Fan-shaped,toric and spherulitic textures of mesomorphic oxadiazoles

When a family of non-symmetrical heterocycled compounds is investigated, a variety of mesophases can be observed with rather different features. Here we report the behaviour of seven different members among a family of such materials, which consists of mesomorphic oxadiazole compounds. In two of these compounds, the optical microscope investigation shows very interesting behaviours. In their smectic phases, fan-shaped and toric textures, sometimes with periodic instability, are observed. Moreover, the nematic phase displays a texture transition. Texture transitions have been previously observed only inside the nematic phase of some compounds belonging to the families of the oxybenzoic and cyclohexane acids. In these two oxadiazole compounds we can observe a nematic phase with a spherulitic texture, heating the samples from the smectic phase. This nematic texture disappears as the sample is further heated, changing into a smooth texture.     

Correlation between adsorption and thermal properties of lanthanide(III) dinicotinates

Structural and thermal properties of the two isostructural lanthanide metal-organic frameworks: [Er₂(pdc)₃(dmf)₂]·dmf (1) and [Tm₂(pdc)₃(dmf)₂]·dmf (2) where pdc = C₅H₃N(COO)₂²⁻ and dmf = N,N′-dimethylformamide, have been investigated. They are characterized by the BET surface area of 302 and 101 m²/g for 1 and 2, respectively. This paper deals with the influence of activation conditions on sorption properties of the investigated complexes. Thermal investigations of as-made and activated complexes point to their entirely different thermal decompositions.     

Eu(III) and Tb(III) luminescent lanthanide systems derived from DTPA-bisamide and DTTA-based ligands incorporating bipyridine antenna

Four new polycarboxylate ligands H₃Lⁿ have been synthesized by the attachment of two or one 2,2′-bipyridine subunits onto a diethylenetriamine pentacarboxylic acid (DTPA-bisamide derivatives: H₃L¹, H₃L²) or a diethylenetriamine tricarboxylic acid (DTTA derivatives: H₃L³, H₃L⁴) core. The neutral Eu^III and Tb^III complexes of these chelates have been prepared and studied from their UV-vis and luminescence data. The main photophysical characteristics of these complexes, i.e. the absorption and luminescence spectra, the metal-centred lifetimes and the overall luminescence yields (Φ) were measured in buffered aqueous solutions. In addition the role played by non-radiative paths (vibrational energy transfer involving coordinated water molecules, involvement of ligand-to-metal charge-transfer excited states, or metal→ligand back-transfer) was investigated. In all complexes, we found that the bidentate bipyridine chromophore is not coordinated to the lanthanide ion, allowing one (LnL¹, LnL²) or two (LnL³, LnL⁴) water molecules to penetrate the first coordination sphere of the metal. Although the bipyridine chromophore behaves as remote (from the binding site) light-harvesting unit for the lanthanide ion in these systems, a sizeable sensitization of the Eu- and Tb-centred luminescence can be effective (LnL², LnL³, Φ=16-19% in aerated D₂O solutions). Our photophysical investigations show that overall non-radiative deactivation is not dependant of thermally activated non-radiative channels but the efficiency of the ligand→Ln intramolecular energy transfer has to be taken into account to explain the obtained results.     

Elastic,nonlinear and plastic behaviour of the smecticA phase

Summary Stress-strain measurements of layer compression in a smecticA liquid crystal are presented. We describe in the instantaneous response a linear regime and a nonlinear behaviour, above the layer undulation instability. The time dependence of the observed stress relaxation is measuredvs. the applied strain. This plastic behavior is discussed in relationship with the observed more or less permanent layer distorsions.

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Riassunto Si presentano misurazioni dello sforzo-deformazione della compression di strato in un cristallo liquido smetticoA. Si descrivono nel responso instantaneo un regime lineare ed un comportamento non lineare, al di sopra dell'instabilità di ondulazione dello strato. Si misura la dipendenza dal tempo della relazione di sforzo osservata rispetto alla deformazione applicata. Questo comportamento plastico è discusso in relazione con le distorsioni di strato piú o meno permanenti osservate.

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Резюме Приводятся результаты измерений зависимости напряжений от деформации при сжатии слоя в смектическомA жидком кристалле. Мы описываем мгновенный отклик в линейном режиме и нелинейное поведение, выше волнообразной неустойчивости слоя. Измеряется временная зависимость наблю даемой релаксации напяжений в зависимости от деформации. Обсуждается пластическое поведение в связи с наблюдаемыми более или менее остаточными деформациями слоя.

     

Synthesis,growth and characterization of 4-dimethylaminobenzaldehyde-4-nitrophenylhydrazone single crystals

4-Dimethylaminobenzaldehyde-4-nitrophenylhydrazone (DANPH) single crystals exhibit polymorphism such as DANPH-G form (greenish red) and DANPH-R form (red). The different polymorphic phases of the grown crystals have been identified by X-ray diffraction studies. The functional groups of the crystals have been identified by FT-IR study. Crystallographically independent environment of polymorphs has been confirmed by NMR study. The thermal properties such as melting and decomposition temperatures of the compound have been analyzed. Optical constants of DANPH polymorph crystals have been calculated.     

Liquid crystals and some of their applications

This paper is a brief review of some of the properties and applications of liquid crystals. By studying the references, a reader can gain a more extensive insight into the liquid crystalline state. Classifications of liquid crystalline materials and nomenclature characteristic of the field give the reader a working knowledge of the subject. Polymorphism is one of the common properties of liquid crystalline materials; the subject is covered in the text and summarized in tabular forms. The fundamental properties of liquid crystals are correlated with some of the behaviors and uses of liquid crystals. Optical properties, curvature elastic properties, surface effects, external field effects and hydrodynamics of the liquid crystalline state are discussed as necessary to describe recent practical applications; these include displays, storage of images and other electrooptic devices. Some of the results presented in this review were obtained under NSF Grant No. GH-34164X.     

Double-stranded helical lanthanide(III) supramolecular networks with rigid diimine ligands: Synthesis, structure, and physical properties

Two lanthanide coordination complexes [Nd(NO₃)₃(CH₃OH)₂(4,4′-bipy)₂] (1) (4,4′-bipy=4,4′-bipyridine) and [4,4′-Hbipy][La(NO₃)₄(H₂O)₂(4,4′-bipy)] (2), with a salt of cationic diprotonated 4,4′-bipy, [2(4,4′-H₂bipy)][4(NO₃)] (3), have been identified and isolated from a methanol solution of Ln(NO₃)₃·6H₂O, 4,4′-bipyridine and pyrazine in 1:2:1 ratio. Their structures have been determined by single-crystal X-ray diffraction analyses, which reveal that 1 has an interesting three-dimensional supramolecular architecture containing 2₁ double-stranded helical chains through hydrogen bonding and π–π interactions, while 2 and 3 have well defined infinite chiral 3D open networks that undergo self-interpenetration. The electrospray ionization mass spectra (ESI-MS) indicate that the covalent complex has higher stability than the electrostatic bonding one. ESI-MS/MS of these ions reveal that the Ln–O bond forms a stronger coordinated bonding than that of Ln–N system and the nitrate anion remains bound to the lanthanide centers after complete dissociation in methanol solution.     

Wave shape of de Haas-van Alphen oscillations and effective mass in the two-dimensional organic conductor α-(BEDT-TTF)2KHg(SCN)4

De Haas-van Alphen (dHvA) oscillations in the two dimensional organic conductor α-(BEDT-TTF)₂KHg(SCN)₄ have been measured by a canti-lever technique at high magnetic fields up to 30 T. The wave shape of the dHvA oscillations undergoes a drastic change around the transition field B_K (24 T). The effective mass shifts 1.5 m₀ in the density wave phase (B<B_K) to 1.65 m₀ in the normal metallic phase (B>B_K). Based on the simulation, we have determined that the primary cause of the characteristic field dependence of the wave shape is the change in the effective mass.     

Synthesis, characterization and analytical applications of Ni(II)-ion imprinted polymer

Ion recognition-based separation techniques have received much attention because of their high selectivity for target ions. In this study, we have prepared a novel ion imprinted polymer (IIP) to remove nickel ions with high selectivity. The imprinted polymer was prepared by copolymerization of 2-hydroxy ethyl methacrylate (HEMA) with nickel vinylbenzoate complex in the presence of ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The polymerization was carried out in bulk with free radical initiation using 2-methoxy ethanol as a solvent and porogen. The adsorbed nickel was completely eluted with 15 mL of 1 M HCl. Control polymer was also prepared by similar experimental conditions without using imprint ion. The above synthesized polymers were characterized by surface area measurements, FT-IR, microanalysis and SEM analysis. The adsorption capacity of IIP and CP was found to be 1.51 and 0.65 mmol g⁻¹, respectively. The optimal pH for quantitative enrichment was 6.5. Nature of eluent, eluent concentration and eluent volume were also studied. The relative selectivity factor (α_r) values of Ni(II)/Zn(II), Ni(II)/Cu(II) and Ni(II)/Co(II) were 78.6, 111.1 and 91.6, respectively. Five replicate determinations of 30 μg L⁻¹ of Ni(II) gave a mean absorbance of 0.067 with a relative standard deviation of 1.06%. The lowest concentration determined by GTA-AAS below which the recovery becomes non-quantitative is 6 μg L⁻¹. IIP was tested for removal of Ni(II) from sea water sample.     

Synthesis/structural and mesomorphic properties of substituted hydrazide based calamitic molecules

A set of rod-shaped molecules with central hydrazide moiety has been synthesized and characterized using standard spectroscopic techniques. The thermal behaviors of the final compounds were established by the combination of differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and high-temperature powder X-ray method (XRD). The structure and conformation of the molecules were achieved by FTIR, ¹H NMR, ¹³C NMR spectroscopy and DFT calculations. It is found that two compounds are non-liquid crystalline and two compounds are liquid crystalline (LC). The structure property correlations with alkyl chain, connecting position, hydrogen bonding and without hydrogen bonding were established. The studies envisaged that LC properties are induced due to hydrogen bonding and elongation of the molecular length.     

Synthesis and structural characterization of a series of lanthanide stannate pyrochlores

A simple hydrothermal method has been employed to prepare a series of lanthanide stannate pyrochlores Ln₂Sn₂O₇ (Ln=Y, La, Pr-Yb) at a relatively low temperature of less than 200 °C successfully. On the basis of structural characterizations by X-ray powder diffraction (XRD), Fourier transform infrared (FT-IR) absorption spectroscopy and Raman spectroscopy, it was found that the positions of bands in vibrational spectra are sensitive to the ionic radius of Ln³⁺, and the linear relationship can be seen between the frequency of Sn-O stretching mode and the lanthanide ionic radius in IR spectrum, as well as the frequency of O-Sn-O bending mode and the lanthanide ionic radius in Raman spectrum.     

IR Absorption and Raman spectroscopic study of reentrant-nematic liquid crystalline N-[4-(4-Octyloxy-benzoyloxy) Benzylidene]-4-Cyanoaniline (OBBC)

Abstract

The IR absorption and Raman scattering of OBBC have been investigated in the solid, ReN, SmA and nematic phases. The intensity of the 2229 cm^?1 band assigned to the C[tbnd]N stretching mode decreases with increasing temperature in the reentrant nematic phase; this is attributed to a change in the overlap of the molecules. While the IR bands at 1728 and 841 cm^?1 also show a remarkable temperature dependence, Raman bands do not show significant temperature dependence in the liquid-crystal phases.     

Mesomorphic and optical properties of undoped and doped azomethines

Three calamitic azomethines were prepared by the condensation of the benzene-1,4-dicarboxaldehyde with the three aliphatic amines (LCOA1–LCOA3). The structures of the azomethines were characterized by means of FTIR, ¹H, ¹³C NMR spectroscopies and elemental analysis; the results showed an agreement with the proposed structure. The azomethines emitted blue or green light. An influence of n-decyl sulfonic acid (DSA) on mesomorphic behaviors, absorption and emission wavelengths was investigated. The liquid crystalline properties of the azomethines were studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and wide and small angle X-ray diffraction (WAXS and SAXS). The mesomorphic properties of the compounds depend on both the length of the outer flexible spacers and the kind of connection between the alkyl groups and the imine group, i.e. directly via aliphatic chain or by phenyl ring. LCOA1–LCOA2 exhibited smectic and nematic phases, whereas the LCOA3 did not exhibit thermotropic liquid crystal properties. Basing on the comparison of thermal behaviors and optoelectronic properties of undoped (LCOAX) and doped (LCOAX/DSA) azomethines it was shown that ionic self-organized processes are powerful and are able to tune: i) the processability, ii) the LC behavior, and iii) the maximum of emission band of the synthesized azomethines.     

Design, synthesis and characterization of a linear hydrogen bonded homologous series

A linear hydrogen bonded liquid crystalline homologous series has been synthesized and characterized. Hydrogen bond is formed between p-n-dodecyloxy benzoic acid and various p-n-alkyl benzoic acids whose alkyl chain vary from octyl to ethyl. Synthesized complexes are characterized by FTIR, ¹H NMR and ¹³C NMR studies for inferring the formation of hydrogen bonds. Polarizing Optical Microscopy (POM) and DSC studies reveal various mesophases and their corresponding transition temperatures along with respective enthalpy values. All the seven synthesized complexes exhibit rich liquid crystalline mesomorphism. A new phase namely smectic X has been observed in five of the complexes with a narrow thermal range. This phase has been characterized by optical textural, DSC, tilt angle and helicoidal pitch studies. Smectic X is sandwiched between traditional smectic C and re-entrant smectic C (designated as C_R) phases. Homeotropic transition in nematic phase is observed in all the mesogens and thus these materials can be used as thermally controlled optical shutters. Tilt angle in smectic C, smectic X and smectic C_R phases have been experimentally elucidated for all the mesogens.     

Synthesis and characterization of hexakis(acetonitrile)chromium(III) tetrafluoroborate, [Cr(NCMe)6][BF4]3. A nonaqueous Cr source

Oxidation of [Cr^II(NCMe)₄][BF₄]₂ with thianthrinium tetrafluoroborate forms [Cr^III(NCMe)₆][BF₄]₃ exhibiting two ν_CN absorptions at 2331 and 2301 cm⁻¹, and has been structurally characterized with an average Cr-N distance of 1.999 Å. From the electronic absorption spectra the ligand field splitting, Δ₀, is 20,160 cm⁻¹, which is slightly larger than [Cr^III(OH₂)₆]³⁺ in accord with the divalent chromium analogues. The 298 K ESR has a resonance at g=1.9884, and the magnetic susceptibility has a 300 K moment of 3.85μ_B characteristic of S=3/2 Cr(III). The field dependence of the magnetization can be fit to the Brillouin function also characteristic of S=3/2.     

钇,钕与双希夫碱2—羟基—3—甲氧基苯甲醛缩联苯胺配合物的 …

在非水体系中首次合成了Ｙ（Ⅲ）、Ｎｄ（Ⅲ）与双希夫碱２－羟基－２－甲氧基苯甲醛缩联苯胺的固体配合物。用元素分析,摩尔电导,红外光谱,紫外光谱,核磁共振谱等方法研究共组成、一般性质和结构。     

Synthesis,spectral and thermal characterization of Bis(diethylammonium) tetrachloromercurate(II)-An nonlinear optical material

A new semiorganic compound, bis(diethylammonium) tetrachloromercurate(II) was grown by slow evaporation solution growth technique at ambient temperature from its aqueous solution. The crystal system and the cell parameters have been identified from the powder X-ray diffraction pattern. The UV–visible absorption of the compound shows absorption at 246 nm and there is absorption observed in the entire visible region indicates that the compound can be used as a nonlinear optical material. The UV–visible transmittance spectrum of grown crystal shows a lower cut-off wavelength at 275 nm and it was found that the crystal is suitable for optoelectronic applications. Thermal studies were carried out to find out the thermal stability and confirm the stoichiometric ratio of the compound. The thermal anomalies in DSC study indicate the occurrence of first order transition in the compound at low temperatures. The FTIR spectrum of the compound characterizes various functional groups. The various kinds of protons and carbons were assigned through NMR (¹H and ¹³C) spectroscopic techniques. The SHG efficiency of the compound was studied by Kurtz-Perry power technique and observed that it has SHG efficiency 1.5 times greater than that of potassium dihydrogen phosphate (KDP). The dielectric constant and dielectric loss of the compound decreases with increase in frequency.     

Charge transfer transitions in the transition metal oxides ABO4:Ln and APO4:ln (A=La, Gd, Y, Lu, Sc; B=V, Nb, Ta; Ln=lanthanide)

We have compiled and analyzed optical and structural properties of lanthanide doped non-metal oxides of the form APO₄:Ln³⁺ with A a rare earth and of transition metal oxides with formula ABO₄:Ln³⁺ with B a transition metal. The main objective is to understand better the interrelationships between the band gap energy, the O²⁻→Ln³⁺ charge transfer energy, and the Ln³⁺→B⁵⁺ inter-valence charge transfer energy. Various models exist for each of these three types of electron transitions in inorganic compounds that appear highly related to each other. When properly interpreted, these optically excited transitions provide the locations of the lanthanide electron donating and electron accepting states relative to the conduction band and the valence band of the hosting compound. These locations in turn determine the luminescent properties and charge carrier trapping properties of that host. Hence, understanding the relationship between the different types of charge transfer processes and its implication for lanthanide level location in the band gap is of technological interest.