （PBD） as electron transport material. The energy transfer mechanism of the devices was also discussed. The lower EL performance of Ir（1-piq）2G1 is ascribed to the inter-ligand energy transfer, indicating that it is important to control the energy level of the cyclometalated and ancillary ligands.展开更多
A novel iridium-complex,（BPPBI） 2 Ir（2-TFDBC）[BPPBI=2-（biphenyl-4-yl）-1-phenyl-1H-benzo[d]imidazole,2-TFDBC=1-（9-ethyl-9H-carbazol-2-yl）-4,4,4-trifluorobutane-1,3-dione],was synthesized,and its structure and c...A novel iridium-complex,（BPPBI） 2 Ir（2-TFDBC）[BPPBI=2-（biphenyl-4-yl）-1-phenyl-1H-benzo[d]imidazole,2-TFDBC=1-（9-ethyl-9H-carbazol-2-yl）-4,4,4-trifluorobutane-1,3-dione],was synthesized,and its structure and component were confirmed by 1 H NMR and element analysis,respectively.UV-Vis absorption and photoluminescent（PL） spectra of（BPPBI） 2 Ir（2-TFDBC） in dichloromethane were investigated.The Ir-complex exhibited a long wavelength excitation of 470 nm,i.e.,low-energy excitation.So,it is a promising candidate for phosphorescent probe and PL material.（BPPBI） 2 Ir（2-TFDBC）-based electroluminescent devices,ITO/MoO 3（10 nm）/NPB（80 nm）/CBP：x（BPPBI） 2 Ir（2-TFDBC）（20 nm）/TPBi（45 nm）/LiF/Al,were fabricated,where x（%） was of 4% or 8% doping concentration（mass fraction）;ITO=indium tin oxides;NBP=N,N＇-bis-（1-naphthalenyl）-N,N＇-bis-phenyl-（1,1＇-biphenyl）4,4＇-diamine,CBP=4,4＇-bis（N-carbazolyl）-1,1＇-biphenyl,TPBi=1,3,5-tris（1-phenyl-1H-benzimidazol-2-yl）benzene.The devices showed a red emission of 620 nm.The maximum current efficiency and brightness were 1.7 cd/A and 4063 cd/m 2 for a device of 8%（mass fraction） doping level,respectively.The moderate luminous efficiency was due to the inadequate energy transfer from the host material to the vip material.展开更多
Pure near-infrared(NIR)phosphorescent materials with emission peak larger than 700 nm are of great significance for the development of optoelectronics and biomedicine.We have designed and synthesized two new B-embedde...Pure near-infrared(NIR)phosphorescent materials with emission peak larger than 700 nm are of great significance for the development of optoelectronics and biomedicine.We have designed and synthesized two new B-embedded pure near-infrared(NIR)-emitting iridium complexes(Ir(Bpiq)2acac and Ir(Bpiq)2dpm)with peaks greater than 720 nm.More importantly,they exhibit very narrow phosphorescent emission with full width at half maximum(FWHM)of only about 50 nm(0.12 e V),resulting in a high NIR content(>90%)in their spectrum.In view of better optical property and solubility,the complex Ir(Bpiq)_(2)dpm was used as the emitting layer of a solution-processed OLED device,and achieved good maximum external quantum efficiency(EQE)(2.8%)peaking at 728 nm.This research provides an important strategy for the design of narrowband NIR-emitting phosphorescent iridium complexes and their optoelectronic applications.展开更多
Green-emitting iridium(Ⅲ)complexes were synthesised using chlorobridged dimer(ppy)_(2)Ir_(2)Cl_(2)(ppy)_(2),3-hydroxy-2-methyl-γ-pyranone,2-ethyl-3-hydroxy-4-pyranone,and 5-hydroxy-2-(hydroxymethyl)-1,4-pyranone as ...Green-emitting iridium(Ⅲ)complexes were synthesised using chlorobridged dimer(ppy)_(2)Ir_(2)Cl_(2)(ppy)_(2),3-hydroxy-2-methyl-γ-pyranone,2-ethyl-3-hydroxy-4-pyranone,and 5-hydroxy-2-(hydroxymethyl)-1,4-pyranone as the auxiliary ligand.The structure of the target product was characterised by nuclear magnetic resonance spectroscopy(~1H-NMR),infrared spectroscopy(IR)and mass spectrometry(MS),and its thermal stability,photophysical properties and electrochemical properties were investigated.The results show that the decomposition temperatures of Ir1,Ir2 and Ir3 are 349,292 and 200℃,respectively.The maximum emission wavelength of Ir1,Ir2 and Ir3 dissolved in dichloromethane is 491 nm.The HOMO energy level of Ir1,Ir2 and Ir3 are 5.39,-5.38,and-5.30 eV.The LUMO energy levels are-2.86,-2.85,and-2.80 eV,respectively.展开更多
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
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 new cyclometalated iridium(III) complex with the formula [Ir(DPQ)2(acac)] (DPQ= 2,3-diphenylquinoxaline; acac=acetylacetone) was prepared. The structure of the complex was confirmed by Elemental Analysis (EA), 1H NM...A new cyclometalated iridium(III) complex with the formula [Ir(DPQ)2(acac)] (DPQ= 2,3-diphenylquinoxaline; acac=acetylacetone) was prepared. The structure of the complex was confirmed by Elemental Analysis (EA), 1H NMR, and mass spectroscopy (MS). The UV-vis absorption and photoluminescent properties of the complex were investigated.展开更多
Three new cyclometalated iridium（m） complexes based on ligands of diphenylquinoline with fluorinated subsfituents were prepared, and characterized by elemental analysis （EA）, ^1H NMR, and mass spectroscopy （MS）....Three new cyclometalated iridium（m） complexes based on ligands of diphenylquinoline with fluorinated subsfituents were prepared, and characterized by elemental analysis （EA）, ^1H NMR, and mass spectroscopy （MS）. The photophysical and electrophosphorescent properties of the complexes were briefly discussed.展开更多
Two new iridium complexes with C^N=N type ligand(i.e.,Ir(BFPPya)3{tris[3,6-bis(4-fluorophenyl)pyridazine]iridium(III)}and Ir(BDFPPya)3{tris[3,6-bis(2,4-di-fluorophenyl)pyridazine]iridium(III)})attaching with fluorine ...Two new iridium complexes with C^N=N type ligand(i.e.,Ir(BFPPya)3{tris[3,6-bis(4-fluorophenyl)pyridazine]iridium(III)}and Ir(BDFPPya)3{tris[3,6-bis(2,4-di-fluorophenyl)pyridazine]iridium(III)})attaching with fluorine atoms,were synthesized and the effects of fluorination on the material properties and device performance were investigated.Compared with our previously reported fluorine-free analogue material,that is Ir(BPPya)3{tris[3,6-bis(phenyl)pyridazine]iridium(III)},blue shifts in the emission spectra as well as in the long wavelength region of the absorptions were observed.The photoluminescence quantum yield(PLQY)(0.44 and 0.84 vs.0.29),phosphoresces lifetime(0.88 and 1.31 vs.0.66 gs),and oxidation potential(1.10 and 1.37 vs.0.95 V)increased obviously after fluorinating the ligand.In contrast,the thermal stability of the iridium complexes decreased slightly(Td:435 and 402 vs.440℃).In the density functional theory(DFT)calculations,by comparing the steric shape of the three ligands within one optimized molecule,orientational differences among the complexes were observed.In OLED device studies,bluish green electroluminescence with peak emission of 500 nm,using the electron-transporting host of TPBI[2,2',2"-(1,3,5-benzenetriyl)tris(1-phenyl-lH-benzimidazole)]and the most fluorinated dopant of Ir(BDFPPya)3,was achieved with maximum efficiency of 20.3 cd/A.On one hand this efficiency is not satisfactory considering a high PLQY of 0.84.On the other hand with the similar device structure,that the(HOMO-LUMO)s of all the dopants are wrapped within that of the host TPBI,and all the triplet energies of the dopants are smaller than that of the host TPBI,it is abnormal that the ordering of device efficiencies is contradictory to that of PLQY.Assisting with the phosphorescent spectrum of TPBI and the absorption spectra of the dopant,the contradiction was interpreted reasonably.展开更多
Iridium(Ⅲ)porphycene complex was synthesized and structurally characterized for the first time.The introduction of the posttransition iridium(Ⅲ)ion not only significantly enhances the absorption intensity at the end...Iridium(Ⅲ)porphycene complex was synthesized and structurally characterized for the first time.The introduction of the posttransition iridium(Ⅲ)ion not only significantly enhances the absorption intensity at the end of visible region,but also displays efficient singlet oxygen quantum yield(76%),which is applicable for photodynamic therapy in living cells.展开更多
Stimuli-triggered release and alleviating resistance of iridium(Ⅲ)-based drugs at tumor sites remains challengeable for clinical hepatoma therapy.Herein,a doxorubicin@iridium-transferrin(DOX@Ir-TF)nanovesicle was syn...Stimuli-triggered release and alleviating resistance of iridium(Ⅲ)-based drugs at tumor sites remains challengeable for clinical hepatoma therapy.Herein,a doxorubicin@iridium-transferrin(DOX@Ir-TF)nanovesicle was synthesized by carboxylated-transferrin(TF)and doxorubicin-loaded amphiphilic iridium-amino with quaternary ammonium(QA)groups and disulfide bonds.The QA groups enhanced photophysical properties and broadened production capacity of photoinduced-reactive oxygen species(ROS),while the disulfide-bridged bonds regulated oxidative stress levels through reacting with glutathione(GSH);simultaneously,modification of TF improved recognition and endocytosis of the nanovesicle for tumor cells.Based on in-vitro results,a controlled-release behavior of DOX upon a dualresponsiveness of GSH and near-infrared ray(NIR)irradiation was presented,along with high-efficiency generation of ROS.After an intravenous injection,the nanovesicle was targeted at tumor sites,realizing TF-navigated photoacoustic imaging guidance and synergistic chemotherapy-photodynamic therapy under NIR/GSH stimulations.Overall,newly-synthesized DOX@Ir-TF nanovesicle provided a potential in subcutaneous hepatocellular carcinoma therapy due to integrations of targeting delivery,dual-stimuli responsive release,synergistic therapy strategy,and real-time monitoring.展开更多
Fluorescent analysis of bone provides valuable insights into bone structures.However,conventional dyes suffer from low specificity on bone tissue,small stokes shift,short fluorescent lifetime,and aggregation-caused qu...Fluorescent analysis of bone provides valuable insights into bone structures.However,conventional dyes suffer from low specificity on bone tissue,small stokes shift,short fluorescent lifetime,and aggregation-caused quenching effect,which result in low efficacy and artifacts.In this work,we design an aggregation-induced emission(AIE)-active iridium(III)complex(Ir-BP2)as a highly selective,convenient,nondestructiveness,and dual-mode staining agent for bone analysis.Ir-BP2 containing phosphonate groups selectively binds to hydroxyapatites,the main component of bone matrix,and exhibits turn-on AIE phosphorescence with prolonged lifetime.Ir-BP2 exhibits promising biosafety and offers higher accuracy in staining calcium deposits than conventional Alizarin Red S staining assay when it is employed in real-time monitoring of osteogenesis differentiation process.A ready-to-use staining spray of Ir-BP2 is fabricated.By using fluorescent imaging and lifetime imaging,Ir-BP2 staining provides valuable insights into bone microstructure analysis,microdamage diagnosis,and bone growth state identification.Further,Ir-BP2 is successfully applied on a human spine vertebra for diagnosing bone invasiveness of eosinophilic granuloma,validating its clinical practice.This work presents a powerful tool in bone analysis and will lead to new approaches for the diagnosis and treatment of bone-related diseases.展开更多
Nonlinear optical materials are one of the key research objects in the field of optics, which mainly research the nonlinear effects of the interaction between luminesce and matter. Compared with inorganic nonlinear op...Nonlinear optical materials are one of the key research objects in the field of optics, which mainly research the nonlinear effects of the interaction between luminesce and matter. Compared with inorganic nonlinear optical materials, organic nonlinear materials have outstanding advantages: strong adaptability, high flexibility, low cost, easy modification and damage resistance. In this review, the electric field induced second harmonic generation (EFISH) experimental technology is used to measure and research the nonlinearity of iridium metal complexes. And because of its structural diversity, people can design molecules according to their needs to get the best nonlinear optical response. Organic molecules with large nonlinear coefficients should have the following characteristics: asymmetric charge distribution, the delocalized nature of π electrons, and easy polarization by external electric fields, and a large π conjugated system. In recent years, metal organic compounds have become a leader in the field of optics, mainly because of their very good nonlinear optical properties. In the future, people will do more investigation on the nonlinearity of metal organic complexes. Researchers have shown great interest in iridium metal organic complexes due in particular to their attractive stability and nonlinear activity. This review mainly studies the nonlinear principle, performance test and Measurement of nonlinearity of iridium metal complexes. The nonlinear properties of other metal-metal organic complexes will not be discussed.展开更多
A general and high-efficiency C-alkylation of oxindoles and barbituric acids has been developed by a Cp*Ir complex[Cp*Ir(2,20-bpyO)(OH)]Na with a bipyridine-based functional ligand.In particular,H_(2)O was selected as...A general and high-efficiency C-alkylation of oxindoles and barbituric acids has been developed by a Cp*Ir complex[Cp*Ir(2,20-bpyO)(OH)]Na with a bipyridine-based functional ligand.In particular,H_(2)O was selected as the solvent instead of the organic solvent in this catalytic system.Through mild reaction conditions gave a variety of corresponding alkylated heterocyclic compounds with good to excellent yields.More importantly,the gramscale C-alkylation reaction was successfully carried out with good yield using a common route with only a single purification by column chromatography.展开更多
Herein,we design and synthesize a series of oligomers[Ir(ppy)2(dabpy)-ODPA]n(D1-n)by copolymerization of[Ir(ppy)2(dabpy)][PF6](D2)with 4,4′-Oxydiphthalic anhydride(ODPA),to resolve the problem of simultaneous improve...Herein,we design and synthesize a series of oligomers[Ir(ppy)2(dabpy)-ODPA]n(D1-n)by copolymerization of[Ir(ppy)2(dabpy)][PF6](D2)with 4,4′-Oxydiphthalic anhydride(ODPA),to resolve the problem of simultaneous improvement of sta-bility and activity of classical iridium complex for photocatalytic water-splitting.Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,solid-state nuclear magnetic resonance,and gel permeation chromatography results indicate that the degree of polymerization(n)of D1-n could be tuned by the syn-thesis method.The best photocatalytic performance is reached by D1-n with n at of 2 and/or 3(D1-2/3),which exhibits a photocatalytic lifetime up to 676 h and a photocatalytic hydrogen evolution of 162055.1 Compared with classicalμmol⋅g-1.iridium complex D2,the photocatalytic lifetime of D1-2/3 is about 38 times longer and the photocatalytic activity is 1.3 times higher.Further increase of n leads to a decrease in both photocatalytic lifetime and activity.According to the spectro-scopic characterizations,photoelectrochemical experiments,and density functional theory calculation,the significantly enhanced photocatalytic performance of D1-2/3 originates from the oligomeric structure.The oligomer chain of D1-2/3 with suit-able length acts as a large steric hindrance to reduce the undesired photoinduced decomposition and prolong its lifetime.The possible coupling of adjacent Ir com-plexes in D1-2/3 lowers the energy gap and increases the utilization of visible light,which overcomes the adverse effect of large steric hindrance andfinally improve the activity.This workfirst provides a simple strategy for constructing oligomeric Ir photosensitizers to simultaneously achieve long lifetime and high activity,it will lay the foundation for the design of highly efficient photosensitizers in the future.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
Two new fluorinated phenylisoquinoline-based iridium（Ⅲ） complexes,[Ir（f2piq）2（bipy）][PF6]（3a） and[Ir（fmpiq）2（bipy）][PF6]（3b）（f2piq = l-（2,4-difluorophenyl）isoquinoline,fmpiq = 1-（4-fluoro-2-methylph...Two new fluorinated phenylisoquinoline-based iridium（Ⅲ） complexes,[Ir（f2piq）2（bipy）][PF6]（3a） and[Ir（fmpiq）2（bipy）][PF6]（3b）（f2piq = l-（2,4-difluorophenyl）isoquinoline,fmpiq = 1-（4-fluoro-2-methylphenyl）isoquinoline,bipy = 2,2＇-bipyridine）,have been synthesized and fully characterized.Single crystal X-ray diffraction study has been undertaken on complexes 3a and 3b,which show that each adopts the distorted octahedral coordination geometry with the cis-C,C＇ and trans-N,N＇ configuration.The photoluminescence spectra of 3a and 3b exhibit yellow and orange emission maxima at 584 and 600 nm,respectively.The frontier molecular orbital diagrams and the lowest-energy electronic transitions of 3a-3b have been calculated with density functional theory（DFT） and time-dependent DFT（TD-DFT）.The absorption and emission spectra of complex 3b is red-shifted relative to those of complex 3a,as a consequence of the nature of the methyl group.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.20272014)the Project of National Education Ministry(Project No.204097)National 973 Project of China(Project No.2002CB613400-5).
文摘A novel cyclometalated iridium complex with 1, 3, 4-oxadiazole moiety was synthesizedand characterized. Its UV and photoluminescent properties were studied. The strong UVabsorption intensity around 462 nm attributed to spin-forbidden triplet metal–ligand charge transferband and photoluminescence at 518 nm were observed. This indicated that achieved iridiumcomplex could be used as an efficient electrophosphorescent material.
基金Supported by the National Natural Science Foundation of China(21572001)the Natural Science Foundation from Bureau of Education of Anhui Province(KJ2013A063)the Anhui Province Undergraduate Innovation and Entrepreneurship Training Program(201510360119)
文摘An ionic iridium（Ⅲ） complex[Ir（F2dpyb）（bzdpp）2Cl][OTf]with 1,3-difluoro-4,6-di（2-pyridinyl） benzene（F2dpybH） terdentate ligand and benzyldiphenylphosphine（bzdpp）ligand was synthesized and characterized.The structure of iridium complex was verified by single-crystal X-ray crystallography.It crystallizes in monoclinic,space group P21/n with a =14.3654（7）,b = 23.0026（10）,c = 15.7964（7） A°,β = 97.6029（11）,V= 5173.9（4） A°3,Z = 4,F（000） =2552,Dc = 1.645 Mg/m^3,Mr = 1281.49 and μ = 0.071 mm^-1.The UV-vis absorption and phosphorescence of the complex were discussed.The complex was ＇aggregation induced emission（AIE）＇ active.It exhibited no emission in CH2Cl2 solution but strong blue-green emission in solid state under ultraviolet light excitation.The complex emitted a strong phosphorescence centered at493 nm when doped in PMMA.Its lifetime is 0.755 μs and quantum yield is approximately 0.134.
基金Project(50803008) supported by the National Natural Science Foundation of ChinaProject(2002CB613403) supported by the Ministry of Science and Technology (MOST) of China+1 种基金Project(09JJ6085) supported by the Natural Science Foundation of Hunan Province,ChinaProject(08hjyh02) supported by the Open Project Program of Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education,China
文摘A new functionalized heteroleptic iridium complex coordinated with 1-phenylisoquinoline （1-piq） and a functionalized fl-diketone （G1）, Ir（1-piq）2G1, was synthesized and characterized by 1H-NMR, mass spectrometry and elemental analysis. The larger conjugation of the replacement of acetylacetone （acac） by a functionalizedβ-diketonate ligand led to a significant decrease in the HOMO level toward vacuum level, while Ir（1-piq）2G1 and Ir（1-piq）2（acac） showed red phosphorescent emissions of about 620 nm in dichloromethane solution. The phosphorescent polymer light-emitting devices were achieved, with the complexes incorporated with polyfluorene （PFO） as a host polymer doped with 30% of 5-（4-biphenylyl）-2-（4-tert-butylphenyl）-1,3,4-oxadiazole （PBD） as electron transport material. The energy transfer mechanism of the devices was also discussed. The lower EL performance of Ir（1-piq）2G1 is ascribed to the inter-ligand energy transfer, indicating that it is important to control the energy level of the cyclometalated and ancillary ligands.
基金Supported by the Natural Science Foundation of Guangdong Province,China(No.10152404801000017)
文摘A novel iridium-complex,（BPPBI） 2 Ir（2-TFDBC）[BPPBI=2-（biphenyl-4-yl）-1-phenyl-1H-benzo[d]imidazole,2-TFDBC=1-（9-ethyl-9H-carbazol-2-yl）-4,4,4-trifluorobutane-1,3-dione],was synthesized,and its structure and component were confirmed by 1 H NMR and element analysis,respectively.UV-Vis absorption and photoluminescent（PL） spectra of（BPPBI） 2 Ir（2-TFDBC） in dichloromethane were investigated.The Ir-complex exhibited a long wavelength excitation of 470 nm,i.e.,low-energy excitation.So,it is a promising candidate for phosphorescent probe and PL material.（BPPBI） 2 Ir（2-TFDBC）-based electroluminescent devices,ITO/MoO 3（10 nm）/NPB（80 nm）/CBP：x（BPPBI） 2 Ir（2-TFDBC）（20 nm）/TPBi（45 nm）/LiF/Al,were fabricated,where x（%） was of 4% or 8% doping concentration（mass fraction）;ITO=indium tin oxides;NBP=N,N＇-bis-（1-naphthalenyl）-N,N＇-bis-phenyl-（1,1＇-biphenyl）4,4＇-diamine,CBP=4,4＇-bis（N-carbazolyl）-1,1＇-biphenyl,TPBi=1,3,5-tris（1-phenyl-1H-benzimidazol-2-yl）benzene.The devices showed a red emission of 620 nm.The maximum current efficiency and brightness were 1.7 cd/A and 4063 cd/m 2 for a device of 8%（mass fraction） doping level,respectively.The moderate luminous efficiency was due to the inadequate energy transfer from the host material to the vip material.
基金support from the National Natural Science Foundation of China(Nos.22171109,52373195 and 22001097)Natural Science Foundation of Jiangsu Province of China(No.BK20201003)+1 种基金the Postdoctoral Research Foundation of China(No.2021M701657)the Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices,Ministry of Education,Jianghan University(No.JDGD-202301)。
文摘Pure near-infrared(NIR)phosphorescent materials with emission peak larger than 700 nm are of great significance for the development of optoelectronics and biomedicine.We have designed and synthesized two new B-embedded pure near-infrared(NIR)-emitting iridium complexes(Ir(Bpiq)2acac and Ir(Bpiq)2dpm)with peaks greater than 720 nm.More importantly,they exhibit very narrow phosphorescent emission with full width at half maximum(FWHM)of only about 50 nm(0.12 e V),resulting in a high NIR content(>90%)in their spectrum.In view of better optical property and solubility,the complex Ir(Bpiq)_(2)dpm was used as the emitting layer of a solution-processed OLED device,and achieved good maximum external quantum efficiency(EQE)(2.8%)peaking at 728 nm.This research provides an important strategy for the design of narrowband NIR-emitting phosphorescent iridium complexes and their optoelectronic applications.
文摘Green-emitting iridium(Ⅲ)complexes were synthesised using chlorobridged dimer(ppy)_(2)Ir_(2)Cl_(2)(ppy)_(2),3-hydroxy-2-methyl-γ-pyranone,2-ethyl-3-hydroxy-4-pyranone,and 5-hydroxy-2-(hydroxymethyl)-1,4-pyranone as the auxiliary ligand.The structure of the target product was characterised by nuclear magnetic resonance spectroscopy(~1H-NMR),infrared spectroscopy(IR)and mass spectrometry(MS),and its thermal stability,photophysical properties and electrochemical properties were investigated.The results show that the decomposition temperatures of Ir1,Ir2 and Ir3 are 349,292 and 200℃,respectively.The maximum emission wavelength of Ir1,Ir2 and Ir3 dissolved in dichloromethane is 491 nm.The HOMO energy level of Ir1,Ir2 and Ir3 are 5.39,-5.38,and-5.30 eV.The LUMO energy levels are-2.86,-2.85,and-2.80 eV,respectively.
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.
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 new cyclometalated iridium(III) complex with the formula [Ir(DPQ)2(acac)] (DPQ= 2,3-diphenylquinoxaline; acac=acetylacetone) was prepared. The structure of the complex was confirmed by Elemental Analysis (EA), 1H NMR, and mass spectroscopy (MS). The UV-vis absorption and photoluminescent properties of the complex were investigated.
基金supported by the National Natural Science Foundation of China(No.20371036 and 20474047)the Program for New Century Excellent Talents in University,the Ministry of Education of Chinathe Hubei Province Science Fund for Distinguished Young Scholar(No.2003ABB008).
文摘Three new cyclometalated iridium（m） complexes based on ligands of diphenylquinoline with fluorinated subsfituents were prepared, and characterized by elemental analysis （EA）, ^1H NMR, and mass spectroscopy （MS）. The photophysical and electrophosphorescent properties of the complexes were briefly discussed.
基金financially supported by the National Natural Science Foundation of China(61077021,61076016)the Nanjing University of Posts and Telecommunications(NY212076,NY212050)
文摘Two new iridium complexes with C^N=N type ligand(i.e.,Ir(BFPPya)3{tris[3,6-bis(4-fluorophenyl)pyridazine]iridium(III)}and Ir(BDFPPya)3{tris[3,6-bis(2,4-di-fluorophenyl)pyridazine]iridium(III)})attaching with fluorine atoms,were synthesized and the effects of fluorination on the material properties and device performance were investigated.Compared with our previously reported fluorine-free analogue material,that is Ir(BPPya)3{tris[3,6-bis(phenyl)pyridazine]iridium(III)},blue shifts in the emission spectra as well as in the long wavelength region of the absorptions were observed.The photoluminescence quantum yield(PLQY)(0.44 and 0.84 vs.0.29),phosphoresces lifetime(0.88 and 1.31 vs.0.66 gs),and oxidation potential(1.10 and 1.37 vs.0.95 V)increased obviously after fluorinating the ligand.In contrast,the thermal stability of the iridium complexes decreased slightly(Td:435 and 402 vs.440℃).In the density functional theory(DFT)calculations,by comparing the steric shape of the three ligands within one optimized molecule,orientational differences among the complexes were observed.In OLED device studies,bluish green electroluminescence with peak emission of 500 nm,using the electron-transporting host of TPBI[2,2',2"-(1,3,5-benzenetriyl)tris(1-phenyl-lH-benzimidazole)]and the most fluorinated dopant of Ir(BDFPPya)3,was achieved with maximum efficiency of 20.3 cd/A.On one hand this efficiency is not satisfactory considering a high PLQY of 0.84.On the other hand with the similar device structure,that the(HOMO-LUMO)s of all the dopants are wrapped within that of the host TPBI,and all the triplet energies of the dopants are smaller than that of the host TPBI,it is abnormal that the ordering of device efficiencies is contradictory to that of PLQY.Assisting with the phosphorescent spectrum of TPBI and the absorption spectra of the dopant,the contradiction was interpreted reasonably.
基金supported by the National Natural Science Foundation of China(21771102,21911540069,21601052,21603062,21877027)the Program for Science Technology Innovation Teams in Universities of Henan Province(19IRTSTHN023)the Key Program for High School of Henan Province(16A150012)。
文摘Iridium(Ⅲ)porphycene complex was synthesized and structurally characterized for the first time.The introduction of the posttransition iridium(Ⅲ)ion not only significantly enhances the absorption intensity at the end of visible region,but also displays efficient singlet oxygen quantum yield(76%),which is applicable for photodynamic therapy in living cells.
基金supported by the National Key R&D Program of China(Nos.2022YFB3808000,2022YFB3808001)the Project for High-Level Talent Innovation and Entrepreneurship of Quanzhou(No.2022C016R)+1 种基金the Medical Innovation Project of Science and Technology Program of Fujian Provincial Health Commission(No.2021CXA006)the Key Program of Qingyuan Innovation Laboratory(No.00221002).
文摘Stimuli-triggered release and alleviating resistance of iridium(Ⅲ)-based drugs at tumor sites remains challengeable for clinical hepatoma therapy.Herein,a doxorubicin@iridium-transferrin(DOX@Ir-TF)nanovesicle was synthesized by carboxylated-transferrin(TF)and doxorubicin-loaded amphiphilic iridium-amino with quaternary ammonium(QA)groups and disulfide bonds.The QA groups enhanced photophysical properties and broadened production capacity of photoinduced-reactive oxygen species(ROS),while the disulfide-bridged bonds regulated oxidative stress levels through reacting with glutathione(GSH);simultaneously,modification of TF improved recognition and endocytosis of the nanovesicle for tumor cells.Based on in-vitro results,a controlled-release behavior of DOX upon a dualresponsiveness of GSH and near-infrared ray(NIR)irradiation was presented,along with high-efficiency generation of ROS.After an intravenous injection,the nanovesicle was targeted at tumor sites,realizing TF-navigated photoacoustic imaging guidance and synergistic chemotherapy-photodynamic therapy under NIR/GSH stimulations.Overall,newly-synthesized DOX@Ir-TF nanovesicle provided a potential in subcutaneous hepatocellular carcinoma therapy due to integrations of targeting delivery,dual-stimuli responsive release,synergistic therapy strategy,and real-time monitoring.
基金National Natural Science Foundation of China,Grant/Award Number:22107087Yong Talent Support Plan of Xi’an Jiaotong University,Grant/Award Number:YX6J024+1 种基金Science and Technology Planning Project of Guangzhou,Grant/Award Number:202002030089Key Projects of Social Welfare and Basic Research of Zhongshan City,Grant/Award Number:2021B2007。
文摘Fluorescent analysis of bone provides valuable insights into bone structures.However,conventional dyes suffer from low specificity on bone tissue,small stokes shift,short fluorescent lifetime,and aggregation-caused quenching effect,which result in low efficacy and artifacts.In this work,we design an aggregation-induced emission(AIE)-active iridium(III)complex(Ir-BP2)as a highly selective,convenient,nondestructiveness,and dual-mode staining agent for bone analysis.Ir-BP2 containing phosphonate groups selectively binds to hydroxyapatites,the main component of bone matrix,and exhibits turn-on AIE phosphorescence with prolonged lifetime.Ir-BP2 exhibits promising biosafety and offers higher accuracy in staining calcium deposits than conventional Alizarin Red S staining assay when it is employed in real-time monitoring of osteogenesis differentiation process.A ready-to-use staining spray of Ir-BP2 is fabricated.By using fluorescent imaging and lifetime imaging,Ir-BP2 staining provides valuable insights into bone microstructure analysis,microdamage diagnosis,and bone growth state identification.Further,Ir-BP2 is successfully applied on a human spine vertebra for diagnosing bone invasiveness of eosinophilic granuloma,validating its clinical practice.This work presents a powerful tool in bone analysis and will lead to new approaches for the diagnosis and treatment of bone-related diseases.
文摘Nonlinear optical materials are one of the key research objects in the field of optics, which mainly research the nonlinear effects of the interaction between luminesce and matter. Compared with inorganic nonlinear optical materials, organic nonlinear materials have outstanding advantages: strong adaptability, high flexibility, low cost, easy modification and damage resistance. In this review, the electric field induced second harmonic generation (EFISH) experimental technology is used to measure and research the nonlinearity of iridium metal complexes. And because of its structural diversity, people can design molecules according to their needs to get the best nonlinear optical response. Organic molecules with large nonlinear coefficients should have the following characteristics: asymmetric charge distribution, the delocalized nature of π electrons, and easy polarization by external electric fields, and a large π conjugated system. In recent years, metal organic compounds have become a leader in the field of optics, mainly because of their very good nonlinear optical properties. In the future, people will do more investigation on the nonlinearity of metal organic complexes. Researchers have shown great interest in iridium metal organic complexes due in particular to their attractive stability and nonlinear activity. This review mainly studies the nonlinear principle, performance test and Measurement of nonlinearity of iridium metal complexes. The nonlinear properties of other metal-metal organic complexes will not be discussed.
基金support from the National Natural Science Foundation of China(No.22005179)the Natural Science Foundation of Shandong Province(Nos.ZR2020QB113,ZR2020MB018 and ZR2021QB049).
文摘A general and high-efficiency C-alkylation of oxindoles and barbituric acids has been developed by a Cp*Ir complex[Cp*Ir(2,20-bpyO)(OH)]Na with a bipyridine-based functional ligand.In particular,H_(2)O was selected as the solvent instead of the organic solvent in this catalytic system.Through mild reaction conditions gave a variety of corresponding alkylated heterocyclic compounds with good to excellent yields.More importantly,the gramscale C-alkylation reaction was successfully carried out with good yield using a common route with only a single purification by column chromatography.
基金National Natural Science Foundation of China,Grant/Award Number:51803208the Youth Innovation Promotion Association CAS,Grant/Award Number:E2202005。
文摘Herein,we design and synthesize a series of oligomers[Ir(ppy)2(dabpy)-ODPA]n(D1-n)by copolymerization of[Ir(ppy)2(dabpy)][PF6](D2)with 4,4′-Oxydiphthalic anhydride(ODPA),to resolve the problem of simultaneous improvement of sta-bility and activity of classical iridium complex for photocatalytic water-splitting.Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,solid-state nuclear magnetic resonance,and gel permeation chromatography results indicate that the degree of polymerization(n)of D1-n could be tuned by the syn-thesis method.The best photocatalytic performance is reached by D1-n with n at of 2 and/or 3(D1-2/3),which exhibits a photocatalytic lifetime up to 676 h and a photocatalytic hydrogen evolution of 162055.1 Compared with classicalμmol⋅g-1.iridium complex D2,the photocatalytic lifetime of D1-2/3 is about 38 times longer and the photocatalytic activity is 1.3 times higher.Further increase of n leads to a decrease in both photocatalytic lifetime and activity.According to the spectro-scopic characterizations,photoelectrochemical experiments,and density functional theory calculation,the significantly enhanced photocatalytic performance of D1-2/3 originates from the oligomeric structure.The oligomer chain of D1-2/3 with suit-able length acts as a large steric hindrance to reduce the undesired photoinduced decomposition and prolong its lifetime.The possible coupling of adjacent Ir com-plexes in D1-2/3 lowers the energy gap and increases the utilization of visible light,which overcomes the adverse effect of large steric hindrance andfinally improve the activity.This workfirst provides a simple strategy for constructing oligomeric Ir photosensitizers to simultaneously achieve long lifetime and high activity,it will lay the foundation for the design of highly efficient photosensitizers in the future.
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supported by the National Natural Science Foundation of China(No.21501037)the Natural Science Foundation of Hainan Province(No.20152017)the Science and Research Project of Education Department of Hainan Province(Nos.Hjkj2013-25 and Hnky2015-27)
文摘Two new fluorinated phenylisoquinoline-based iridium（Ⅲ） complexes,[Ir（f2piq）2（bipy）][PF6]（3a） and[Ir（fmpiq）2（bipy）][PF6]（3b）（f2piq = l-（2,4-difluorophenyl）isoquinoline,fmpiq = 1-（4-fluoro-2-methylphenyl）isoquinoline,bipy = 2,2＇-bipyridine）,have been synthesized and fully characterized.Single crystal X-ray diffraction study has been undertaken on complexes 3a and 3b,which show that each adopts the distorted octahedral coordination geometry with the cis-C,C＇ and trans-N,N＇ configuration.The photoluminescence spectra of 3a and 3b exhibit yellow and orange emission maxima at 584 and 600 nm,respectively.The frontier molecular orbital diagrams and the lowest-energy electronic transitions of 3a-3b have been calculated with density functional theory（DFT） and time-dependent DFT（TD-DFT）.The absorption and emission spectra of complex 3b is red-shifted relative to those of complex 3a,as a consequence of the nature of the methyl group.
