Pressure-temperature phase diagrams of smectogenic 4'-alkyl-4-cyanobiphenyls (9CB, 10CB, 11CB and 12CB)

The pressure-temperature ( p - T ) phase diagrams for four smectogenic members of the 4'-alkyl-4-cyanobiphenyl homologous series ( n CB, n =9, 10, 11 and 12) over the temperature range 320-410 K and pressure range 0.1-300 MPa (3 kbar) were constructed using DTA. At 1 atm 9CB exhibits nematic and smectic A d phases, while the other members show only the smectic A d phase. However, at elevated pressures the clearing line splits in the case of 10CB and 11CB which indicates the induction of a nematic phase. It was found that the triple point, where the isotropic, nematic and smectic phases coexist, is strongly shifted to higher pressures with increasing chain length. This was interpreted as being caused by a loss of the rod-like shape of the molecules containing longer alkyl tails which explore a range of conformations. The slope of the clearing line, d T /d p , depends strongly on the length of the alkyl chain for the n CB series, but does not show a step-wise change between the nematogenic and smectogenic members.     

Orientational characteristics of liquid crystals (5CB) by means of optical study

Information on molecular dynamics of the nematic liquid crystal 4-n-pentyl-4'-cyanobiphenyl (5CB) doped with the dyes DMANS and DMANAB has been obtained by luminescence and Raman measurements. Temperature dependences of reorientational correlation times are not the same for different molecular motions. Mechanisms responsible for the marked deviation of the time values obtained by different optical methods are discussed.     

Synthesis, growth, optical, mechanical, dielectric and thermal properties of 4-chloro-4'-chlorobenzylidene aniline single crystal

The organic material 4-chloro-4′-chlorobenzylidene aniline (CCBA) was synthesized and confirmed by NMR and FTIR spectral analyses. CCBA crystal was grown from chloroform by slow evaporation at room temperature and the single crystal cell parameters were determined by single crystal X-ray diffraction method. The perfection of the grown crystal was analyzed by high resolution X-ray diffraction rocking curve analysis. Fluorescence spectrum indicated violet emission at 428 nm. The range of optical absorbance was ascertained by recording UV–vis–NIR spectrum. Load dependant microhardness measurements on this crystal revealed the mechanical behavior of the material. Stiffness constant, Meyer index and yield strength of CCBA crystal were calculated. Dielectric studies were carried out to estimate the dielectric parameters of the grown crystal in the frequency range from 100 Hz to 100 kHz. The thermal behavior of CCBA was investigated using differential scanning calorimetry (DSC) and no phase transition was identified in the temperature region 30–100 °C. Further, the CCBA crystal was subjected to open aperture Z-scan studies in order to investigate the third order nonlinear optical (NLO) properties of CCBA crystal.     

Elastic, dielectric and optical constants of 4'-pentyl-4-cyanobiphenyl

4'-n-Pentyl-4-cyanobiphenyl (5CB) is a room temperature nematic liquid crystal with a high positive dielectric anisotropy and a high chemical stability. Many experimental results concerning the elastic and dielectric constants of 5CB are available in the literature, although there is often no satisfactory agreement between the experimental data obtained by different groups, especially as far as the dielectric constants are concerned. Furthermore, no detailed investigation of the temperature dependence of the elastic and dielectric constants close to the nematic-isotropic transition temperature T_NI has yet been reported. In this paper, we report the measurement of the elastic and dielectric constants of 5CB, and the temperature behaviour close to T_NI has been investigated in detail. The experiment consists in the measurement of the director deformation induced by an electric field using simultaneously both a dielectric and an optical method. The simultaneous use of these two methods provides an indirect check on the reliability of the measurements. Special attention has been devoted to control possible sources of uncertainty. In particular, the effects of finite anchoring energy and of finite pretilt angle have been considered. The temperature dependence of the anisotropy of the refractive indices is also obtained in the experiment.     

Elastic,dielectric and optical constants of 4'-pentyl-4-cyanobiphenyl

4'-n-Pentyl-4-cyanobiphenyl (5CB) is a room temperature nematic liquid crystal with a high positive dielectric anisotropy and a high chemical stability. Many experimental results concerning the elastic and dielectric constants of 5CB are available in the literature, although there is often no satisfactory agreement between the experimental data obtained by different groups, especially as far as the dielectric constants are concerned. Furthermore, no detailed investigation of the temperature dependence of the elastic and dielectric constants close to the nematic-isotropic transition temperature T _NI has yet been reported. In this paper, we report the measurement of the elastic and dielectric constants of 5CB, and the temperature behaviour close to T _NI has been investigated in detail. The experiment consists in the measurement of the director deformation induced by an electric field using simultaneously both a dielectric and an optical method. The simultaneous use of these two methods provides an indirect check on the reliability of the measurements. Special attention has been devoted to control possible sources of uncertainty. In particular, the effects of finite anchoring energy and of finite pretilt angle have been considered. The temperature dependence of the anisotropy of the refractive indices is also obtained in the experiment.     

Coordination properties of 4(5)-hydroxymethylimidazole and 4(5)-hydroxymethyl-5(4)-methylimidazole towards cobalt(II) ions

Two new complexes of imidazole alcohols, 4-hydroxymethylimidazole (4-CH₂OHim) and 4-hydroxymethyl-5-methylimidazole (4-CH₂OH-5-CH₃im), with cobalt(II) of formula [CoL₂(H₂O)₂](NO₃)₂ were obtained. These compounds were described through single X-ray diffraction studies, spectroscopic (Ir. Far-IR, UV-Vis-NIR) and magnetic measurements. In the present complexes imidazole ligands are bidentate coordinating the heterocyclic ring through pyridine-like nitrogen and the oxygen atom of the hydroxymethyl group (chromophore CoN₂O₄). The shape of Co(II) coordination polyhedra is that of a distorted octahedron, with the equatorial plane defined by the 4-CH₂OHim (or 4-CH₂OH-5-CH₃im) bidentate ligands and two water molecules occupying axial positions (i.e. trans to each other). Formation of successive cobalt(II) complexes with 4-CH₂OH-5-CH₃im in aqueous solution was followed quantitatively by potentiometry.     

Synthesis and properties of analogs of 5(4)-aminoimidazole-4(5)-carboxamide (AICA)

A new analog of AICA — 5(4)-hydrazinoimidazole-4(5)-carboxamide — forms the corresponding hydrazones with carbonyl-containing compounds and reacts with sodium nitrite to give 5(4)-azidoimidazole-4(5)-carboxamide, the structure of which was proved on the basis of IR spectroscopic data.See [1] for communication I.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 94–95, January, 1973.     

Synthesis, structure, and optical properties of LiEu(PO3)4 nanoparticles

A wet chemical approach was employed for the preparation of LiEu(PO(3))(4) nanoparticles. XRD, Raman spectroscopy, TEM, SAED, and IR measurements were used in order to determine the crystal structure and morphology of the obtained product. Complete optical studies including absorption, excitation, emission, and kinetic measurements were performed. At least two components of the (5)D(0) → (7)F(0) transition were found, indicating the existence of more than one crystallographic position of the Eu(3+) ions. Asymmetry parameter R as well as the covalence of the Eu-O bond were found to decrease with the grain growth.     

Synthesis,structure, and optical properties of CsU2(PO4)3

CsU₂(PO₄)₃ was synthesized in highest yield by the reaction in a fused-silica tube of U, P, and Se in a CsCl flux at 1273 K. It crystallizes with four formula units in space group P2₁/n of the monoclinic system in a new structure type. The structure of CsU₂(PO₄)₃ is composed of U and Cs atoms coordinated by PO₄^3? units in distorted octahedral arrangements. Each U atom corner shares with six PO₄^3? units. Each Cs atom face shares with one, edge shares with two, and corner shares with three PO₄^3? units. The structure shares some features with the sodium zirconium phosphate structure type. X-ray powder diffraction results demonstrate that the present CsU₂(PO₄)₃ compound crystallizes in a structure different from the previously reported β′- and γ-CsU₂(PO₄)₃ compounds. CsU₂(PO₄)₃ is highly pleochroic, as demonstrated by single-crystal optical absorption measurements.     

金属硫氰酸根配合物FeHg(SCN)~4, MnHg(SCN)~4的合成、晶体结 构与非线性光 学性质的研究

合成了配合物晶体FeHg(SCN)~4和MnHg(SCN)~4。用单晶X射线衍射方法测定了这两个晶体的结构。以尿素为标准样品用粉末晶体倍频1064nm的Nd:YAG激光,测得其倍频光强度分别为:FeHg(SCN)~4,0.6倍于尿素;MnHg(SCN)~4,50倍于尿素,后者显示了作为新的非线性光学材料的发展前景。     

Ba2AgInS4 and Ba4MGa5Se12 (M = Ag, Li): syntheses, structures, and optical properties

The first two members in alkaline-earth/group XI/group XIII/chalcogen system, namely Ba(2)AgInS(4) and Ba(4)AgGa(5)Se(12), were synthesized along with a Li analogue Ba(4)LiGa(5)Se(12). Ba(2)AgInS(4) crystallizes in space group P2(1)/c. It contains [AgInS(4)](4-) layers built from AgS(3) triangles and InS(4) tetrahedra with Ba(2+) cations inserted between the layers. Ba(4)AgGa(5)Se(12) and Ba(4)LiGa(5)Se(12) adopt two closely-related structure types in space group P4[combining macron]2(1)c with structural difference originating from the different positions of Ag and Li in them. The three-dimensional framework in Ba(4)AgGa(5)Se(12) is composed of GaSe(4) tetrahedra with the Ba and Ag atoms occupying the large and small channels respectively, whereas that in Ba(4)LiGa(5)Se(12) is built from LiSe(4) and GaSe(4) tetrahedra with channels to accommodate the Ba atoms. As deduced from the diffuse reflectance spectra measurement, the optical band gaps were 2.32 (2) eV, 2.52 (2) eV, and 2.65 (2) eV for Ba(2)AgInS(4), Ba(4)AgGa(5)Se(12), and Ba(4)LiGa(5)Se(12), respectively.     

Thermodynamic properties of chiral liquid crystalline material (S)-4-(2-methylbutyl)-4′-cyanobiphenyl (5*CB)

As a part of a project of clarifying the physical properties and dynamics of cyanobiphenyls with chiral molecules, thermodynamic properties of (S)-4-(2-methylbutyl)-4′-cyanobiphenyl (5*CB) were investigated by adiabatic calorimetry between T = (5 and 350) K. The complicated phase behaviour was solved and the thermodynamic functions were determined. A new glass transition was identified in the phase II (metastable crystal) at T = 105 K. No inversion of the stability between two crystalline phases was found, being contrary to the expectations from the previous neutron scattering studies.     

Mesomorphic properties of 2-acyloxy5-(4-alkoxyphenylazo)tropones, 2-acyloxy-5-(4-alkylphenylazo)tropones,and 2-acyloxy-5-(4-alkoxycarbonylphenylazo)tropones

Three series of mesomorphic 2-acyloxy-5-phenylazotropones with alkoxy, alkyl, and alkoxycarbonyl groups at C-4 on the phenyl ring were prepared. It was known that the corresponding 5-phenylazotropolone derivatives and their methyl ethers were not mesomorphic. 2-Acetyl-5-(4-hexyloxyphenylazo)tropone, however, shows a monotropic smectic A phase. Even an acetyl group is therefore able to induce a mesophase. The effects of terminal substitution of the tropone ring by groups such as alkoxy, alkoxycarbonyl, and alkyl on the clearing points are discussed.     

Mesomorphic properties of 2-acyloxy5-(4-alkoxyphenylazo)tropones, 2-acyloxy-5-(4-alkylphenylazo)tropones, and 2-acyloxy-5-(4-alkoxycarbonylphenylazo)tropones

Three series of mesomorphic 2-acyloxy-5-phenylazotropones with alkoxy, alkyl, and alkoxycarbonyl groups at C-4 on the phenyl ring were prepared. It was known that the corresponding 5-phenylazotropolone derivatives and their methyl ethers were not mesomorphic. 2-Acetyl-5-(4-hexyloxyphenylazo)tropone, however, shows a monotropic smectic A phase. Even an acetyl group is therefore able to induce a mesophase. The effects of terminal substitution of the tropone ring by groups such as alkoxy, alkoxycarbonyl, and alkyl on the clearing points are discussed.     

Crystal structures of 4-cyano-4-hexylbiphenyl (6CB) and 4-cyano-4-heptylbiphenyl (7CB) in relation to odd-even effects

Crystal structures of 4-cyano-4-hexylbiphenyl (6CB) and 4-cyano-4-heptylbiphenyl (7CB) with low melting points (13.5 and 30 C, respectively) have been determined at 73 and 33 C, respectively, and compared with previously reported structures of other homologues (n = 2-5, 8-11). In the crystal of 7CB, chains and cores stack alternately, where core regions are largely overlapped with distances of 3.575(2) and 3.597(2)A for N (in CN)... C (in phenyl), showing almost the same packing mode as those of 9CB and 11CB. In the crystal of 6CB, CN groups are antiparallel between neighbouring molecules though the interatomic distances are much longer N ... C, 3.673(3) and 3.563(3)A than in 8CB and 10CB (3.28-3.43A), resulting in a quite different packing mode from those of 8CB and 10CB, which had been found to be similar, with CN-CN interactions. Systematic comparison of the homologous series (n = 2-11) reveals odd-even effects, CN-phenyl and CN-CN interactions for odd and even members, respectively, in the crystal structures, except for 5CB and 6CB.     

NH2(C2H4)2O]MX5: a new family of morpholinium nonlinear optical materials among halogenoantimonate(III) and halogenobismuthate(III) compounds. Structural characterization, dielectric and piezoelectric properties

This paper presents the structural features of ionic complexes formed by morpholine and metal ions which belong to group VA, namely Sb(III) and Bi(III). A series of target inorganic-organic hybrid compounds of the general formula [NH(2)(C(2)H(4))(2)O](2)MX(5) (where M = Sb, Bi; X = Cl, Br) has been synthesized by incorporating the organic component (morpholine) into the highly polarizable one-dimensional halogenoantimonate(III)/halogenobismuthate(III) chain network. Among the studied compounds, four were found to crystallize in the room temperature phase in the piezoelectric, orthorhombic space group P2(1)2(1)2(1), Z = 4, the feature being confirmed by the powder second harmonic generation of light and piezoelectric measurements. Dielectric dispersion studies between 200 Hz and 2 MHz disclosed a relaxation process below room temperature well described by the Cole-Cole equation. Based on crystal structures available in Cambridge Structural Database (version 5.32, November 2010) we attempt to show a relationship between the acentric symmetry of compounds and the type of anionic network within the R(2)MX(5)-subgroup (where R denotes organic cation) of halogenoantimonates(III) and halogenobismuthates(III).     

Synthesis,structure and dielectric properties of a novel Gd coordination polymer based on 2-（ pyridin-4-yl ）- 1H-i midazole-4,B -dicarboxylate

A new Gd coordination polymer based on 2-（pyridin-4-yl）-I H-imidazole-4,5-dicarboxylate （H3PIDC） has been synthesized under hydrothermal conditions, formulated as {[Gd3（HPIDC）3（PIDC）（H2O）4].3H2O}n （1）. The compound crystallizes in the monoclinic system, space group C2/c with a=20.951（7）, b = 9.515（3）, c = 27.483（10） A,β= 106.176（6）°, Z = 4, V= 5262（3） A3, C40 H45 Gd3 N12 O30, Dc = 2.071 g/cm3, Mr=1645.63, λ （MoKa）=0.71073A, μ=3.846mm-1, F（000）=3204, the final R=0.0390 and wR= 0.1332. Complex 1 is a two-dimensional MOF built up from T-shaped 3-connected HPIDC2 , PIDC3 and 4-connected metal nodes. Dielectric constant of complex 1 was measured at different frequencies with temperature variation.     

Synthesis and properties of analogs of 5(4)-aminoimidazole-4(5)-carboxamide and purines. 14. Acylation of 5(4)-aminoimidazole derivatives

The acylation of 5(4)-aminoimidazole derivatives was studied. It is shown that acylation by means of carboxylic acid anhydrides and chlorides takes place at the amino group, whereas acylation by means of chlorocarbonic acid esters takes place at the nitrogen atoms of the imidazole ring. Methods for the selective introduction of a carbomethoxy group in the 1, 3, and 5 positions of the 5(4)-aminoimidazole-4(5)-carboxamide molecule were developed.See [1] for communication 13.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 247–252, February, 1984.