Orientation and Molecular Structure of 1,5 and 1,8 Dichloroanthraquinones by PMR in a Nematic Solution

The structures and the order parameters of 1,5 and 1,8 dichloroanthraquinones have been determined from the dipolar couplings between the protons in the nematic solutions. The results show the effect of steric interactions on the molecular structure. The aromatic rings of 1,8 dichloroanthraquinone are in different planes making an angle of 15° while 1,5 dichlo-roanthraqutnone appears to be flat. The two molecules show peculiar differences in orientation. The “in-plane” order parameters of the 1,8 derivative are about equal while the 1,5 derivative has a strongly preferred alignment axis close to the Cl, Cl internuclear axis.     

Computer Simulation Studies of Anisotropic Systems,III. Two-Dimensional Nematic Liquid Crystals

We have studied a two-dimensional ensemble of cylindrically symmetric particles interacting via a weak anisotropic potential using the Monte Carlo technique of computer simulation. The calculation is simplified by confining the particles to the sites of a triangular lattice. The internal energy, specific heat, second rank orientational order parameter and second rank orientational pair correlation function were calculated at various temperatures. The variation of the order parameter and pair correlation function shows that the system exhibits a transition from an orientationally disordered to a partially ordered phase. The temperature dependence of the specific heat suggests that the transition is second order or higher.

The possibility of the existence of order-disorder transitions in two dimensions is discussed. The results of the simulation are then compared with the predictions of a molecular field theory of orientational phase transitions. As expected the theory is found to be in poor agreement with the calculations.     

Orientational Order and Linear Dichroism of a Water Soluble Porphine in a Lyotropic Nematic Liquid Crystal

Aqueous lyotropic nematic liquid crystals can be homogeneously oriented by magnetic fields and are therefore well suited to be used as anisotropic solvents for optical polarization studies of water soluble dye molecules. The potassium laurate (KL)/KCl/H₂O nematic phase, composed of rod-like or cylindrical micelles, was used as a matrix for the study of orientational order and linear dichroism of a substituted free-base porphine (TPPS₄). The results indicate that a significant portion of porphine molecules are incorporated into the micelles with their planes on the average perpendicular to the optic axis of the lyotropic rods. The order parameter of TPPS₄ is much higher in this system than in other nematic lyophases such as KL/decanol/H₂O in which preferential hydrogen bonding occurs between TPPS₄ molecules and the hydroxyl groups of decanol molecules which presumably occupy the surface of the cylindrical micelles. All observed electronic transitions in the 350-700 nm range are found to be polarized in the plane of the porphine ring.     

Structure of the Nematic Phase of Pbaba

X-ray diffraction investigations of the nematic phase (191°C - 276°C) of p-n-propyloxybenzylidene-p-amino benzoic acid have shown that this phase is a skewed cybotactic nematic phase. The diffraction patterns, obtained with aligned samples, reveal an additional surprising structural feature, - the presence of one dimensional molecular correlation in a direction parallel to the nematic director. At 192°C, it is found that the molecular unit, thus correlated, is about 37 Å in length (dimer length) and the correlation range extends up to about seven such units. This l-d correlation persists up to the N-I transition.     

The Structure of a Lyotropic Liquid Crystalline Phase that Orients in a Magnetic Field

Abstract

The structure of a lyotropic liquid crystalline phase with positive diamagnetic anisotropy (type I), that spontaneously orients in a magnetic field has been studied by means of water NMR quadrupole splittings, NMR diffusion and polarized absorption spectroscopy. It is concluded that this phase is built up of long rodlike aggregates. A preliminary study of a sample with negative diamagnetic anisotropy (type II) shows that this phase probably consists of lamellar aggregates. It is suggested that these phases are suitable as orientation matrices for studies of chromophores with polarized light spectroscopy.     

Microscopic Studies of 2H-NbSe2 Probed by Positive Muon

Abstract

The microscopic state of the positively charged light particle in the transition metal dichalcogenide 2H-NbSe₂ was studied using the muon spin relaxation method (μ⁺SR) and muon level crossing resonance method (μ-LCR). Muons are expected to stay at interlayer position and behaves as a hydrogen like intercalant. We discuss the relation between conduction electron properties and the muon's behavior.     

Monomeric and Dimeric Erbium(III) Complexes: Crystal Structure and Photoluminescence Studies

Abstract  

The crystal structure and photoluminescence (PL) studies of the monomeric and dimeric Er(III) complexes with two different chelating ligands (anthracene-9-carboxylic acid, 9-ACA; pentaethylene glycol, EO5; and picric acid, HPic) are reviewed. The Er(III) metal ion was coordinated to the attached ligands in eight- and nine-coordination number. The dimeric [Er₂(9-AC)₆(DMF)₂(H₂O)₂] complex shows the presence of deprotonated 9-AC anions with the negatively charged oxygen atoms bridged two Er(III) ions leads to a great coordinative flexibility via three possibilities of coordination modes, i.e. monodentate, chelation bidentate, chelating–bridging tridentate, where 9-AC = anthracene-9-carboxylate anion. The monomeric [Er(Pic)₂(EO5)](Pic) complex displays the important flexible structure of the acyclic EO5 ligand and the role of Pic anions act as bidentate and monodentate chelations. The PL spectra of both Er(III) complexes show a broad band with the center peak position being dependent on the attached aromatic ligands. The heavier lanthanide complexes show the difference in structures, coordination geometry environment, and luminescence properties compared to the lighter lanthanide complexes. The energy transfer process in the complexes could be optimized with maximize the overlap between the emission spectrum of donor atom and absorption spectrum of acceptor atom.     

The Electron Microscopic Approach to the Structure and Reactivities of Organic Solids

In this paper we continue investigations started in Refs. 1 and 2 studying the effect of a magnetic field on electrohydrodynamics of liquid crystalling complex ethers with dielectric constant anisotropy close to zero. The investigations were made with 100 μm thick layers having initial planar “first” structure of B and C mixtures described in Ref. 2.

Figure 1 shows dependences of optical layer transmittance on the intensity of the magnetic field (H) directed normal to bearing surfaces, and in the absence of an electric field in the absence of an electric field (curves I and II). For some threshold values H = H_th all the samples showed an increased transmission arising due to Fredericks transition.³     

Effect of Paa Molecular Structure on the Nematic Liquid Crystal Phase

The dipole moment and the valence electron density of p-azoxvanizole (PAA) molecule were calculated using the theoretical semiempirical method CNDO/2. On the basis of these results a model of the nematic liquid crystal phase ordering was proposed.     

Calorific Effect of the Magnetically Induced Phase Transition in Induced Chiral Nematic Systems

The study of the calorific effect of the magnetically-induced phase transition in doped nematic phases is described. The systems examined consisted of PCB as a nematic host phase and S-N-1-phenylethyl-4n-alkylbenzamides as non-mesogenic optically active dopants. The calorific effect was estimated indirectly from the temperature dependence of the magnetic-field-threshold of the helical unwinding and of the reverse process; i.e. the helical winding. It appears that it is the ratio of the length of an optically active dopant and that of the nematic host which determines the temperature dependencies of such parameters as the helical pitch, microscopic twisting power, and latent heat. A comparison with the magnetocaloric effect in nematic liquid crystals¹ is also made.     

Refractive Indices and Dielectric Studies of Three Phenylcyclohexane Liquid Crystals in the Nematic Phase

The refractive indices n_e, n_o and densities and the dielectric primittivities ε_∥ and ε_⊥ of three P-cyano-P-alkylcyclohexanes (PHC-3, PCH-5, PCH-7) have been measured at different temperatures. The order parameters calculated by using Neugebauer and Vuks' methods were comparable. A comparison of order parameters of the PCH with the corresponding alkylcyanobiphenyls at reduced temperatures τ (= T-T_NI/T_NI) shows that the replacement of a phenyl ring with a cyclohexyl ring decreases the order parameter appreciably. The experimental values of dielectric permittivities ε_⊥ in each of the PCHs are found to be less than half of the ε_⊥-value calculated from Maier and Meier equations using the polarizability and the order parameter obtained from refactive index measurements. This was explained as due to short range antiparallel ordering of strongly polar molecules in the nematic phase, as proposed by Chandrasekhar and Madhusudan, which was not taken into consideration in Maier and Meiers' theory     

Self-Assembly and Phase Behavior of Short Chain Phosphonic Acid-Water Systems in a Wide Concentration Range Microscopic,NMR, and X-ray Diffraction Studies

The phase behavior of n-octane and n-hexane phosphonic acid-D₂O systems was studied in the concentration range from 0.1 to 90 wt.% and in a temperature range from 10° to 130°C by polarizing and dark field microscopy and by ¹H, ²D and, ³¹P NMR. Further, electron microscopy, X-ray diffraction and surface tension measurements were performed. For the first time, a widely spaced lamellar phase was observed over large concentration and temperature ranges in an essentially two-component system. By using the sonication or injection methods, unilamellar liposomes were obtained below 1 wt.%. At high temperatures, the clouding phenomenon was observed. The importance of hydrogen bond formation between polar groups for building up stable lamellae even at high dilution is stressed. The results are discussed with respect to some existing points of view concerning the possibility of lamellar structure formation from single short chain amphiphilic compounds including lipids.     

The Crystal Structure and Conformational Studies of Acridinedione Derivatives

Abstract  

Two crystal structures of acridinediones namely, TMHAD and MPHAD were studied by X-ray crystallographic method in view of their occurrence in numerous commercial products including pharmaceuticals, fragrances and dyes. Crystal data of TMHAD are: C₁₇H₂₃NO₂, orthorhombic, Fdd2, with cell parameters a = 40.417(6) ?, b = 5.744(1) ?, c = 12.979(2) ?, V = 3013.1(7) ?³, Z = 8, D_cal = 1.205 Mg/m³, μ = 0.078 mm⁻¹. Crystal data of MPHAD are: C₂₀H₁₈NO₃; monoclinic, P2₁/c with cell parameters a = 10.182(9) ?, b = 17.105(14) ?, c = 10.895(9) ?, β = 117.857(1)°, V = 1678(2) ?³, Z = 4, D_cal = 1.268 Mg/m³, μ = 0.085 mm⁻¹. Both data were collected using λ (MoK_α) = 0.71073 ?. The central ring in the acridinedione moieties tends to be planar while the outer two rings adopt sofa conformations. Intermolecular interactions of C–H···O type of hydrogen bond help the molecules to stabilize into the crystal packing. Interestingly, a week forces of C–H···π interactions also helps the molecules for stabilization.     

Structural Studies of Two Isoelectronic Tetrakis Isocyano Complexes

Abstract  

Two isoelectronic tetrakis isocyano compounds, tetra(p-isocyanoanisole)nickel(0) and tetra(p-isocyanoanisole)copper(I) hexafluorophosphate were synthesized from nickel bis cyclooctadiene and copper (I) tetra acetonitrile hexafluorophosphate and the isonitrile, respectively, and their structures were determined. The nickel complex crystallizes in the orthorhombic space group P2₁2₁2₁ with a = 9.6709(8), b = 15.2324(13), c = 19.0955(16) ? and Z = 4. The copper salt forms crystals with a tetragonal setting in P4/n with a = b = 15.8206(5), c = 6.5848(4) ? and Z = 2. Both complexes exhibit the approximate tetrahedral coordination environment expected for 18 valence electron complexes with soft σ-donor π-acceptor ligands. Packing in the nickel complex is dominated by weak π–π stacking, C–H···π_phenyl, and C–H···π interactions towards the isonitrile carbon and nitrogen atoms, and several slightly stronger C–H···O interactions. In the copper complex the presence of the PF₆ anion allows for the formation of stronger C–H···F interactions, and these in combination with π–π stacking and C–H···O hydrogen bonds dominate the packing.     

The Heterogeneity of Chain Lengths,A Factor in Lyotropic Polymorphism

The paraffinic medium of the lamellar phase. of a potassium soap is perturbed by introducing a soap with a different chain length, while the water content of the phase is kept constant. Structural changes are observed which depend upon the concentration and the length of the solute soap.     

Structural Studies of 1:1 Quinone-Hydroquinone Complexes

The structures of the 1:1 quinone-hydroquinone complexes of 2-phenyl and of 2-(4′-chloro) phenylbenzoquinone have been studied by X-ray methods. A superficial study would indicate that the quinhydrones are centrosymmetric and belong to the space group P2₁/c. However, other evidence indicates that the true crystal structure may belong to either the space group P2₁ or to Pc, or that the crystal may contain regions that would coresspond to each of these two non-centrosymmetric space groups. Some possible consequences of such a structural arrangement are briefly discussed.     

Reactions Occurring in Gels of Lithium Tetraalkyl Borates Promoted by Supermolecular Structure of Complexes

As Li[BOR'(OR)₃] and Li[B(OR)₄] complexes, where R’ and R are alkyls of iso- and normal structure, are formed from boron alkoxides and lithium in solutions of low dielectric permittivity, they are involved in autocatalytic polyassociation to give viscoelastic systems (gels) possessing a mechanical memory [1].