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.

Influence of molecular topology on the static and dynamic properties of single polymer chain in solution

The influence of molecular topology on the structural and dynamic properties of polymer chain in solution with ring structure, three-arm branched structure, and linear structure are studied by molecular dynamics simulation. At the same degree of polymerization (N), the ring-shaped chain possesses the smallest size and largest diffusion coefficient. With increasing N, the difference of the radii of gyration between the three types of polymer chains increases, whereas the difference of the diffusion coefficients among them decreases. However, the influence of the molecular topology on the static and the dynamic scaling exponents is small. The static scaling exponents decrease slightly, and the dynamic scaling exponents increase slightly, when the topology of the polymer chain is changed from linear to ring-shaped or three-arm branched architecture. The dynamics of these three types of polymer chain in solution is Zimm-like according to the dynamic scaling exponents and the dynamic structure factors.

Effect of main-chain rigidity on the phase transitional behavior of comblike polymers

The influence of the rigidity of polymer backbones on the side-chain crystallization and phase transition behavior was systematically investigated by a combination of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FTIR), and high-resolution solid-state nuclear magnetic resonance spectroscopy (NMR). DSC investigation indicated that the crystallization number of alkyl carbon atoms of the side chains grafted onto the rigid polymer backbone, poly(p-benzamide) (PBA), is much lower than that of the alkyl carbon atoms of the side chains grafted onto the flexible polymer backbone, poly(ethyleneimine) (PEI), implying that the conformational state of the polymer backbones has a strong effect on the side-chain crystallization behavior in comblike polymers. WAXD and FTIR results proved that these two comblike polymers pack into hexagonal (PBA18C) and orthorhombic (PEI18C) crystals, respectively, depending on the adjusting ability of the polymer backbones for particular conformational states. It was also found that the presence of the crystalline-amorphous interphase (delta = 31.6 ppm) in PBA18C detected by solid-state C-13 NMR spectroscopy can be attributed to the rigid PBA backbone, which restricts the mobility of the alkyl side chains.

Naphthyl and thionaphthyl end-capped oligothiophenes as organic semiconductors: Effect of chain length and end-capping groups

Two series of oligothiophenes (OThs), NaTn and TNTn (n = 2-6 represents the number of thiophene rings), end-capped with naphthyl and thionaphthyl units have been synthesized by means of Stille coupling. Their thermal properties, optical properties, single crystal structures, and organic field-effect transistor performance have been characterized. All oligomers display great thermal stability and crystallinity. ne crystallographic structures of NaT2, NaT3, TNT2, and TNT3 have been determined. The crystals of NaT2 and NaT3 are monoclinic with space group P2(1)/C, while those of TNT2 and TNT3 are triclinic and orthorhombic with space groups P-1(-) and P2(1)2(1)2(1), respectively. All oligomers adopt the well-known herringbone packing-mode in crystals with packing parameters dependent on the structure of the end-capping units and the number of thiophene rings. The shorter intermolecular distance in NaT3 compared to NaT2 indicates that the intermolecular interaction principally increases with increasing molecular length. X-ray diffraction and atomic force microscopy (AFM) characterization indicate that the NaTn oligomers can form films with better morphology and high molecular order than TNTn oligomers with the same number of thiophene rings. The NaTn oligomers exhibit mobilities that are much higher than those for TNTn oligomers (0.028-0.39 cm(2) V-1 s(-1) versus 0.010-0.055 cm(2) V-1 s(-1), respectively).

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.

Conversion process of the dominant electroluminescence mechanism in a molecularly doped organic light-emitting device with only electron trapping

In this work, the detailed conversion process of the dominant electroluminescence (EL) mechanism in a device with Eu(TTA)(3)phen (TTA=thenoyltrifluoroacetone, phen=1,10-phenanthroline) doped CBP (4,4(')-N,N-'-dicarbazole-biphenyl) film as the emitting layer was investigated by analyzing the evolution of carrier distribution on dye and host molecules with increasing voltage. Firstly, it was confirmed that only electrons can be trapped in Eu(TTA)(3)phen doped CBP. As a result, holes and electrons would be situated on CBP and Eu(TTA)(3)phen molecules, respectively, and thus creates an unbalanced carrier distribution on both dye and host molecules. With the help of EL and photoluminescence spectra, the distribution of holes and electrons on both Eu(TTA)(3)phen and CBP molecules was demonstrated to change gradually with increasing voltage. Therefore, the dominant EL mechanism in this device changes gradually from carrier trapping at relatively low voltage to Forster energy transfer at relatively high voltage.

Extended-chain lamellar packing of poly(3-butylthiophene) in single crystals

We developed an approach, i.e. solvent-assist crystallization (SAC), for growing high quality single crystals of head-to-tail regio-regular poly(3-butylthiophene) (P3BT). By means of atomic force microscopy, electron diffraction and X-ray diffraction, we found that P3BT macromolecules formed lamella single crystals through gradient crystallization, and in the single crystals, molecules packed normal to the lamella with extended-chain conformation with alkyl side chains in the growth front during crystallization.

Chain propagation kinetics on melt grafting reaction

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetic studies on reactive extrusion have been carried out because of the inherent difficulties, as expected. In this work, we have studied chain propagation kinetics on melt grafting using pre-irradiated linear low density polyethylene (LLDPE) and three monomers, acrylic acid (AA), methacrylic acid (MAA), and methyl methacrylate (MMA), as the model system. We measured the apparent chain propagation rate coefficients of grafting (k(p,g)) and homopolymerization (k(p,h)) at an initial stage for the melt grafting by FT-IR spectroscopy and electron spin resonance spectroscopy. It was observed that the convective mixing affected the rate coefficients. The magnitude of k(p,h) and k(p,g) were in the same order, but k(p,h) was slightly larger than k(p,g) The k(p,g) of the three grafting systems increased in the order: LLDPE/MMA < LLDPE/MAA < LLDPE/AA. These results are explained in terms of phase separation, solubility, and inherent reactivity of the monomer.

Phase conversion and spectral properties of long lasting phosphor Zn-3 (PO4)(2): Mn2+, Ga3+

A red long lasting phosphor Zn-3(PO4)(2): Mn2+ Ga3+ (ZPMG) was prepared by ceramic method, and phase conversion and spectral properties were investigated. Results indicated that the phase conversion from alpha-Zn-3(PO4), beta-Zn-3(PO4)(2) to gamma-Zn-3(PO4)(2) occurs with different manganese concentration incorporated and sinter process. The structural change induced by the phase transformation results in a remarkable difference in the spectral properties. The possible luminescence mechanism for this red LLP with different forms has been illustrated.

2-cyanoprop-2-yl dithiobenzoate mediated reversible addition-fragmentation chain transfer polymerization of acrylonitrile targeting a polymer with a higher molecular weight

The reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylonitrile (AN) mediated by 2-cyanoprop-2-yl dithiobenzoate was first applied to synthesize polyacrylonitrile (PAN) with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29. The key to success was ascribed to the optimization of the experimental conditions to increase the fragmentation reaction efficiency of the intermediate radical. In accordance with the atom transfer radical polymerization of AN, ethylene carbonate was also a better solvent candidate for providing higher controlled/living RAFT polymerization behaviors than dimethylformamide and dimethyl sulfoxide. The various experimental parameters, including the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the molecular weight and polydispersity index. The molecular weights of PANS were validated by gel permeation chromatography along with a universal calibration procedure and intrinsic viscosity measurements. H-1 NMR analysis confirmed the high chain-end functionality of the resultant polymers.

Self-assembly of a water chain with tetrameric and decameric clusters in the channel of a mixed-valence (CuCuII)-Cu-I complex

The reaction of Cu(BF4)(2) with pyridine-2,6-dicarboxylic acid (H(2)pydc) and trans-1,2-bis(4-pyridyl)ethylene (bpe) under hydrothermal conditions afforded a porous mixed-valence (CuCuII)-Cu-I coordination polymer. Coexistence of tetrameric and decameric water clusters within the channels of the complex leads to a novel water chain. The metal-organic framework provides both hydrophilic and hydrophobic environments for stabilizing the clusters and retains its integrity upon dehydration and rehydration.

White electroluminescence from a single-polymer system with simultaneous two-color emission: Polyfluorene as blue host and 2,1,3-benzothiadiazole derivatives as orange dopants on the side chain

Four single polymers with two kinds of attachment of orange chromophore to blue polymer host for white electroluminescence (EL) were designed. The effect of the side-chain attachment and main-chain attachment on the EL efficiencies of the resulting polymers was compared. The side-chain-type single polymers are found to exhibit more efficient white EL than that of the main-chain-type single polymers. Based on the side-chain-type white single polymer with 4-(4-alkyloxy-phenyl)-7-(4-diphenylamino-phenyl)-2,1,3-benzothiadiazoles as the orange-dopant unit and polyfluorene as the blue polymer host, white EL with simultaneous orange (lambda(max) = 545 nm) and blue emission (lambda(max) = 432 nm/460 nm) is realised. A single-layer device (indium tin oxide/poly(3,4-ethylenedioxythiophene)/polymer/Ca/Al) made of these polymers emits white light with the Commission Internationale de l'Eclairage coordinates of (0.30,0.40), possesses a turn-on voltage of 3.5 V, luminous efficiency of 10.66 cd A(-1), power efficiency of 6.68 lm W-1, and a maximum brightness of 21240 cd m(-2).

Synthesis and characterization of white-light-emitting polyfluorenes containing orange phosphorescent moieties in the side chain

Two orange phosphorescent iridium complex monomers, 9-hexyl-9-(iridium (III)bis(2-(4'-fluorophenyl)-4-phenylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-PIr) and 9-hexyl-9-(iridium(III)bis(2-(4'-fluorophenyl)-4-methylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-MIr), were successfully synthesized. The Suzuki polycondensation of 2,7-bis(trimethylene boronate)-9,9-dioctylfluorene with 2,7-dibromo-9,9-dioetylfluorene and Br-Plr or Br-MIr afforded two series of copolymers, PIrPFs and MIrPFs, in good yields, in which the concentrations of the phosphorescent moieties were kept small (0.5-3 mol % feed ratio) to realize incomplete energy transfer. The photoluminescence (PL) of the copolymers showed blue- and orange-emission peaks. A white-light-emitting diode with a configuration of indium tin oxide/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/PIr05PF (0.5 mol % feed ratio of Br-PIr)/Ca/Al exhibited a luminous efficiency of 4.49 cd/A and a power efficiency of 2.35 lm/W at 6.0 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.46, 0.33). The CIE coordinates were improved to (0.34, 0.33) when copolymer MIr10PF (1.0 mol % feed ratio of Br-MIr) was employed as the white-emissive layer. The strong orange emission in the electroluminescence spectra in comparison with PL for these kinds of polymers was attributed to the additional contribution of charge trapping in the phosphorescent dopants.

Ordering-induced micro-bands in thin films of a main-chain liquid crystalline chloro-poly(aryl ether ketone)

Micro-banded textures developed from thin films of a main-chain thermotropic liquid crystalline chloro-poly(aryl ether ketone) in the melt were investigated using transmission electron microscopy (TEM). selective area electron diffraction, and atomic force microscopy techniques. The micro-banded textures were formed in the copolymer thin films after annealing at temperatures between 320 and 330degreesC, where a highly ordered smectic crystalline phase is formed without mechanical shearing. The micro-banded textures displayed a sinusoidal-like periodicity with a spacing of 150 nm and an amplitude of 2 rim. The long axis of the banded texture was parallel to the b-axis of an orthorhombic unit cell. In the convex regions, the molecular chains exhibited a homeotropic alignment, i.e. the chain direction was parallel to the film normal. In the concave re-ions, the molecular chains possessed a tilted alignment. In addition to the effects of annealing temperatures and times, the thickness of the film played a vital role in the formation of the banded texture. A possible formation mechanism of this banded texture vas also suggested and discussed. It was suggested that the micro-bands were formed during cooling.

Electric-field-induced molecular alignment of side-chain liquid-crystalline polyacetylenes containing biphenyl mesogens

Electric-field-induced molecular alignments of side-chain liquid-crystalline polyacetylenes [-{HC=C[(CH2)(m)OCO-biph-OC7H15]}-, where biph is 4,4'-biphenylyl and m is 3 (PA3EO7) or 9 (PA9EO7)] were studied with X-ray diffraction and polarized optical microscopy. An orientation as high as 0.84 was obtained for PA9EO7. Furthermore, the molecular orientation of]PA9EO7 was achieved within a temperature range between the isotropic-to-smectic A transition temperature and 115 degreesC, and this suggested that the orientational packing was affected by the thermal fluctuation of the isotropic liquid and the mobility of the mesogenic moieties. The maximum achievable orientation for PA9EO7 was much greater than that for PA3EO7. This was the first time that the electric-field-induced molecular orientation of a side-chain liquid-crystalline polymer with a stiff backbone was studied.