Synthesis and Characterization of New Dibenzothiophene-based Host Materials for Blue Phosphorescent Organic Light-Emitting Diodes

A series of bipolar host materials containing dibenzo[b,d]thiophene (DBT) or dibenzo[b,d]thiophene 5,5-dioxide core were successfully synthesized, and their physical, photophysical, and electrochemical properties were investigated. The three host materials showed well-localized electron distribution at the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) states, as evidenced by theoretical calculations. Triplet energies of the new host materials are higher than 2.6 eV, and the blend film with bis[2-(4,6-difluorophenyl)pyridinato-C² Misra, A. et al. (2006). Semicond. Sci. Technol., 21, R35.[Crossref], [Web of Science ®] , [Google Scholar],N](picolinato)iridium(III) (FIrpic) as a blue phosphorescent dopant showed highly efficient energy transfer between the host material and dopant.     

Crystallochemical modeling, synthesis, and study of new tantalum and niobium phosphates with a framework structure

A crystallochemical approach is used to model the compositions of phosphates of pentavalent elements with the expected structure. New phosphates with a framework structure of the T ₂ ^I T ₃ ^2/III T ₁ ^2/V (PO₄)₃ type (T ^I = Na or K; T ^III = Al, Cr, or Fe; and T ^V = Nb or Ta) are synthesized and characterized by X-ray diffraction analysis (including high-temperature diffraction) and IR spectroscopy. It is established that, depending on the nature of the alkali cation (Na or K), these compounds are crystallized in two structural modifications: rhombohedral and cubic (sp. gr. R $\bar 3$ c and P2₁3, respectively). The unit-cell parameters and the thermal expansion coefficients of the phosphates under study are determined and the dependences of these characteristics on the nature of cations are established.     

“Synthesis,design and characterization of supramolecular self-assembly of calix[4]resorcinare substituted LCs”

A new class of supramolecular calix[4 (a) Kuang, G.C., Jia, X.R., Teng, M.J., Chen, E.Q., Li, W.S., Ji, Y., Chem Mater. 2012, 24,71–80; (b) Macros, M., Omenat, A., Serrano, J.L., and Ezcurra, A., Adv. Mater. 1992, 4, 285–287.[Crossref], [Web of Science ®] , [Google Scholar], [Google Scholar]]resorcinarene substituted alkoxy side chain (-OC₅H₁₁, -OC₈H₁₇, -OC₁₀H₂₁) has been synthesized and well characterized. These supramolecular compounds were investigated by polarizing optical microscope (POM), differential scanning calorimetry (DSC), thermogravimmetric analysis (TGA) and high-temperature X-ray diffraction studies (XRD). The present synthesized supramolecular derivatives are promising to stabilize the hexagonal columnar phase over a broad thermal range. All the synthesized derivatives showed hexagonal columnar phase at lower temperature and showed enantiotropical nature. Compound 2a with small alkyl spacer on eight side showed higher thermal stability as compare to higher alkyl spacer substituted compounds 2b and compound 2c. These research results suggest that calix[4 (a) Kuang, G.C., Jia, X.R., Teng, M.J., Chen, E.Q., Li, W.S., Ji, Y., Chem Mater. 2012, 24,71–80; (b) Macros, M., Omenat, A., Serrano, J.L., and Ezcurra, A., Adv. Mater. 1992, 4, 285–287.[Crossref], [Web of Science ®] , [Google Scholar], [Google Scholar]]resorcinarene was a good platform to construct bowl-shaped derivatives to exhibits the columnar liquid crystal phase and the observed liquid crystalline properties were greatly effected by the substituted alkoxy side chain on eight side of calix[4 (a) Kuang, G.C., Jia, X.R., Teng, M.J., Chen, E.Q., Li, W.S., Ji, Y., Chem Mater. 2012, 24,71–80; (b) Macros, M., Omenat, A., Serrano, J.L., and Ezcurra, A., Adv. Mater. 1992, 4, 285–287.[Crossref], [Web of Science ®] , [Google Scholar], [Google Scholar]]resorcinarene skeletone. All the synthesized compounds were characterized by FT-IR, ¹H NMR and ¹³C NMR spectroscopy.     

Photo Alignment and Patterning of Liquid Crystal Polymer Films and Optical Devices by Side-Chain Photopolymers

Prerequisite for virtually all nematic field-effects on which liquid crystal displays (LCDs) are based is stable, uniaxial surface alignment with defined bias tilt angle between the long liquid crystal (LC) axes and their display boundaries. Since the invention of the TN-LCD [1 Schadt, M., & Helfrich, W. (1972). Mol. Cryst. Liq. Cryst., 17, 355.[Taylor & Francis Online], [Web of Science ®] , [Google Scholar]] in 1970 until recently this was achieved by confining liquid crystals between mechanically brushed surfaces [2 Cognard, J. (1982). J. Mol. Cryst. Liq. Cryst. Suppl. Ser., 1, 1–74. [Google Scholar]–4 Aoyama, H., Yamazaki, Y., Matsuura, N., Mada, H., & Kobayashi, S. (1981). Mol. Cryst. Liq. Cryst. Lett., 72, 127.[Taylor & Francis Online], [Web of Science ®] , [Google Scholar]]. We have first shown in the 1990s that, non-mechanical, uniaxial, tilted and patterned LC-alignment is possible by anisotropic Van der Waals surface interactions [5 Schadt, M., Seiberle, H., & Schuster, A. (1996). Nature, 381, 212. US Patent (1995) US-6, 215, 539.[Crossref], [Web of Science ®] , [Google Scholar]], namely by directional polymerization of photo-sensitive side-chain polymers films [5 Schadt, M., Seiberle, H., & Schuster, A. (1996). Nature, 381, 212. US Patent (1995) US-6, 215, 539.[Crossref], [Web of Science ®] , [Google Scholar], 6 Schadt, M., Schmitt, K., Kozinkov, V. & Chigrinov, V.G. (1992). Jpn. J. Appl. Phys., 31, 2155. US patent (1991) US 5,389,698.[Crossref], [Web of Science ®] , [Google Scholar]] by linear polarized UV light. The LPP model is reviewed and its applications enabling high resolution multi-domain liquid crystal displays operated in transmission and reflection are discussed. Examples are given for optical retarders integrated into LCDs, anisotropic liquid crystal polymer (LCP)-films for 3D imaging, interference color filters, wide-view films and anisotropic polymer surface topologies.     

Synthesis,structure, and mesomorphism of novel liquid crystalline acrylate monomers and polymers

A series of novel liquid crystalline monomers (M₁?M₈) and side chain polymers base polyacrylate backbone were synthesized. The chemical structures were characterized by FT-IR and ¹H-NMR spectra. The mesomorphism and thermal behavior was investigated by polarizing optical microscopy, differential scanning calorimetry, and thermogravimetric analysis. The relationships of structure and mesomorphism are discussed in detail. The eight monomers and their corresponding polymers all show enantiotropic nematic phase. With increasing the spacer length or flexibility of the terminal group, the melting temperature (T_m) and isotropic temperature (T_i) of the corresponding monomers and polymers all decreased. However, with increasing the rigidity of the mesogenic core, T_m and T_i of the corresponding monomers and polymers all increased. TGA showed that all the polymers obtained in this study had excellent thermal stability.     

Synthesis and Nonlinear Optical Properties of Novel Polyester Containing Nitrophenylazonitroresorcinoxy Group

A new X-type polyester (4) containing nitrophenylazonitroresorcinoxy groups as NLO chromophores, which are components of the polymer backbone was prepared. Polyester 4 is soluble in common organic solvents such as N,N-dimethylformamide and dimethylsulfoxide. It shows a thermal stability up to 280°C from thermogravimetric analysis with glass-transition temperature (T_g) obtained from differential scanning calorimetry near 120°C. The second harmonic generation (SHG) coefficient (d₃₃) of poled polymer films at the 1064 nm fundamental wavelength is around 5.08 × 10^?9 esu. The dipole alignment exhibits a thermal stability even at 5°C higher than T_g, and no SHG decay was observed below 125°C due to the partial main-chain character of polymer structure, which is acceptable for NLO device applications.     

The effect of tourmaline additives in TiO2 photoanode for high-efficiency dye sensitized solar cells

Tourmaline is a kind of borosilicatemineral and has spontaneous polarization property. Due to this property, it can generate a feeble current around 0.06 mA[1 O'Regan, B., &; Grätzel, M. (1991). Nature 353, 737.[Crossref], [Web of Science ®] , [Google Scholar]]. We fabricated the TiO₂ photoanode with different wt.% ratio of tourmaline and investigated the effect of tourmaline additive on dye sensitized solar cells (DSSCs). We carried out electrochemical impedance spectroscopy (EIS) and current density-voltage (J-V) measurement. The results showed that the electron lifetime and the power conversion efficiency of the DSSCs with TiO₂ photoanode containing 3wt% tourmaline were enhanced by about 42% and 20%, respectively, as compared to the DSSCs using pristine TiO₂ photoanode.     

New icosahedral nanoclusters in crystal structures of intermetallic compounds: Topological types of 50-atom deltahedra D50 in samson phases β-Mg2Al3 and ?-Mg23Al30

A database of intermetallic compounds has been compiled using the TOPOS program package. This database includes 514 topological types, containing 12- and 13-atom icosahedral i clusters. An isolated group of 1649 i clusters is described by 14 point groups and their maximum symmetry D _3d ( $\bar 3$ m) and T _h (m $\bar 3$ ) is established, respectively, in 47 and 25 types of crystal structures. A structural analysis of the outer quasispherical shells showed that local 63-atom i configurations 1@12@50, which contain 50 atoms in the second layer, are implemented in 8 out of 19 cases. Examples of new topologically different types of 50-atom D50 deltahedra in the Samson phases ?-Mg₂₃Al₃₀ and ??-Mg₂Al₃ are presented. Four topologically different sites with coordination numbers of 5, 6, 6, or 7 are established in the ? shell and seven sites with coordination numbers of 5, 5, 6, 6, 6, 6, or 7 are found in the ?? shell. The inner i clusters for the ??-Mg₂Al₃ structure (with the symmetry $\bar 3$ m) and the ?-Mg₂₃Al₃₀ structure (with the symmetry $\bar 3$ ) have a similar chemical composition, i.e., Mg₇Al₆ and Mg₆Al₇, and their 50-atom shells are chemically identical to 18Mg + 32Al. The configurations found supplement the series of known two-layer icosahedral Bergman and Mackay clusters in the form of deltahedra with 32- and 42-atom shells.     

Specific features of the crystal structure and magnetic properties of KTaO<Subscript>3</Subscript> produced by electrolysis of melts

The magnetic susceptibility χ(T) at 4.2 K < T < 293 K; the dependence of the magnetic moment on the magnetic field strength, M(H), at 4.2, 77, and 293 K; and the electrical resistivity ρ(T) at 4.2 K < T < 293 K are studied for samples of perovskite-phase KTaO₃ obtained by both solid-phase synthesis (KTaO ₃ ^s ) and deposition on a cathode during electrolysis of melts (KTaO ₃ ^e ). Yellowish white KTaO ₃ ^s powders are diamagnetic and reveal dielectric properties. Dark polycrystalline KTaO ₃ ^e samples with metallic luster are characterized by the dependence ρ(T) typical of metals and additional paramagnetic contribution to the paramagnetic susceptibility as compared with KTaO ₃ ^e . Changes in the properties of KTaO₃ during electrocrystallization are attributed to partial reduction of tantalum. They are revealed in the structural features of KTaO ₃ ^e (excess of tantalum as compared to the stoichiometric composition of KTaO ₃ ^e , deficiency of the oxygen sublattice, and clearly pronounced anharmonicity of atomic vibrations). A change of the cation-anion-cation interactions, occurring owing to the overlapping of oxygen p orbitals with tantalum t_2g orbitals and the formation of impurity levels near the conduction band, leads to the generation of free carriers, which make a paramagnetic contribution to the magnetic susceptibility.     

Growth, thermal and spectral properties of Nd-doped NaGd(MoO4)2 crystal

Nd³⁺-doped NaGd(MoO₄)₂ crystal with dimensions were grown by Czochralski method. Nd³⁺:NaGd(MoO₄)₂ crystal melts at 1182 °C. The hardness of Nd³⁺:NaGd(MoO₄)₂ crystal is 334 VDH. The specific heat is 72.6 cal/mol K. The thermal expansion coefficients are for c-axis and for a-axis, respectively. The absorption cross-sections of Nd³⁺:NaGd(MoO₄)₂ crystal are with a FWHM of 9 nm at the 804 nm for π-polarization and with a FWHM of 17 nm at 807 nm for σ-polarization, respectively. The emission cross-section σ_em are at 1063 nm for π-polarization and 1.94×10^-20 at 1070 nm cm² for σ-polarization, respectively. The fluorescence lifetime τ_f is 93.9 μs at room temperature.     

New chiral liquid crystal materials based on menthol: Synthesis and phase behavior

To study structure-mesomorphism relationships of chiral materials based on menthol, a series of chiral compounds containing menthyl group were synthesized. Their chemical structures, formula, and the purity were characterized by Fourier transform infrared (FTIR), proton nuclear magnetic resonance (¹H NMR), and elemental analyses. The corresponding phase behavior was investigated with differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). The effect of the mesogenic core, flexible spacer, and terminal groups on the mesophase formation and type was discussed. The compound 4-menthyloxyacetoxybenzoyloxy-4′- (6-bromohexyloxy)biphenyl showed the smectic A (S_A) and cholesteric phases on heating cycle, and a cubic Blue Phase, chiral smectic C (S_C^*), S_A and cholesteric phases on cooling cycle. However, the compound 4-menthyloxyacetoxybenzoyloxy-4′-(4-bromobutoxy)biphenyl showed enantiotropic S_C^*, S_A and cholesteric phases, moreover, the platelet texture of a cubic Blue Phase was also observed on cooling cycle. The methacrylate monomer with six flexible methylene units and three phenyl rings as mesogenic core only showed cholesteric phase, while the methacrylate monomer with four methylene unit and three phenyl rings showed the S_C^* and cholesteric phases. However, when the terminal methacryloyloxy groups in the monomers were substituted by thiophenylacryloyloxy groups, the corresponding monomers all show no mesophase. With increasing the rigidity of mesogenic core or decreasing the flexible methylene spacer length, the corresponding melting temperature (T_m) or isotropic temperature (T_i) increased.     

Synthesis and an X-ray diffraction study of Rb<Subscript>2</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript>]

The synthesis and X-ray diffraction study of compound Rb₂[(UO₂)₂(C₂O₄)₃], which crystallizes in the monoclinic crystal system, are performed. The unit cell parameters are as follows: a = 7.9996(6) Å, b = 8.8259(8) Å, c = 11.3220(7) Å, β = 105.394(2)°, and V = 770.7(1) ų; space group P2₁/n, Z = 2, and R ₁ = 0.0271. [(UO₂)₂(C₂O₄)₃]^2? layers belonging to the AK _0.5 ⁰² T ¹¹ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , K ⁰² = C₂O ₄ ^2? , and T ¹¹ = C₂O ₄ ^2? ) are uranium-containing structural units of the crystals. The layers are connected with outer-sphere rubidium cations by electrostatic interactions.     

Synthesis and Properties of Novel Nonlinear Optical Polyester Containing Cyanovinylnitroresorcinoxy Group

Novel X-type polyester 5 containing 4-(2’-carbomethoxy-2’-cyano)vinyl-6-nitroresorcinoxy group as nonlinear optical (NLO) chromophore, which constitutes parts of the polymer backbone, was prepared and characterized. Polyester 5 is soluble in common organic solvents such as N,N-dimethylformamide and acetone. Polyester 5 shows a thermal stability up to 280°C from thermogravimetric analysis with glass-transition temperature obtained from differential scanning calorimetry of near 116°C. The second harmonic generation (SHG) coefficient (d₃₃) of poled polymer film at the 1064 nm fundamental wavelength is 4.25 × 10^?9 esu. The dipole alignment exhibits a thermal stability even at 4°C higher than glass-transition temperature (T_g), and no significant SHG decay is observed below 120°C due to the partial main-chain character of polymer structure, which is acceptable for NLO device applications.     

Phase transitions in Cs5(HSO4)2(H2PO4)3 crystal

The symmetry (sp. gr.I $\bar 4$ 3d) and lattice parameters have been determined for the first time for Cs₅(H₂SO₄)₂(H₂PO₄)₃ crystals in the temperature range from 172 to 390 K. The thermal and optical properties of crystals, as well as their conductivity, have been investigated at elevated temperatures. It is shown that a crystal heated to T = 365 K undergoes a phase transition with symmetry lowering to the tetragonal phase (with the parameters a = 4.965(1) Å and c = 5.016(1) Å), while at T ≈ 390 K a phase transition to the cubic phase is presumably observed. With a decrease in temperature, a phase transition without a change in symmetry occurs at T = 240 K.     

Synthesis and Nonlinear Optical Properties of Novel Polyurethane Containing Cyanovinylnitroresorcinoxy Group

Novel X-type polyurethane 5 containing 4-(2′-carbomethoxy-2′-cyano)vinyl-6-nitroresorcinoxy groups as nonlinear optical (NLO) chromophores, which constitute part of the polymer backbone, was prepared and characterized. Polyurethane 5 is soluble in common organic solvents such as acetone and N,N-dimethylformamide. It shows thermal stabilities up to 260°C from thermogravimetric analysis with glass transition temperature obtained from differential scanning calorimetry near 108°C. The second harmonic generation (SHG) coefficient (d₃₃) of poled polymer film at 1064 nm fundamental wavelength is 9.83 × 10^?9 esu. Polymer 5 exhibits a high thermal stability even at 2°C higher than T_g, and no significant SHG decay is observed below 110°C, which is acceptable for nonlinear optical device applications.     

293-K conductivity optimization for single crystals of solid electrolytes with tysonite structure (LaF3): I. Nonstoichiometric phases R 1−yCayF3−y (R = La-Lu,Y)

The systematic optimization of single-crystal fluoride-conducting solid electrolytes R _{1 ? y} Ca _y F_{3 ? y} with a tysonite type structure (LaF₃) with respect to the conductivity at room temperature, σ(293 K), is based on high-temperature measurements of σ(T) of stoichiometric fluorides of rare earth elements, RF₃ (R = La-Nd), in dependence of the radius \(R^{3 + } (r_{R^{3 + } } )\) ; two-component stoichiometric La_{1 ? y} R _y F₃ phases (R = Pr, Nd) in dependence on the average cation radius (r _cat ); and two-component nonstoichiometric phases R _{1 ? y} Ca _y F_{3 ? y} (R = La-Lu, Y) in dependence of the CaF₂ content. The optimization of the composition with respect to thermal stability is based on studying the phase diagrams of CaF₂-RF₃ systems and the behavior of R _{1 ? y} Ca _y F_{3 ? y} crystals upon heating when measuring temperature dependences σ(T). Singlecrystal samples of a number of investigated R _{1 ? y} Ca _y F_{3 ? y} compounds has σ(293 K) values high enough to be applied in solid-state electrochemical devices operating at room temperature (chemical sensors, fluorine-ion batteries, and accumulators) and in devices subjected to thermal cycling.     

Nuclear57Fe relaxation in Fe2+-containing NiFe2O4 and CoFe2O4 single crystals

Spin-lattice (T ₁) and spin-spin (T ₂) relaxation times of ⁵⁷Fe nuclei in the single-crystal NiFe₂O₄ and CoFe₂O₄ ferrites containing Fe²⁺ ions have been studied in the temperature range of 4.2–100 K by a spin-echo technique. The peaks of relaxation rates T ₁ ^?1 and T ₂ ^?1 caused by the presence of Fe²⁺ ions were observed for both ferrites in the ranges 38–42 and 28–32 K, respectively. The analysis of the results obtained with invocation of the data on ferromagnetic resonance and the measurements of the temperature dependence of resistivity shows that the mechanism of nuclear relaxation responsible for “impurity” peaks and is a slow relaxation process caused by electron exchange Fe²⁺ ? Fe³⁺, characterized by a low activation energy.     

Synthesis and crystal structure of Na<Subscript>3</Subscript>(H<Subscript>3</Subscript>O)[UO<Subscript>2</Subscript>(SeO<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>· H<Subscript>2</Subscript>O

Single crystals of the compound Na₃(H₃O)[UO₂(SeO₃)₂]₂ · H₂O (I) have been synthesized, and their structure has been investigated using X-ray diffraction. Compound I crystallizes in the triclinic system with the unit cell parameters a = 9.543(6)Å, b = 9.602(7)Å, c = 11.742(8)Å, α = 66.693(16)°, β = 84.10(2)°, γ = 63.686(14)°, space group P \(\bar 1\), Z = 2, and R = 0.0734. The uranium-containing structural units of the crystals are [UO₂(SeO₃)₂]^2? chains, which belong to the crystal-chemical group AB ² B ¹¹ (A = UO ₂ ²⁺ , B ² = SeO ₃ ^2? , B ¹¹ = SeO ₃ ^2? ) of the uranyl complexes. The structures of the compounds containing the [UO₂(SeO₃)₂]^2? anionic complexes are compared.     

Phase transitions in bubble domain structures upon spin reorientation near the compensation point in ferrite-garnet films

The behavior of a hexagonal lattice of bubble domains in a uniaxial thin film of (BiTm)₃(FeGa)₅O₁₂ ferrite garnet with a compensation temperature of 120 K was studied experimentally in a range of change in anisotropy from the easy magnetization axis to the easy magnetization plane. It is shown that the spin reorientation occurs in the temperature range 185–160 K, in which the angular phase (either \(\Phi _{\left\langle {1\bar 1\bar 1} \right\rangle }\) or \(\Phi _{\left\langle {\bar 111} \right\rangle }\)) and the axial phase Φ:_〈111〉 coexist. At 172 K, when the percentages of the angular and axial phases are equal, the lattice parameters of the bubble domains and the domain-wall width change stepwise. At T < 160 K, only a plane magnetic phase exists.