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A red fluorescent BODIPY probe for iridium (III) ion and its application in living cells
摘要： A new red fluorescent probe 1 based on BODIPY skeleton has been successfully synthesized through introduction of 2-(thiophen-2-yl) quinoline moiety at meso- and 3-position, which exhibits excellent optical performance, including high fluorescence quantum yield, large pseudo Stokes’ shift as well as high selectivity and sensitivity towards iridium (III) ion in aqueous solution and in living cells.
关键词： iridium (III) ion probe,fluorescence imaging,BODIPY probe
更新于2025-11-21 11:08:12
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Synthesis, Photophysical and Electroluminescent Properties of Iridium(III) Complexes with 2-Aryl-thiazole and Oxadiazol-substituted Amide Derivative Ligands
摘要： By using aryl-thiazole as cyclometalated ligand and oxadiazol-substituted amide as ancillary ligand, three novel iridium(III) complexes have been synthesized and characterized, and the photophysical and electrochemical properties have been investigated. Complexes 1–3 exhibit efficient phosphorescence emissions at 542, 555 and 585 nm with photoluminescence quantum yields (PLQYs) of 0.04, 0.03 and 0.02 in CH3CN solutions, respectively. In the 10 wt% doped 2,4-diphenyl-6-bis(12-phenylindolo)[2,3-a]carbazole-11-yl)-1,3,5-triazine (Dictrz) film, the PLQYs (0.88 for complex 1, 0.47 for complex 2 and 0.37 for complex 3) increase significantly owing to the great restriction of rotations and vibrations in rigid host. The organic light-emitting diodes based on these complexes show good performance with the maximum current efficiencies of 20.06, 22.20 and 13.45 cd A-1 and maximum power efficiencies of 13.54, 17.31 and 9.48 lm W?1 with the CIE coordinates of (0.46, 0.53), (0.49, 0.50) and (0.59, 0.40) for complexes 1?3, respectively.
关键词： Iridium complex,Aryl-thiazole,Organic light-emitting diodes,Oxadiazol-substituted amide
更新于2025-11-19 16:56:35
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Blue-green-emitting cationic iridium complexes with oxadiazole-type counter-anions and their use for highly efficient solution-processed organic light-emitting diodes
摘要： Cationic iridium complexes are promising phosphorescent dopants for solution-processed organic light-emitting diodes (OLEDs) and counter-anion control has emerged as a facile approach to tailor their properties for high-performance devices. A series of oxadiazole-type anions, 3-(5-phenyl-1,3,4-oxadiazol-2-yl)benzenesulfonate (OXD-SO3?), 3-(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl)benzenesulfonate (tBuOXD-SO3?) and (3-(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl)phenyl)trifluoroborate (tBuOXD-BF3?), have been prepared as counter-anions for blue-green-emitting cationic iridium complexes. The photophysical and electrochemical properties of the anions and the complexes have been comprehensively characterized. The anions do not affect the emission properties of the phosphorescent cation and efficiently transfer their energy to the cations in films. Solution-processed, double-layer OLEDs using the complexes as dopants have shown much higher (～1.4) efficiencies than the device using the reference complex with a PF6? counter-anion, owing to the improvement of carrier transport/recombination balance by the electron-trapping effect of oxadiazole-type anions. In particular, the blue-green device using the complex with the OXD-SO3? counter-anion affords a peak current efficiency of 37.6 cd A?1 and a peak external quantum efficiency (EQE) of 15.2%, which is the highest for solution-processed OLEDs based on cationic iridium complexes reported so far.
关键词： solution-processed OLEDs,oxadiazole-type counter-anions,phosphorescent dopants,cationic iridium complexes,high-performance devices
更新于2025-11-14 15:23:50
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Dose distribution verification in high-dose-rate brachytherapy using a highly sensitive normoxic N-vinylpyrrolidone polymer gel dosimeter
摘要： Rapid technological advances in high-dose-rate brachytherapy have led to a requirement for greater accuracy in treatment planning system calculations and in the verification of dose distributions. In high-dose-rate brachytherapy, it is important to measure the dose distribution in the low-dose region at a position away from the source in addition to the high-dose range in the proximity of the source. The aim of this study was to investigate the accuracy of a treatment plan designed for prostate cancer in the low-dose range using a normoxic N-vinylpyrrolidone-based polymer gel (VIPET gel) dosimeter containing inorganic salt as a sensitizer (iVIPET). The dose response was evaluated on the basis of the transverse relaxation rate (R2) measured by magnetic resonance scanning. In the verification of the treatment plan, gamma analysis showed that the dose distributions obtained from the polymer gel dosimeter were in good agreement with those calculated by the treatment planning system. The gamma passing rate according to the 2%/2 mm criterion was 97.9%. The iVIPET gel dosimeter provided better accuracy for low doses than the normal VIPET gel dosimeter, demonstrating the potential to be a useful tool for quality assurance of the dose distribution delivered by high-dose-rate brachytherapy.
关键词： Iridium-192,MRI,High-dose-rate brachytherapy,Polymer gel dosimeter
更新于2025-09-23 15:23:52
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New blue phosphorescence from trifluorosulfonyl-substituted iridium complexes
摘要： For color-pure phosphorescence organic light emitting diodes (PHOLEDs), we synthesized the trifluoromethyl sulfonyl substituted ligand and two new blue Iridium complexes with perfluoro-sulfonyl group (SOCF3pic and SOCF3mpic). The both iridium complexes showed similar photophysical and thermal properties while the HOMO energy leves of two Iridium complexes slightly differnet to be -5.84 eV for SOCF3pic and -5.74 eV for SOCF3mpic, respectively. The device with the SOCF3mpic dopant exhibited higher device efficiencies of 7.17 cd/A and 3.7 % compared to that with the SOCF3pic dopant (4.03 cd/A and 2.78 %). Two-dimensional GIXD images of scattered X-ray intensity from surface to full depth for SOCF3pic-doped and SOCF3mpic-doped TCTA:4PTPS films were characterized for preferential orientation along the out-of-plane direction.
关键词： preferential orientation along the out-of-plane direction,blue phosphorescence,iridium complex,grazing incidence wide-angle X-ray diffraction,organic light emitting diodes
更新于2025-09-23 15:23:52
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Ru(II) and Ir(III) complexes containing ADA and DAD triple hydrogen bonding motifs: Potential tectons for the assembly of functional materials.
摘要： The synthesis and characterisation of series of [Ru(II)(bpy)2L] and [Ir(ppy)2L] complexes containing ligands L with the potential to engage in triple hydrogen bonding interactions is described. L1 and L2 comprise pyridyl triazole chelating units with pendant diaminotriazine units, capable of donor-acceptor-donor (DAD) hydrogen bonding, while L3 and L4 contain ADA hydrogen bonding units proximal to N^N and N^O cleating sites, respectively. X-ray crystallography shows the L1 and L2 containing Ru(II) complexes to assemble via R22(8) hydrogen bonding dimers, while [Ru(II)(bpy)2L4] assembles via extended hydrogen bonding motifs to form one dimensional chains. By contrast, the expected hydrogen bonding patterns are not observed for the Ru(II) and Ir(III) complexes of L3. Spectroscopic studies show that the absorption spectra of the complexes result from combinations of MLCT and LLCT transitions. The L1 and L2 complexes of Ir(III) and Ru(II) complexes are emissive in the solid state and it seems likely that hydrogen bonding to complementary species may facilitate tuning of their 3ILCT emission. Low frequency Raman spectra provide further evidence for ordered interactions in the solid state for the L4 complexes, consistent with the results from X-ray crystallography.
关键词： crystal engineering,ruthenium,Hydrogen bonding,iridium,X-ray crystallography
更新于2025-09-23 15:23:52
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New heteroleptic iridium(III) nitro complexes derived from fac-[Ir(NO2)3(H2O)3]
摘要： An aqueous solution of fac-[Ir(H2O)3(NO2)3] (1) was utilized as a starting material for preparation of the new heteroleptic iridium complex [Ir(H2O)(bpy)(NO2)3] (2). From alkaline solutions of 2, the salt Na[Ir(OH)(NO2)3(bpy)]·2H2O was isolated and its structure was determined by X-ray structure analysis. Structures of new compounds 2 and 3 as well as the parent complex 1 was characterized using multinuclear magnetic resonance spectroscopy and mass spectrometry. The structures of parent fac-[Ir(H2O)3(NO2)3] and complexes 2 and 3 were probed by employing density functional theory (DFT) calculations.
关键词： Nitrocomplexes,Iridium,DFT,NMR,Aquacomplexes,X-ray structure
更新于2025-09-23 15:23:52
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Operando observation of chemical transformations of iridium oxide during photoelectrochemical water oxidation
摘要： Iridium oxide is one of the few catalysts capable of catalyzing the oxygen evolution reaction (OER) in both acidic and basic conditions. Understanding the mechanism of IrOx under realistic photoelectrochemical conditions is important for the development of integrated water splitting systems. Herein, we have developed a highly efficient OER photoanode in pH 1 aqueous solutions based on a sputtered IrOx film and a p+n-Si light absorber, interfaced with sputtered Au layer. Operando high energy resolution fluorescence detection X-ray absorption spectroscopy (HERFD XAS) was employed to monitor the oxidation state changes of IrOx during both electrochemical and photoelectrochemical (PEC) water oxidation reactions in pH 1 aqueous solutions. We observed a gradual increase of the average oxidation state of Ir with increasing anodic potential in the pre-catalytic region, followed by a reduction of Ir under O2 evolution conditions. Consistent results were obtained on dark anodes and illuminated photoanodes. However, when the thickness of IrO2 was increased to 2 and 3 nm, the spectral changes became much less pronounced and the reduction of Ir oxidation state after the OER onset was not observed. This is due to the lower surface to bulk ratio, where lattice oxygen sites in the bulk are not accessible for the formation of hydroxide. More generally, the operando method developed here can be extended to other materials, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.
关键词： oxygen evolution reaction (OER),electrochemical and photoelectrochemical (PEC),high energy resolution fluorescence detection X-ray absorption spectroscopy (HERFD XAS),iridium oxide,Operando method
更新于2025-09-23 15:23:52
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Sequential activation of methane by Ir+: An IRMPD and theoretical investigation
摘要： The sequential activation of up to 4 CH4 molecules by Ir+ is investigated through a gas-phase infrared multiple photon dissociation (IRMPD) experiment and theoretical calculations. A molecular beam apparatus was used to generate Ir+ by laser ablation and expose it to controlled amounts of CH4. Product ions were irradiated with IR light from a free electron laser over the 500–1800 cm?1 spectral range and photodissociation was monitored using a time-of-flight mass spectrometer. Experimental spectra were obtained for five distinct species: [Ir,3C,8 H]+, [Ir,3C,10 H]+, [Ir,4C,10 H]+, [Ir,4C,12 H]+, and [Ir,O,3C,12 H]+. To identify these species, B3LYP/def2-TZVPPD geometry optimizations were performed on a variety of possible structures, with computed IR spectra compared to the experimental IRMPD spectra. This has led to the following assignments: [Ir,3C,8 H]+ = IrCH2(CH3)2+, [Ir,3C,10 H]+ = HIr(CH3)3+, [Ir,4C,10 H]+ = Ir(CH3)2(C2H4)+, [Ir,4C,12 H]+ = a mixture of HIr(CH3)(C2H4)+(CH4), HIr(CH3)2(C2H5)+, Ir(CH3)4+, and (H2)Ir(CH3)2(C2H4)+, and [Ir,O,3C,12 H]+ = (H2O)HIr(CH3)3+. Notably, evidence for C C coupling is observed upon reaction with a fourth methane. Mechanisms for the formation of the observed products were also explored computationally by examining the reaction coordinate pathways for the reactions of methane with HIrCH+, IrCH2+, Ir(CH3)2+, HIrCH2(CH3)+, HIr(CH3)3+, and IrCH2(CH3)2+.
关键词： Iridium,Carbon-carbon coupling,Methane activation,Dehydrogenation,Infrared multiple photon dissociation,Reaction coordinate pathway
更新于2025-09-23 15:22:29
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Gas Sensing with Iridium Oxide Nanoparticle Decorated Carbon Nanotubes
摘要： The properties of multi-wall carbon nanotubes decorated with iridium oxide nanoparticles (IrOx-MWCNTs) are studied to detect harmful gases such as nitrogen dioxide and ammonia. IrOx nanoparticles were synthetized using a two-step method, based on a hydrolysis and acid condensation growth mechanism. The metal oxide nanoparticles obtained were employed for decorating the sidewalls of carbon nanotubes. Iridium-oxide nanoparticle decorated carbon nanotube material showed higher and more stable responses towards NH3 and NO2 than bare carbon nanotubes under different experimental conditions, establishing the optimal operating temperatures and estimating the limits of detection and quantification. Furthermore, the nanomaterials employed were studied using different morphological and compositional characterization techniques and a gas sensing mechanism is proposed.
关键词： carbon nanotubes,relative humidity effect,metal nanoparticles,iridium oxide,chemoresistive gas sensor
更新于2025-09-23 15:22:29