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.

Synthesis of Aromatic Oxide-Oxadiazoles Containing Pyridine Ring and Study on Their Spectral Properties

In order to explore new highly organic electroluminescent materials, six symmetrical aromatic oxide-oxadiazoles containing pyridine ring 4a similar to 4f were synthesized through cyclization of substituted benzoic acid (2) with 2,6-dihydrazide pyridine (3) by "one-pot" method in POCl3. Their structures were confirmed by MS, IR, H-1 NMR techniques and elemental analysis. The fluorescence spectra of the target compounds showed that the A,m ranged from 347 to 507 nm, and the maximum A,m were close to 384 nm, which showed that these compounds have good fluorescence with strong fluorescence intensity. When the 5-Br group was introduced into the aromatic ring (4e and 4f), the fluorescent emission wavelength took place Einstein shift, and the fluorescent intensity decreased a little. Using quinine bisulphate as a reference, the fluorescence quantum yields were all tested, and the introduction of 5-Br group had no visible effect on fluorescence quantum yield.

LaF3, CeF3, CeF3 : Tb3+, and CeF3 : Tb3+@LaF3 (core-shell) nanoplates: Hydrothermal synthesis and luminescence properties

LaF3. CeF3, CeF3:Tb3+, and CeF3:Tb3+ @LaF3 (core-shell) 2D nanoplates have been successfully synthesized by a facile and effective hydrothermal process. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL) spectra as well as kinetic decays were used to characterize the samples. The experimental results indicate that the organic additive, trisodium citrate (Cit(3-)), as a shape modifier has the dynamic effect by adjusting the growth rate of different crystal facets, resulting in forming the anisotropic geometries of the final products. The possible formation mechanisms for different products have been presented. The CeF3, CeF3:Tb3+, and CeF3:Tb3+ @LaF3 (core/shell) nanoplates show characteristic emission of Ce3+ (5d-4f) and Tb3+ (f-f), respectively.

Shape-controllable synthesis and upconversion properties of lutetium fluoride (doped with Yb3+/Er3+) microcrystals by hydrothermal process

Lutetium fluorides with different compositions, crystal phases, and morphologies, such as beta-NaLuF4 hexagonal microprisms, microdisks, mirotubes, alpha-NaLuF4 submicrospheres, LuF3 octahedra, and NH4Lu2F7 icosahedra, prolate ellipsoids and spherical particles have been successfully synthesized via a facile hydrothermal route. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, selected area electron diffraction, and photoluminescence spectra were used to characterize the samples. The intrinsic structural feature of lutetium fluorides, the solution pH values, F- sources, and organic additives (Cit(3-) and EDTA) account for the ultimate shape evolutions of the final products. The possible formation mechanisms for products with various architectures have been presented. Additionally, we investigated the upconversion luminescence properties of beta-NaLuF4: 20% Yb3+/2% Er3+ with different morphologies.

Rational Design, Synthesis, and Optical Properties of Film-Forming, Near-Infrared Absorbing, and Fluorescent Chiromophores with Multidonors and Large Heterocyclic Acceptors

A new series of film-forming, low-bandgap chromophores (1a,b and 2a,b) were rationally designed with aid of a computational study., and then synthesized and characterized. To realize absorption and emission above the 1000 nm wavelength, the molecular design focuses on lowering the LUMO level by fusing common heterocyclic units into a large conjugated core that acts an electron acceptor and increasing the charge transfer by attaching the multiple electron-donating groups at the appropriate positions of the acceptor core. The chromophores have bandgap levels of 1.27-0.71 eV, and accordingly absorb at 746-1003 nm and emit at 1035-1290 nm in solution. By design, the relatively high molecular weight (up to 2400 g mol(-1)) and non-coplanar structure allow these near-infrared (NIR) chromophores to be readily spin-coated as uniform thin films and doped with other organic semiconductors for potential device applications. Doping with [6,6]-phenyl-C-61 butyric acid methyl ester leads to a red shift in the absorption on]), for la and 2a. An interesting NIR electrochromism was found for 2a, with absorption being turned on at 1034 nm when electrochemically switched (at 1000 mV) from its neutral state to a radical cation state. Furthermore, a large Stokes shift (256-318 nm) is also unique for this multidonor-acceptor type of chromophore.

Facile Hydrothermal Synthesis and Luminescent Properties of Large-Scale GdVO4:Eu3+ Nanowires

Large-scale GdVO4:Eu3+ nanowires with diameters of about 15 nm and lengths of several micrometers were achieved by a facile hydrothermal method in the presence of disodium ethylenediamine tetraacetate (Na2H2L). The influences of several parameters, such as pH value, reaction temperature, and molar ratio of Na2H2L to Gd3+ on the final products were investigated. The formation mechanism of the as-obtained GdVO4:Eu3+ nanowires is proposed on the basis of time-dependent experiments. It is found that the organic additive Na2H2L, which acts as a shape modifier, has a dynamic effect by adjusting the growth rates of different facets, resulting in the formation of the GdVO4:Eu3+ nanowires. The luminescent spectrum of GdVO4:Eu3+ nanowires shows the strong characteristic dominant emission of the Eu3+ ions at 614 nm.

Facile synthesis of highly uniform octahedral LuVO4 microcrystals by a facile chemical conversion method

Uniform octahedral LuVO4 microcrystals have been successfully prepared through a designed two-step hydrothermal method. One-dimensional lutetium precursor was first prepared through a simple hydrothermal route. Subsequently, a well-shaped octahedral LuVO4 sample was synthesized at the expense of the wirelike precursors during the hydrothermal process. The whole process in this method was carried out in aqueous conditions without the use of any organic solvents, surfactant, or catalyst. The conversion process from nanowire precursor to octahedral product has been investigated in detail. The LuVO4 : Ln(3+) (Ln Eu, Dy, Sm, and Er) phosphors show strong light emissions with different colors coming from different activator ions under ultraviolet light excitation or low-voltage electron beam excitation. Furthermore, this general and facile method may be of much significance in the synthesis of many other lanthanide compounds with polyhedral morphology.

Facile shape-controlled synthesis of luminescent europium benzene-1,3,5-tricarboxylate architectures at room temperature

The large-scale synthesis of the metal-organic framework Eu(1,3,5-BTC)center dot 6H(2)O nanocrystallites with delicate morphologies such as sheaflike, butterflylike, and flowerlike superstructures composed of nanowires have been realized via a simple solution phase method at room temperature. Time-dependent experiments indicate that these superstructures were constructed by the splitting crystal growth mechanism, as has been noted in some minerals in nature. The synthetic parameters such as reaction time, concentration and molar ratio of reactants, surfactant, and reaction temperature all affected the morphology of the Eu(1,3,5-BTC)center dot 6H(2)O architectures. These well-arranged architectures exhibit red emission corresponding to the D-5(0) -> F-7(2) transition of the Eu3+ ions under UV light excitation, and the lifetime is determined to be about 0.22 ms.

Facile chemical conversion synthesis and luminescence properties of uniform Ln3+ (Ln = Eu, Tb)-doped NaLuF4 nanowires and LuBO3 microdisks

Uniform NaLuF(4) nanowires and LuBO(3) microdisks have been successfully prepared by a designed chemical conversion method. The lutetium precursor nanowires were first prepared through a simple hydrothermal process. Subsequently, uniform NaLuF(4) nanowires and LuBO(3) microdisks were synthesized at the expense of the precursor by a hydrothermal conversion process. The whole process was carried out in aqueous condition without any organic solvents, surfactant, or catalyst. The conversion processes from precursor to the final products have been investigated in detail. The as-obtained Eu(3+) and Tb(3+)-doped LuBO(3) microdisks and NaLuF(4) nanowires show strong characteristic red and green emissions under ultraviolet excitation or low-voltage electron beam excitation. Moreover, the luminescence colors of the Eu(3+) and Tb(3+) codoped LuBO(3) samples can be tuned from red, orange, yellow, and green-yellow to green by simply adjusting the relative doping concentrations of the activator ions under a single wavelength excitation, which might find potential applications in the fields such as light display systems and optoelectronic devices.

Uniform Lanthanide Orthoborates LnBO(3) (Ln = Gd, Nd, Sm, Eu, Tb, and Dy) Microplates: General Synthesis and Luminescence Properties

A variety of uniform lanthanide orthoborates LnBO(3) (Ln = Gd, Nd, Sm, Eu, Tb, and Dy) microplates have been successfully prepared by a general and facile conversion method. One-dimensional (ID) lanthanide hydroxides were first prepared through a simple hydrothermal process. Subsequently, uniform LnBO(3) microplates were synthesized at the expense of the ID precursors during a hydrothermal conversion process. The whole process in this method was carried out in aqueous condition without the use of any organic solvents, surfactant, or catalyst. The as-obtained rare earth ions doped GdBO3 and TbBO3 microplates show strong light emissions with different colors coming from different activator ions under ultraviolet excitation or low-voltage electron beam excitation, which might find potential applications in fields such as light phosphor powders and advanced flat panel display devices.

PIFA-Mediated Oxidative Cyclization of 1-Carbamoyl-1-oximylcycloalkanes: Synthesis of Spiro-Fused Pyrazolin-5-one N-Oxides

convenient and efficient synthesis of spiro-fused pyrazolin-5-one N-oxides starting from readily available 1-carbamoyl-1-oximylcycloalkanes is developed. This general protocol features a novel and facile way for access to the five-membered azaheterocycles by formation of a new N-N single bond. The key cyclization step utilizes the formation of an N-oxonitrenium intermediate, mediated by the hypervalent iodine reagent PIFA, and its subsequent intramolecular trapping by the amide moiety under rather mild experimental conditions.

A Facile and Efficient One-Pot Synthesis of Substituted Quinolines from alpha-Arylamino Ketones Under Vilsmeier Conditions

An efficient one-pot synthesis of substituted quinolines from alpha-arylamino ketones in the presence of PBr3 in DMF has been developed. This general protocol provides a novel and facile access to substituted quinolines by sequential Vilsmeier-Haack reaction, intramolecular cyclization and aromatization reactions of alpha-arylamino ketones. PBr3 plays a dual role in the quinoline synthesis: as a key component of the Vilsmeier reagent (PBr3/DMF) and as a reducing reagent.

Synthesis and luminescent properties of europium (III) schiff base complexes covalently bonded to silica xerogels

A new kind of luminescent organic-inorganic hydrid material consisting of Eu(III)-schiff base complex covalently bonded to silica xerogel was synthesized via the sol-gel method using a Eu (N-propylene salicylimine ligand) complex modified with pendant triethoxysilane groups (Eu(III)(salenHSi)). The Eu(III)(salenHSi) complex is characterized by Fourier transform infrared (FT-IR) spectroscopy. Luminescent properties of the complex and the resulted hybrid silica xerogels have been investigated at room temperature.

Synthesis and properties of novel organosoluble polyimides derived from 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride and various aromatic diamines

A novel triptycene-based dianhydride, 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride, was prepared from 4-nitro-N-methylphthalimide and potassium phenolate of 1,4-dihydroxytriptycene (1). The aromatic nucleophilic substitution reaction between 4-nitro-N-methylphthalimide and I afforded triptycene-based bis(N-methylphthalimide) (2), which hydrolyzed and subsequently dehydrated to give the corresponding dianhydride (3). A series of new polyimides containing triptycene moieties were prepared from the dianhydride monomer (3) and various diamines in in-cresol via conventional one-step polycondensation method. Most of the resulting polyimides were soluble in common organic solvents, such as chloroform, THF, DMAc and DMSO. The polyimides exhibited excellent thermal and thermo-oxidative stabilities with the onset decomposition temperature and 10% weight loss temperature ranging from 448 to 486 degrees C and 526 to 565 degrees C in nitrogen atmosphere, respectively. The glass transition temperatures of the polyimides were in the range of 221-296 degrees C. The polyimide films were found to be transparent, flexible, and tough. The films had tensile strengths, elongations at break, and tensile moduli in the ranges 95-118 MPa, 5.3-16.2%, and 1.03-1.38 GPa, respectively. Wide-angle X-ray diffraction measurements revealed that these polyimides were amorphous.

Synthesis and gas transport property of polyimide from 2,2 '-disubstituted biphenyltetracarboxylic dianhydrides (BPDA)

A series of dianhydride monomers, 2,2'-disubstituted-4,4',5,5'-biphenyltetracarboxylic dianhydride (substituents = phenoxy, p-methylphenoxy, p-tert-butylphenoxy, nitro, and methoxy) were synthesized by the nitration of an N-methyl protected 3,3',4,4'-biphenyttetracarboxylic dianhydride (BPDA) and subsequent aromatic nucleophilic substitutions with aroxides (NaOAr) or methoxide. These dianhydrides were polymerized with various aromatic diamines in refluxing m-cresol containing isoquinoline to afford a series of aromatic polyintides. The effects of varying 2,2'-substituents of the dianhydride (BPDA) moiety on the properties of polyimides were investigated. It was found that polyimides from the dianhydrides containing phenoxy, p-methylphenoxy, and p-tert-butylphenoxy side groups possessed excellent solubility and film forming capability whereas polyimides from 2,2'-dinitro-BPDA and 2,2'-dimethoxy-BPDA were less soluble in organic solvent. The soluble polymers formed flexible, tough and transparent films. The films had a tensile strength, elongation at break, and Young's modulus in the ranges 102-168 MPa, 8-21%, 2.02-2.38 GPa, respectively. The polymer gas permeability coefficients (P) and ideal selectivities for N-2, O-2, CO2 and CH4 were determined for the -OAr substituted polyimides. The oxygen permeability coefficient (P-O2) and permselectivity of oxygen to nitrogen (PO2/N-2) of the films were in the ranges 3.4-11.3 barrer and 3.8-4.6, respectively.