Synthesis and phosphorescent properties of two novel iridium (Ⅲ) complexes bearing bulky tert-butyl substituents

The synthesis and phosphorescence properties of two novel Ir(Ⅲ)complexes bearing tert-butyl substituents,bis(4-tert-butyl-2- phenylbenzothiozolato-N,C^(2′))iridium(Ⅲ)(acetylacetonate)[(tbt)_2Ir(acac)]and bis(4-tert-butyl-1-phenyl-1H-benzimidazolato- N,C^(2′))iridium(Ⅲ)(acetylacetonate)[(tpbi)_2Ir(acac)],are reported,their molecular structures are confirmed by^1H NMR,ESI-MS and elementary analysis.Photoluminescence(PL)studies revealed that they can emit strong green and orange phosphorescence in high quantum yields.Compared to their prototypes lacking of tert-butyl substituents,the two novel iridium(Ⅲ)complexes both have shorter lifetimes and improved or nearly similar PL quantum efficiencies,implying that the exciton quenching is inhibited effectively when molecular steric hindrance increases.The two chelates have great potential to be used as electrophosphorescent materials.

Room-Temperature Phosphorescence and Lifetime of Fossil Resins (Amber) from Dominican Republic, Mexico, Baltic Sea, Myanmar, and Fushun, China

Amber can emit room temperature phosphorescence(RTP)under the well-known 365 nm fluorescence ultraviolet light.This paper is devoted to the phosphorescence study of 20 pieces of amber materials from the Dominican Republic,Mexico,Baltic sea,Myanmar,and Fushun,China.The results show that amber from the same geographic origin has similar shape in phosphorescence spectra.However,the shape of the amber phosphorescence spectra varies depending on their different localities.Burmite(amber from Myanmar)and Fushun amber have a bright yellow phosphorescence with a long lifetime,while the Dominican and Mexican ones are weaker and last shorter.The irradiation of Baltic amber becomes faint or even inert.Phosphorescence spectral Gaussian fitting results suggest an emission maximum near 550 nm in most amber samples.Their phosphorescence lifetime,analyzed through the exponential function fitting,is up to 1 second in Burmite and Fushun samples,shorter in the Dominican and Mexican ones,about 0.230 s,and the shortest in Baltic amber,close to 0.151 s.These variations of phosphorescence lifetime and intensity are related to the relative geological ages of these amber.It indicated that the phosphorescence agent was probably formed during the long geological time.While the anomaly occurred in Baltic amber,the only one found in a sea secondary deposit form,it demonstrated that the terrestrial geological environment these amber preserved has prevented the phosphorescence agent to be deactivated.

Phosphorescent Cationic Iridium（Ⅲ） Complexes with 1,3,4-Oxadiazole Cyclometalating Ligands： Solvent-Dependent Excited-State Dynamics

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.

Preparation of Phosphors MAl_2O_4∶Eu^(2+)(M=Ca,Sr,Ba) by Microwave Heating Technique and Their Phosphorescence

The phosphors of the alkaline earth aluminates coactivated with europium and other rare earths were successfully obtained by microwave radiation heating technique.These phosphors have bright phosphorescence and maintain their afterglow for a fairly long duration.

Sol-gel preparation and phosphorescence property of Mn^(2+)-doped zinc boro-silicate glass thin films

Mn2＋-doped zinc borosilicate （ZBSM） glass thin films were first synthesized by sol-gel method. In the experiment, a thin gel film was depos-ited onto quartz glass substrates by dip-coating method and then heat-treated to form a Mn2＋-doped zinc borosilicate glass thin film. Long lasting phosphorescence （LLP） and photo-stimulated long lasting phosphorescence （PSLLP） were found in the film sample. According to fluorescence spectra, LLP emission spectra, and PSLLP emission spectra, both LLP and PSLLP emissions are attributed to the energy level transition of 4Eg→4A1g from Mn2＋. Both the phosphorescence intensity decay curves contain a fast decay component and another slow decay one. The thermoluminescence （TL） spectra show that the sample has two kinds of traps at least and their energy level values are about 0.8 eV and 1.02 eV, which could be estimated by the Randall and Willcins formula. The infrared absorption spectra （IR） consist of characteristic vi-bration bands of Si-O-Si, Si-O-Zn, B-O in [BO3], B-O group, and Zn-O in [ZnO4]. Moreover, image storage and logical operation of the ZBSM film were carried out successfully through an experiment analogues of optical storage.

A pilot study of the dynamics of tissue oxygenation in vivo using time-resolved phosphorescence imaging

Oxygenation of tissues plays an important role in the development and progression of tumor to treatment effects.Method of metalloporphyrines phosphorescence quenching by oxygen is one of the ways to measure dynamics of the oxygen concentration in the tissues by phosphorescence lifetime imaging of meso-tetra(sulfophenyl)tetrabenzoporphyrin Pd(Ⅱ)(TBP)using the time-correlated single photon counting(TCSPC)method.It has been shown that phosphorescence lifetime of the sensor in S37 tumor in vivo varied in the range of 130 to 290μs after both topical and intravenous administration of TBP.It indicates that oxygen level in tumors was lower compared to normal tissues where TBP phosphorescence has not been detected.Phosphorescence lifetimes of TBP increased in the solid tumor and in the muscle after photodynamic therapy of solid tumor that demonstrates oxygen consumption during treatment and possibly stopping the blood flow and hence the oxygen supply to the tissues.

Preparation of the Phosphors BaAl_2O_4:Eu, RE (RE=Dy, Ho) by Microwave Heating Technique and Observation of Long Phosphorescence

The phosphors BaAl2O4: Eu2+. RE (RE=Dy. Ho) have been prepared by the microwave heating technique. The long-lasting phosphorescence in the phosphors of the barium aluminate activated with europium and other rare earths has been observed for the first time.

Highly efficient polymer phosphorescent light-emitting devices based on a new polyfluorene derivative as host

Several highly efficient iridium-complex polymer light-emitting devices （PLEDs） are fabricated, with a newly synthesized blue conjugated polymer, poly[（9,9-bis（4-（2-ethylhexyloxy）phenyl）-fluorene）-co-（3,7-dibenziothiene-S,S- dioxide15）] （PPF-3,TSO15）, chosen as host. High luminous efficiencies of 7.4 cd.A-1 and 27.4 cd.A-1 are achieved in red and green PLEDs, respectively, by optimizing the doping concentrations of red phosphorescent dye iridium bis（1- phenylisoquinoline） （acetylacetonate） （Ir（piq）） and green phosphorescent dye iridium tris（2-（4-tolyl）pyridinato-N, C2＇） （Ir（mppy）3）.Furthermore, highly efficient white PLEDs （WPLEDs） with the Commission Internationale de l＇Eclairage （CIE） coordinates of （0.35, 0.38） are successfully produced by carefully controlling the doping concentration of the irid- ium complex. The obtained WPLEDs show maximal efficiencies of 14.4 cd.A-1 and 10.1 lm.W-1, which are comparable to those of incandescent bulbs. Moreover, the electroluminescent spectrum of the white device with an initial luminance of about 1000 cd.m-2 is stable, subject to constant applied current stress, indicating that good device stability can be obtained in this system.

Long Lasting Phosphorescence in Eu^(2+) and Ce^(3+) Co-Doped Strontium Borate Glasses

Long lasting phosphorescence (LLP) was observed in Eu2+, Ce3+ co-doped strontium borate glasses prepared under the reducing atmosphere due to the emission of both Eu2 + and Ce3+ . The methods of photoluminescence, thermolu-minescence and phosphorescence were used to study the samples, and possible mechanism was suggested. The co-doping of Ce3 + ions poisoned the phosphorescence emission of Eu2 + because of the competition to obtain the trapped electron . The phosphorescence of Ce3 + in the sample decays more quickly than that of Eu2 + , which is suggested for the reason that the emission energy of Ce3 + is higher or the distance between Ce3 + and electron traps of the glasses is longer.

Study on the Interaction of Mitomycin C with ct-DNA by Pd-Porphin Room Temperature Phosphorescence Probe

Anticancer drug Mitomycin C (MMC) quenches remarkably phosphorescence and reduces lifetime of phosphorescence probe, Pd-meso-tetrakis-(4-trimethylaminophenyl)porphin (Pd-TAPP), in the presence of calf thymus DNA. These results may be attributed to the site competition of MMC with the probe and electron transfer between MMC and probe. MMC also increases polarization degree of the probe by covalent drug-DNA or DNA-drug-DNA crosslinking.

BRIGHT LONG AFTERGLOW PHOSPHORESCENCE GLASS MADE OF SrAl_(2)O_(4): Eu^(2+), Dy^(3+) AND GLASS FRITS

Bright long afterglow phosphorescence glasses were prepared by using SrAl2O4： Eu^2＋, Dy^3＋ phosphors and suitable glass frits together. The SrAl2O4： Eu^2＋, Dy^3＋ phosphors were initially prepared by the solid reaction method. Three kinds of glass frits were prepared to match the SrAl2O4： Eu^2＋, Dy^3＋ phosphors. Effects of the compositions of the glass frits, the ratios of the phosphors to the frits us well us the firing temperature and firing times on the properties of the samples were discussed. XRD analysis indicated the samples exhibited the typical diffraction peaks of SrAlwO4： Eu^2＋, Dy^3＋. The emission spectra of the samples showed broad bands peaking at 510nm.The excitation spectra of the samples showed broad bands ranging from 300 to 480hm. These are believed due to the 5d4f-4f transitions of Eu^2＋ in the SrAl2O4： Eu^2＋, Dy^3＋ phosphors. The afterglow luminescence of the samples excited by a 40W fluorescence lamp for 30min can be observed in the dark for more lOh with the naked eyes. It can find wide applications in many fields.

Highly Efficient Greenish-Yellow Phosphorescent Organic Light-Emitting Diodes Based on a Novel 2,3-Diphenylimidazo[1,2-a]Pyridine Iridium(Ⅲ) Complex

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.

Determination of trace arsenic(V) by catalytic solid substrate-room temperature phosphorescence quenching method

In the H2SO4 medium and in the presence of dodecylbenzene sulfonic acid sodiumsalt (DBS), dimethyl yellow (R) could emit strong and stable solid substrate room temperature phosphorescence (RTP) on filter paper. And NaIO4 could oxidize R to cause the RTP quenching. Arsenic(V) could catalyze the reaction of NaIO4 oxidizing R, which caused the RTP sharply quenching. The reducing value of phosphorescence intensity (ΔIp) for the system with DBS is 3.3 times higher than that without DBS. Moreover, the ΔIp is proportional to the concentration of As(V). Based on the facts above, a new RTP quenching method for the determination of trace As(V) has been established.

Probing defects in ZnO by persistent phosphorescence

Native point defects in ZnO are so complicated that most of them are still debating issues, although they have been studied for decades. In this paper, we experimentally reveal two sub-components usually hidden in the low energy tail of the main broad green luminescence band peaking at 547 nm （-2.267 eV） in intentionally undoped ZnO single crystal by selecting the below-band-gap （BBG） optical excitations （e.g. light wavelengths of 385 nm and 450 nm）. Moreover, both sub-components are manifested as long persistent phosphorescence once the BBG excitations are removed. With the aid of a newly developed model, the energy depths of two electron traps involved within the long lived orange luminescence are determined to be 44 meV and 300 meV, respectively. The candidates of these two electron traps are argued to be most likely hydrogen and zinc interstitials in ZnO.

Enhancement of electroluminescent properties of organic optoelectronic integrated device by doping phosphorescent dye

Organic optoelectronic integrated devices（OIDs） with ultraviolet（UV） photodetectivity and different color emitting were constructed by using a thermally activated delayed fluorescence（TADF） material 4, 5-bis（carbazol-9-yl）-1, 2-dicyanobenzene（2 CzPN） as host. The OIDs doping with typical red phosphorescent dye [tris（1-phenylisoquinoline）iridium（Ⅲ）, Ir（piq）3], orange phosphorescent dye {bis[2-（4-tertbutylphenyl）benzothiazolato-N,C-（2＇）]iridium（acetylacetonate）,（tbt）2 Ir（acac）}, and blue phosphorescent dye [bis（2, 4-di-fluorophenylpyridinato）-tetrakis（1-pyrazolyl）borate iridium（Ⅲ）, FIr6] were investigated and compared. The（tbt）2 Ir（acac）-doped orange device showed better performance than those of red and blue devices, which was ascribed to more effective energy transfer. Meanwhile, at a low dopant concentration of 3 wt.%, the（tbt）2 Ir（acac）-doped OIDs showed the maximum luminance, current efficiency, power efficiency of 70786 cd/m^2, 39.55 cd/A, and 23.92 lm/W, respectively, and a decent detectivity of 1.07 × 10^11 Jones at a bias of -2 V under the UV-350 nm illumination. This work may arouse widespread interest in constructing high efficiency and luminance OIDs based on doping phosphorescent dye.

Preparation of Long-Lasting Phosphorescence (LLP) Glass-Ceramic Materials

Three kinds of glass-ceramics, i.e., Mn 2+ doped zinc borosilicate, Eu 2+, Dy 3+ co-doped strontium aluminoborate and Eu 2+, Nd 3+ co-doped calcium aluminoborate were prepared, whose phosphorescence emission band peaks at 525, 516 and 464 nm, respectively. In preparation of these glass-ceramics the base glasses were gained by heating the mixed starting materials at high temperature to get the transparent glasses; then those glasses were heat-treated and turned to opaque glass-ceramics. X-ray diffraction (XRD) shows that the crystallites are ZnSiO 4, SrAl 2O 4 and α-CaAl 2B 2O 7, respectively. It is a useful way to get new LLP materials by the method reported in this work that may be considered as “from glass to crystal”.

High-efficiency organic light-emitting diodes based on ultrathin blue phosphorescent modification layer

Yellow organic light-emitting devices （YOLEDs） with a novel structure of ITO/MoO3（5 nm）/NPB（40 nm）/ TCTA（15 nm）/CBP：（tbt）zIr（acac）（x%）（25 nm）/FIrpic（y nm）/TPBi（35 nm）/Mg：Ag are fabricated. The ultrathin blue phosphorescent bis[（4,6-difluorophenyl）-pyridi-nato-N,C2＇]（picolinate） iridium （III） （FIrpic） layer is regarded as a high- performance modification layer. By adjusting the thickness of FIrpic and the concentration of （tbt）2Ir（acac）, a YOLED achieves a high luminance of 41618 cd/m2, power efficiency of 49.7 lm/W, current efficiency of 67.3 cd/A, external quan- tum efficiency （EQE） of 18%, and a low efficiency roll-off at high luminance. The results show that phosphorescent material of FIrpic plays a significant role in improving YOLED performance. The ultrathin FIrpic modification layer blocks excitons in EML. In the meantime, the high triplet energy of FIrpic （2.75 eV） alleviates the exciton energy transport from EML to FIrpic.

Metal nanoparticle-enhanced room temperature phosphorescence of diiodofluorescein on the filter paper substrate

Metal-enhanced room temperature phosphorescence of diiodofluorescein was first observed on filter paper surface.The phosphorescence intensity is 2.5-fold brighter from diiodofluorescein on silver nanoparticles-deposited filter paper as compared with an identical control sample without silver nanoparticles.Furthermore,enhanced absorption was also observed for the same system.Our findings suggest that both singlet and triplet states can couple to surface plasmons and enhance phosphorescence quantum yields at ...

Synthesis and Photoluminescence of a New Red PhosphorescentIridium(III) Quinoxaline Complex

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.

High-Efficiency Green Phosphorescent Organic Light-Emitting Diode Based on Simplified Device Structures

A high-efficiency green phosphorescent organic light emitting diode with a simplified structure is achieved that is free of a hole transport layer. The design of this kind of device structure not only saves the consumption of organic materials but also greatly reduces the structural heterogeneities and effectively facilitates the charge injection into the emissive layer. The resulting green phosphorescent organic light-emitting diodes （PHOLEDs） exhibit higher electroluminescent efficiency. The maximum external quantum efficiency and current efficiency reach 23.7% and 88 cd/A, respectively. Moreover the device demonstrates satisfactory stability, keeping 23.7% and 88cd/A, 22% and 82cd/A, respectively, at a luminance of 100 and 1000cd/m2. The working mechanism for achieving high efficiency based on such a simple device structure is discussed correspondingly. The improved charge carrier injection and transport balance are proved to prominently contribute to achieve the high efficiency and great stability at high luminance in the green PHOLEDs.