Synthesis, characterization, photophysics and electrophosphorescent applications of phosphorescent platinum cyclometalated complexes with 9-arylcarbazole moieties

A series of cyclometalating platinum(II) complexes with substituted 9-arylcarbazolyl chromophores have been synthesized and characterized. These complexes are thermally stable and most of them have been characterized by X-ray crystallography. The phosphorescence emissions of the complexes are dominated by (MLCT)-M-3 excited states. The excited state properties of these complexes can be modulated by varying the electronic characteristics of the cyclometalating ligands via substituent effects, thus allowing the emission to be tuned from bright green to yellow, orange and red light. The correlation between the functional properties of these metallophosphors and the results of density functional theory calculations was made. Because of the propensity of the electron-rich carbazolyl group to facilitate hole injection/transport, the presence of such moiety can increase the highest occupied molecular orbital levels and improve the charge balance in the resulting complexes relative to the parent platinum(II) phosphor with 2-phenylpyridine ligand.

Novel Oligo-9,9 '-spirobifluorenes through ortho-Linkage as Full Hydrocarbon Host for Highly Efficient Phosphorescent OLEDs

4-Bromo-9,9'-spirobifluorene is facilely synthesized, and from this precursor, two ortho-linked oligo-9,9'-spirobifluorenes, 44BSF and 24TSF, are constructed. Devices with 24TSF as the full-hydrocarbon host material and Ir(ppy)(3) or (ppq)(2)Ir(acac) as the triplet emitter show maximum external quantum efficiencies of 12.6 and 10.5% for green and red electrophosphorescence, respectively.

Diarylmethylene-bridged 4,4 '-(bis(9-carbazolyl))biphenyl: morphological stable host material for highly efficient electrophosphorescence

novel compound (BCBP) based on the modification of a well-known host material 4,4'-(bis(9-carbazolyl))biphenyl (CBP) through arylmethylene bridge linkage was synthesized, and fully characterized. Its thermal, electrochemical, electronic absorption and photoluminescent properties were studied. A high glass transition temperature (T-g) of 173 degrees C is observed for BCBP due to the introduction of the bridged structure, remarkably contrasting with a low T-g of 62 degrees C for CBP. Furthermore, the bridged structure enhances the conjugation and raises the HOMO energy, thus facilitating hole-injection and leading to a low turn-on voltage in an electroluminescent device. With the device structure of ITO/MoO3/NPB/Ir complex: BCBP/BCP/Alq(3)/LiF/Al, maximum power efficiencies of 41.3 lm/W and 6.3 lm/W for green- and blue-emitting OLED were achieved, respectively.

Phosphorescence Color Tuning by Ligand, and Substituent Effects of Multifunctional Iridium(III) Cyclometalates with 9-Arylcarbazole Moieties

The synthesis, isomeric studies, and photophysical characterization of a series of multifunctional cyclometalated iridium(III) complexes containing a fluoro- or methyl-substituted 2[3-(N-plienylcarbazolyl)]pyridine molecular framework are presented. All of the complexes are thermally stable solids and highly efficient electrophosphors. The optical, electrochemical, photo-, and electrophosphorescence traits of these iridium phosphors have been studied in terms of the electronic nature and coordinating site of the aryl or pyridyl ring substituents. The correlation between the functional properties of these phosphors and the results of density functional theory calculations was made. Arising from the propensity of the electron-rich carbazolyl group to facilitate hole injection/transport, the presence of such a moiety can increase the highest-occupied molecular orbital levels and improve the charge balance in the resulting complexes relative to the parent phosphor with 2-phenylpyridine ligands. Remarkably, the excited-state properties can be manipulated through ligand and substituent effects that allow the tuning of phosphorescence energies from bluish green to deep red.

(Ce_(0.9)Nd_(0.1))_(1-x)Mo_xO_(2-δ)(0.00≤x≤0.10)的合成、表征与电性能

采用溶胶-凝胶法合成(Ce0.9Nd0.1)1-xMoxO2-δ(x=0.00、0.02、0.05、0.10)氧化物,通过X射线衍射(XRD)、场发射扫描电镜(FESEM)等手段对氧化物进行结构表征,交流阻抗谱测试电性能.结果表明:所有样品均为单一萤石立方结构;少量MoO3的加入提高了材料的致密性,降低了材料的总电阻、晶界电阻和晶界电阻在总电阻中所占比例,提高了材料的电导率.1200℃烧结样品24h,测试温度700℃时,(Ce0.9Nd0.1)1-xMoxO2-δ(x=0.00)总电导率和晶界电导率分别为0.05和0.19S·m-1,掺Mo材料(Ce0.9Nd0.1)1-xMoxO2-δ(x=0.02)的总电导率和晶界电导率分别为2.42和3.96S·m-1.

Luminescence properties of Y0.9-xGdxEu0.1Al3(BO3)(4) (0 <= x <= 0.9) phosphors prepared by spray pyrolysis process

Starting from metal nitrate aqueous solutions and H3BO3, Y0.9-xGdxEu0.1Al3(BO3)(4) (0 <= x <= 0.9) phosphors were synthesized by spray pyrolysis followed by annealing at high temperature. The obtained phosphor particles have spherical morphology with size in the range 0.5-2 mu m. Independent of the x values in Y0.9-xGdxEu0.1Al3(BO3)(4) (0 <= x <= 0.9) phosphors, the Eu3+ ion shows its characteristic D-5(0), (1)-F-7(J) (J = 0, 1, 2, 3, 4) transitions with D-5(0)-F-7(2) red emission (612 nm) as the most prominent group. The photoluminescence intensity of phosphors increases with the increase of x value in Y0.9-xGdxEu0.1Al3(BO3)(4) (0 <= x <= 0.9) due to an energy migration process like Gd3+-(Gd3+)(n)-Eu3+ that occurred in the host materials.

Synthesis and chain-length dependent properties of monodisperse oligo(9,9-di-n-octylfluorene-2,7-vinylene)s

A series of monodisperse oligo(9,9-di-n-octylfluorene-2,7-vinylene)s (OFVs) with fluorene units up to 11 has been synthesized following a divergent approach. Chain length was found to affect not only photophysical properties but also thermal properties. Absorption and photoluminescence spectra are red-shifted with increasing chain length. The effective conjugated length has been extrapolated to be as long as 19 fluorene vinylene units, indicative of a well-conjugated system. With the number of fluorene units > 5, the oligomers exhibit nematic mesomorphism. Glass transition temperature (T-g) and clearing point temperature (T-c) increase with increasing molecular length and with those of OFV11 up to 71 and 230 degrees C, respectively. The oligomers can form uniform films by solution casting for fabrication of light-emitting diodes. With a device structure of ITO/ PEDOT:PSS/OFV11/Ca/Al, a current efficiency of 0.8 cd.A(-1) at a brightness of 1300 cd.m(-2) along with a maximum brightness of 2690 cd.m(-2) have been realized. This performance is notably superior to that of the corresponding polymer.

Synthesis and characterization of Y0.9-xGdxEu0.1BO3 phosphors by spray drying process

Y0.9-xGdxEu0.1BO3 phosphors were synthesized by spray drying (SD) method, and the results were compared with those by conventional solid state (SS) and citrate gel (GC) methods. The PL intensity of phosphors increases with the increase of x value in Y0.9-xGdxEu0.1BO3 (prepared by SD) due to an energy migration process like Gd3+ - (Gd3+)(n) - Eu3+ occurred in the material. Compared with the latter two methods, the phosphor particles prepared by spray drying method have a better morphology, such as homogeneous size (about 1similar to3 mum) with spherical shape and smooth surface. Furthermore, the spray drying-derived phosphors have higher photoluminescence (PL) intensity than those by citrate gel method, but still a little lower than those by the solid state method.

Synthesis and characterization of soluble oligo (9,10-bisalkynylanthrylene)s

Soluble oligo(9,10-bialkynylanthryiene)s up to pentamers were synthesized by means of the Suzuki coupling reaction. A solution processed thin film field-effect transistor from pentamer OA-5b shows a charge carrier mobility of 2.95 x 10(-3) cm(2)/V center dot s.

6,7,8,9-Tetrahydro-5H-pyrido[2,3-b]azepine-5,8-dione: a hydrogen-bonded dimer structure

In the title compound, C9H8N2O2, two crystallographically independent molecules form a dimer structure, in which two N-H center dot center dot center dot N hydrogen bonds generate an intermolecular R-2(2)( 8) ring.

Preparation, patterning and luminescent properties of oxyapatite La-9.33(SiO6)(4)O-2 : A (A = Eu3+, Tb3+, Ce3+) phosphor films by sol-gel soft lithography

Silicate oxyapatite La-9.33 (SiO6)(4)O-2:A (A = Eu3+, Tb3+ and/or Ce3+) phosphor films and their patterning were fabricated by a sol-gel process combined with soft lithography. X-ray diffraction (XRD), Fourier transform infrared spectroscopy, atomic force microscopy, optical microscopy and photoluminescence spectra, as well as lifetimes, were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 800degreesC and the crystallinity increased with the increase in annealing temperatures. Transparent nonpatterned phosphor films were uniform and crack-free, which mainly consisted of rodlike grains with a size between 150 and 210 nm. Patterned thin films with different bandwidths (20, 50 mum) were obtained by the micromoulding in capillaries technique. The doped rare earth ions (Eu3+, Tb3+ and Ce3+) showed their characteristic emission in crystalline La-9.33(SiO6)(4)O-2 phosphor films, i.e. Eu3+ D-5(0)-F-7(J) (J = 0, 1, 2, 3, 4), Tb3+ D-5(3,4)-F-7(J) (J = 3, 4, 5, 6) and Ce3+ 5d (D-2)-4f (F-2(2/5), F-2(2/7)) emissions, respectively. Both the lifetimes and PL intensity of the Eu3+, Tb3+ ions increased with increasing annealing temperature from 800 to 1100 degreesC, and the optimum concentrations for Eu3+, Tb3+ were determined to be 9 and 7 mol% of La3+ in La-9.33(SiO6)(4)O-2 films, respectively. An energy transfer from Ce3+ to Tb3+ was observed in the La-9.33(SiO6)(4)O-2:Ce, Tb phosphor films, and the energy transfer efficiency was estimated as a function of Tb3+ concentration.

4,7-(氯磺酸基苯基)-1,10-菲啰啉-2,9-二羧酸-铕标记甲胎蛋白抗体

在合成BCPDA基础上 ,对甲胎蛋白抗体与BCPDA连接及与铕离子螯合条件进行了研究。BCPDA与甲胎蛋白抗体反应后 ,分离纯化最佳淋洗液为pH9.1的0.1mol/L碳酸盐缓冲溶液 ,BCPDA用量为甲胎蛋白抗体量 (mol)的120～160倍;反应时间为30min。讨论了Eu3+ BCPDA AFP抗体螯合物的荧光光谱 ,最佳温育时间为60min,体系pH值为7.8的Tris HCl溶液。当Eu3+ 浓度为10-6mol/L时,BCPDA的检出限为4.3×10-11mol/L。

A highly reduced polyoxoanion with phosphorus-centered alternate layers of Mo/V oxides, [(PMo2Mo6V4O40)-Mo-V-V-VI-O-IV((VO)-O-IV)(2)](9-)

An unusual polyoxometalate [H2N(C2H4)(2)NH2](4)(H3O)[(PMO2Mo6V4O40)-Mo-V-V-VI-O-IV((VO)-O-IV)(2)].H2O is hydrothermally synthesized and characterized by IR, UV-VIS, elemental analyses, X-ray photoelectron spectrum, ESR, TG and Single crystal X-ray diffraction. The title compound crystallizes in the orthorhombic space group Pbca with a = 15-227(5), b = 19.491(4), c = 18.737(3) Angstrom, V = 5123(2) Angstrom(3), Z = 4, and R-1 (wR(2)) = 0.0726(0.1416). The compound contains an unusual highly reduced pseudo-Keggin type polyoxoanion and exhibits an interesting phosphorus-centered alternate arrangement of layers of molybdenum and vanadium oxides.

Layer-by-layer multilayer films self-assembled from a rare-earth-containing poly-oxometalate Na-9[Eu(W5O18)(2)] and poly (allylamine hydrochloride) and their photoluminescent properties

Ultrathin multilayer films of a rare-earth-containing polyoxometalate Na-9[Eu(W5O18)(2)] (EW) and Poly (allyamine hydrochloride) (PAH) have been prepared by layer-by-layer self-assembly from dilute aqueous solutions. The fabrication process of the EW/PAH multilayer films was followed by UV-vis spectroscopy and ellipsometry, which show that the deposition process is linear and highly reproducible from layer to layer. An average EW/PAH bilayer thickness of ca. 2.1 nm was determine,by ellipsometry. In addition, the scanning electron microscopy (SEM) image of the EW/PAH film indicates that the film sufface is relatively uniform and smooth. The photoluminescent properties of these films were also investigated by fluoresence spectroscopy.

Photoluminescent organic-inorganic composite films layer-by-layer self-assembled from the rare-earth-containing polyoxometalate Na-9[EuW10O36] and poly(allylamine hydrochloride)

Photoluminescent organic-inorganic composite films incorporating the rare-earth-containing polyoxometalate Na-9[EuW10O36] (EW) and poly(allylamine hydrochloride) (PAH) have been prepared by the layer-by-layer self-assembly method. UV-vis spectroscopy and ellipsometry were used to follow the fabrication process of the EW/PAH composite films. The experimental results show that the deposition process is linear and highly reproducible from layer to layer. An average EW/PAH bilayer thickness of ca. 2.1 nm was determined by ellipsometry. In addition, scanning electron microscopy and atomic force microscopy images of the EW/PAH composite films indicate that the film surface is relatively uniform and smooth. The photoluminescent properties of these films were investigated by fluorescence spectroscopy.