Dielectric and optical rotatory power investigations of an antiferroelectric liquid crystal 12OF1M7 in a homeotropic cell: implications for models of the structure of ferrielectric phases

The antiferroelectric liquid crystal (AFLC) under investigation possesses different helical smectic phases. Measurements of the optical rotatory power (ORP) of these phases have elucidated the quality of this method for finding the phase transitions between several phases and for investigating their helical structure. The optical rotatory power as a function of temperature for seven wavelengths of light in the range 441 to 665 nm was measured for different phases of the AFLC material investigated, (R)-1-methylheptyl 4-(4'-n-dodecyloxybiphenyl-4-yl-carbonyloxy)-3-fluorobenzoate, with acronym 12OF1M7. The values of the pitch and the optical anisotropy in the plane of the smectic layers for the FiLC (SmC*_FI3) phase and SmC*_Aphase have been calculated from the ORP data. The results of the ORP rule out the simple clock model for describing the structure of the SmC* (SmC*_I1) and AF (SmC*_FI2) phases. The results for these phases can be explained either in terms of the modified Ising model or the highly distorted clock model. The ORP measurements establish the existence of SmC*_FI3 found already from dielectric, polarization and polarized IR spectroscopy.     

Electric field-induced birefringence, optical rotatory power and conoscopic measurements of a chiral antiferroelectric smectic liquid crystal

Using a photoelastic modulator-based novel set-up, the electric field-induced in-plane birefringence and the optical rotatory power (ORP) were measured of an antiferroelectric liquid crystalline compound (12OF1M7) in its various phases using 30 µm homeotropic cells. Some specific signatures of the in-plane birefringence and of the ORP for the various phases are being established. A relatively small threshold field is needed for the unwinding process of the antiferroelectric phase with a unit cell of four layers [SmC_A*(1/2)] compared with that for two layers [SmC_A*(0)]. On application of the electric field on the high temperature side of the SmC_A*(1/2) phase (80.1-81.5°C), a field-induced phase transition is shown to occur directly to the SmC* phase, whereas on the lower temperature side (79.4-80.1°C) the transition takes place to SmC* via the SmC_A*(1/3) phase. The in-plane birefringence exhibits a critical power law dependence for the SmC*-SmA transition. The ORP changes sign within the temperature range of the phase with a unit cell of three layers, reflecting a change in the handedness during this phase. Using tilted conoscopy, the results for the biaxiality and the apparent tilt angle for a smectic liquid crystal with a tilt angle greater than 18° in the ferroelectric phase are reported. The biaxiality implies the difference in the refractive indices between the two minor axes of the refractive index ellipsoid. The optical transmittance at visible and IR wavelengths for free-standing films reveal characteristic reflection bands for these phases. The modulated structures of the reflected bands appear just above the SmC_A* phase and below SmC_A*(1/3); these are possibly due to an easy deformation of the phase by the surfaces.     

Orientational instability of nematic liquid crystal in a homeotropic cell with boundary conditions controlled by an electric field

We study the orientational instability of the director in a homeotropic nematic liquid crystal (NLC) cell in a DC electric field. The electric field is applied along or perpendicular to a cell surface depending on whether anisotropy of dielectric permittivity of NLC is positive or negative. The easy axis on one of the cell polymer substrates is allowed to deviate in perpendicular to the substrate plane due to the influence of the NLC and the electric field. It was established that the orientational instability of the director can have a threshold as well as be thresholdless which depends on the character of the coupling of the easy axis with the electric field. The temporal behaviour of a director and the easy axis during transition to the stationary state after turning on electric field and returning to the initial homogeneous state after turning off the field was investigated. In the case of the negative anisotropy of the static permittivity, the comparison of experimental and calculated time dependences of the easy axis reorientation angle let us to estimate values of the mobile easy axis viscosity coefficient and coupling parameter describing the coupling between the easy axis and the electric field.     

Evolution of a lamellar domain structure for an equilibrating lyotropic liquid crystal

Aerosol OT/water exhibits a lamellar phase over a wide range of concentrations. We show, by magnetic resonance (NMR) and scanning electron microscopy (SEM), that the morphology of the lamellar phase varies significantly across that range and that the rate of equilibration depends strongly on concentration (25, 33, and 50 wt %) with, paradoxically, the faster equilibration at higher surfactant concentrations. We find that the 25 wt % sample exhibits a defect-rich local structure, characteristic of a superposed L(3) character. Further into the lamellar region, at 33 wt %, this defect-rich structure persists heterogeneously, while, at 50 wt %, the lamellar phase domains are highly ordered. The NMR methods used here included (2)H spectroscopy and the two-dimensional NMR method, diffusion-diffusion exchange spectroscopy (DEXSY). The latter was used to obtain quantitative information on the domain sizes and defects within the polydomain lamellar mesophase. Comparison of the NMR with the SEM results suggests that, at 25 wt % AOT, bilayer defects play an important role in influencing the (2)H NMR and DEXSY NMR results.     

Nanoporous crystal 12CaO.7Al2O3: a playground for studies of ultraviolet optical absorption of negative ions

A novel nanoporous material 12CaO.7Al2O3 (C12A7) offers a possibility of incorporating large concentrations (>1021 cm-3) of a wide range of extraframework anions inside its nanopores. We have investigated, both experimentally and theoretically, optical absorption associated with several types of such anions, including F-, OH-, O-, O2-, O2-, and O22-, and assigned their optical absorption bands. It is demonstrated that the chemical identity and concentration of extraframework anions can be controlled by an appropriate treatment of "as grown" C12A7. We also show that the position of the adsorption edge is, in turn, determined by the chemical identity of the extraframework species and can be varied in the range of approximately 4-6 eV. We suggest that C12A7 is a unique host material, which can be used as a playground for studying negatively charged species that are unstable in other environments.     

A model for the chevron structure obtained by cooling a smectic A liquid crystal in a cell of finite thickness

We propose a simple model for the chevron structure observed in recent experiments by cooling a smectic A liquid crystal. We discuss the influence of the cell thickness and of the anchoring conditions on the temperature dependence of the layer tilt angle, and the formation of this structure in the vicinity of a smectic A—nematic transition. Below this critical point, a transition between a bookshelf structure and a chevron one appears. This transition is second order, with continuity of the tilt angle, the threshold being a function of the cell thickness. In addition to a classical layer thinning mechanism, we discuss another possibly based on the temperature dependence of the elastic moduli. We also propose an explanation for the existence of a critical thickness below which the chevrons do not appear.     

Synthesis, crystal structure, and optical properties of a three-dimensional quaternary Hg-In-S-Cl chalcohalide: Hg7InS6Cl5

A crystalline three-dimensional (3D) quaternary chalcohalide, Hg(7)InS(6)Cl(5) (1), has been synthesized through a solid-state reaction under medium temperature. It is the first example in the family of the Hg-IIIA-Q-X (Q = S, Se, Te; X = F, Cl, Br, I) systems. Compound 1 features a 3D network and has an optical band gap of 2.54 eV.     

Syntheses and crystal structures of the closo-borates M2[B7H7] and M[B7H8] (M = PPh4, PNP, and N(n-Bu4)): the missing crystal structure in the series [B(n)H(n)]2- (n = 6-12)

Oxidation of [N(n-Bu(4))](2)[B(9)H(9)] with oxygen in a mixture of dimethoxyethane and CH(2)Cl(2) leads to salts of the [B(7)H(7)](2-) dianion. This is the first convenient synthesis for a seven-vertex hydro-closo-borate anion. Protonation with NEt(3)·HCl resulted in salts of the [B(7)H(8)](-) monoanion. Both closo-borate anions were isolated and characterized by (1)H, (1)H{(11)B}, (11)B, and (11)B{(1)H} NMR spectroscopy. The temperature-dependent (1)H{(11)B}, (11)B, and (11)B{(1)H} NMR spectra of [B(7)H(8)](-) were also measured. The structure of [B(7)H(7)](2-) as well as of [B(7)H(8)](-) were determined by single-crystal X-ray diffraction.     

Orientation and frequency dependence of the deuterium spin-lattice relaxation in multilamellar phospholip1d dispersions: implications for dynamic models of membrane structure

Rapid lateral diffusion of phospholipid molecules in multilamellar dispersions is shown to prevent the observation, in powder pattern spectra, of the orientation dependence of ²H nuclear magnetic spin-lattice relaxation. The spin-lattice relaxation rate is found to have a frequency dependence suggestive of collective director fluctuations.     

Synthesis, solution thermodynamics, and X-ray study of CuII [12]metallacrown-4 with GABA hydroxamic acid: an unprecedented crystal structure of a [12]MC-4 with a gamma-aminohydroxamate

The solution equilibria of gamma-aminobutanehydroxamic acid (GABAha) with H+ and Cu2+ were investigated by potentiometry, titration calorimetry, spectrophotometry, NMR spectroscopy, and ESI-MS. The thermodynamic parameters of the CuII [12]metallacrown-4 obtained for GABAha were compared with those of the corresponding complexes of (S)-alpha-Alaha and beta-Alaha. The stability (-DeltaG0) sequence was beta-Alaha>alpha-Alaha>GABAha, whereas the order of formation enthalpies (-DeltaH0) was beta-Alaha>GABAha>alpha-Alaha. These data were interpreted on the basis of the dimensions of the chelate rings and the planarity of the metallamacrocycles. The CuII [12]metallacrown-4 ([12]MC-4) complex of GABAha was isolated and its crystal structure, which is the first reported for a [12]MC-4 of a gamma-aminohydroxamic acid, fully supports the structural features interpreted from the thermodynamic data.     

Synthesis, crystal structure and properties of a new candidate for nonlinear optical material in the IR region: Hg2BrI3

The synthesis, crystal structure, nonlinear optical (NLO) property and some other properties of a new material, Hg(2)BrI(3), are reported. The crystal structure has been established by single crystal X-ray diffraction studies. Hg(2)BrI(3) belongs to the HgBrI type and crystallizes in the orthorhombic space group Cmc21 (No. 36). The compound shows a phase-matchable second harmonic generation (SHG) of about 1.2 times as strong as that of KTiOPO(4) (KTP) based on the powder SHG measurement. It exhibits a wide transparency in the IR region (from 2.5 to 30 μm), and a good thermal stability. It is believed that Hg(2)BrI(3) is a new candidate for NLO materials in the IR region.     

Syntheses and structural studies of molybdenum-iron-sulfur compounds: I. The synthesis and crystal structure of (Et4N)1[Mo2Fe7S8(SPh)12]

Through the reactions of ferrous thiolates with tetrathiomolybdate, we discussed the reaction pathways and possible intermediates during the formation of double-cubane type Mo-Fe-S cluster compounds. We also reported the synthesis, crystal structure, IR and magnetic susceptibility measurements of the title compound 2. The crystal of 2 belongs to triclinic system, M_r = 2670.3; ; a = 12.755(4) Å, b = 13.076(3) Å, c = 20.576(4) Å; α = 80.00 (2)°, β = 81.39(2)°, γ = 61.51(2)°; V = 2966.3(14) ų; Z = 1; D_c = 1.495 g/cm². Final R factor is 0.077 for 4031 observed reflections. The compound was obtained through the reaction of (Et₄N)₂[Fe₄(SPh)₁₀] (1) with (Et₄N)₂MoS₄ in acetonitrile solution. The structure of anion 2 is two cubane clusters bridged by a Fe(SPh)₆ group. The Mo… Mo' distance of 7.188 Å is the longest among all double-cubane cluster compounds of known structures.     

Impetus for solvothermal synthesis technique: synthesis and structure of a novel 1-D borophosphate using ionic liquid as medium

A novel borophosphate compound has been synthesized under solvothermal conditions using ionic liquid as a medium and structurally characterized by single-crystal X-ray diffractions. The compound crystallizes in the monoclinic, space group P2(1)/n, a=8.089(8) Å, b=13.977(12) Å, c=8.441(8) Å, β=112.517(11)°, Z=2, V=881.7(14) Å³, R₁=0.03, wR₂=0.079 and S=1.01. Its structure consists of a 1-D straight chain that is built of the alternative linkage of mutually perpendicular four-member rings. Other characterizations by IR and thermal and elemental analyses are also described.     

Synthesis, crystal structure and optical investigation of the new phosphates: Na7Mg13Ln(PO4)12 (Ln=La, Eu)

Two new isostructural rare earth phosphates Na₇Mg₁₃Ln(PO₄)₁₂ (Ln=La, Eu) have been synthesized and investigated by X-ray diffraction and optical measurements. They crystallize in the orthorhombic system with the Cmc2₁ space group (Z=4). The crystal structure exhibits a new type of framework built up from LnO₈ (Ln=La, Eu), MO₆ (M=0.5Mg+0.5Na) and MgO_x (x=5, 6) polyhedra and PO₄ tetrahedra linked by common corner, edge or face. It can be described in terms of [Mg₄MP₄O₂₂]_∞ layers stacked along the a direction. These layers are interconnected by [Mg₄LnP₄O₃₆]_∞ undulating chains spreading along the b direction. This framework delimits 6 distinct cavities occupied by Na⁺ cations. The results of the optical study of Na₇Mg₁₃La_1−xEu_x(PO₄)₁₂ (x=0, 0.02, 0.1, 1) reveal the presence of two different Eu³⁺ ion environments whereas the X-ray study predicts the existence of only one Eu site. This difference can be explained by the possible presence of the europium element in the sodium sites with small occupancies which cannot be detected by the X-ray structural determination.     

Straightforward synthesis and structure of a new starting material for niobium cluster phases: [Nb6Cl(i)12(CH3OH)a4Cla2].6CH3OH

A new, fast, and straightforward synthetic route for the new cluster compound [Nb(6)Cl(i)(12)(CH(3)OH)(a)(4)Cl(a)(2)].6CH(3)OH, taking advantage of the special solubility properties of tetracyanoborate salts has been established, and the single-crystal X-ray structure of this compound, which is a promising starting material for new cluster phases, has been determined.     

NMR solution structure of an oligonucleotide hairpin with a 2'F-ANA/RNA stem: implications for RNase H specificity toward DNA/RNA hybrid duplexes.

The first structure of a 2'-deoxy-2'-fluoro-D-arabinose nucleic acid (2'F-ANA)/RNA duplex is presented. We report the structural characterization by NMR spectroscopy of a small hybrid hairpin, r(GGAC)d(TTCG)2'F-a(GTCC), containing a 2'F-ANA/RNA stem and a four-residue DNA loop. Complete (1)H, (13)C, (19)F, and (31)P resonance assignments, scalar coupling constants, and NOE constraints were obtained from homonuclear and heteronuclear 2D spectra. In the chimeric duplex, the RNA strand adopts a classic A-form structure having C3' endo sugar puckers. The 2'F-ANA strand is neither A-form nor B-form and contains O4' endo sugar puckers. This contrasts strongly with the dynamic sugar conformations previously observed in the DNA strands of DNA/RNA hybrid duplexes. Structural parameters for the duplex, such as minor groove width, x-displacement, and inclination, were intermediate between those of A-form and B-form duplexes and similar to those of DNA/RNA duplexes. These results rationalize the enhanced stability of 2'F-ANA/RNA duplexes and their ability to elicit RNase H activity. The results are relevant for the design of new antisense drugs based on sugar-modified nucleic acids.     

Synthesis of a new chiral source, (1R,2S)-1-Phenylphospholane-2-carboxylic acid, via a key intermediate alpha-phenylphospholanyllithium borane complex: configurational stability and X-ray crystal structure of an alpha-monophosphinoalkyllithium borane complex

A synthetic route to enantiomerically pure (1R,2S)-1-phenylphospholane-2-carboxylic acid (1), which is a phosphorus analogue of proline, has been established. A key step is the deprotonation-carboxylation of the 1-phenylphospholane borane complex 3 by using sBuLi/1,2-dipiperidinoethane (DPE). Configurational stability of the key intermediate, the amine-coordinated alpha-phosphinoalkyllithium borane complex 4, was investigated by employing lithiodestannylation-carboxylation of both diastereomers of the 1-phenyl-2-trimethylstannylphospholane borane complex 7 in the presence of several kinds of amines, and as a result, 4 was found to be configurationally labile even at -100 degrees C. The key intermediate, the DPE-coordinated trans-1-phenyl-2-phospholanyllithium borane complex 9, was isolated, and the structure was identified by X-ray crystal structure analysis. This is the first X-ray crystal structure determined for an alpha-monophosphinoalkyllithium borane complex. Remarkably, the alkyllithium complex is monomeric and tricoordinate at the lithium center with a slightly pyramidalized environment, and the existence of a Li--C bond (2.170 A) has been confirmed. Moreover, (1)H-(7)Li HOESY and (6)Li NMR analyses suggested the structure of 9 in solution as well as the existence of an equilibrium between 9, its cis isomer, and the ion pair 8 at room temperature, which was extremely biased towards 9 at -100 degrees C. Finally, 1 was used as a chiral ligand in a palladium-catalyzed allylic substitution, and the desired product was obtained in high yield with good enantioselectivity.     

Crystal structure of the thortveitite‐related M phase, (MnxZn1–x)2V2O7 (0.75 < x < 0.913): a combined synchrotron powder and single‐crystal X‐ray study

The determination of the crystal structure of the M phase, (Mn_xZn_1–x)₂V₂O₇ (0.75 < x < 0.913), in the pseudobinary Mn₂V₂O₇–Zn₂V₂O₇ system for x ≃ 0.8 shows that the previously published triclinic unit‐cell parameters for this thortveitite‐related phase do not describe a true lattice for this phase. Instead, single‐crystal X‐ray data and Rietveld refinement of synchrotron X‐ray powder data show that the M phase has a different triclinic structure in the space group P with Z = 2. As prior work has suggested, the crystal structure can be described as a distorted version of the thortveitite crystal structure of β‐Mn₂V₂O₇. A twofold superstructure in diffraction patterns of crystals of the M phase used for single‐crystal X‐ray diffraction work arises from twinning by reticular pseudomerohedry. This superstructure can be described as a commensurate modulation of a pseudo‐monoclinic basis structure closely related to the crystal structure of β‐Mn₂V₂O₇. In comparison with the distortions introduced when β‐Mn₂V₂O₇ transforms at low temperature to α‐Mn₂V₂O₇, the distortions which give rise to the M phase from the β‐Mn₂V₂O₇ prototype are noticeably less pronounced.