2H nuclear magnetic resonance study on the molecular motion in cyanoadamantane. II. Orientationally ordered and glassy crystalline phase

The orientationally ordered crystalline and glassy plastically crystalline phase of cyanoadamantane were investigated using (2)H NMR. Solid-echo line shape, two-dimensional spectrum, and spin-lattice relaxation were analyzed. In both phases, the molecules display solely a rotation around the molecular C(3) symmetry axis. For the orientationally ordered phase, a single correlation time characterizes the motion, and the time constant shows an Arrhenius temperature dependence. In contrast, a broad distribution G[ln(tau)] of correlation times is observed for the glassy plastically crystalline phase that leads to characteristically different NMR features such as "two-phase" spectra and pronounced nonexponential relaxation. The distribution G[ln(tau)] can be derived from a temperature independent distribution of activation energies g(E(a)), with its mean value lying significantly below the activation energy corresponding to the ordered phase. Thus, the molecular uniaxial rotation proves to be a sensitive probe for the energy landscape of the orientationally disordered glassy crystalline phase of cyanoadamantane.     

Orientational melting and reorientational motion in a cubane molecular crystal: a molecular simulation study

Detailed molecular simulations are carried out to investigate the effect of temperature on orientational order in cubane molecular crystal. We report a transition from an orientationally ordered to an orientationally disordered plastic crystalline phase in the temperature range 425-450 K. This is similar to the experimentally reported transition at 395 K. The nature of this transition is first order and is associated with a 4.8% increase in unit cell volume that is comparable to the experimentally reported unit cell volume change of 5.4% (Phys. Rev. Lett. 1997, 78, 4938). An orientational order parameter, eta(T), has been defined in terms of average angle of libration of a molecular 3-fold axis and the orientational melting has been characterized by using eta(T). The orientational melting is associated with an anomaly in specific heat at constant pressure (C(P)) and compressibility (kappa). The enthalpy of transition and entropy of transition associated with this orientational melting are 20.8 J mol(-1) and 0.046 J mol(-1) K(-1), respectively. The structure of crystalline as well as plastic crystalline phases is characterized by using various radial distribution functions and orientational distribution functions. The coefficient of thermal expansion of the plastic crystalline phase is more than twice that of the crystalline phase.     

Plastic and glassy crystal states of caffeine

The present paper focuses on the high temperature form I of caffeine and on its low temperature metastable form. Structural, dynamic, and kinetic information has been obtained by X-ray, dielectric, and calorimetric investigations. This study shows the following features: (1) The high temperature phase (I) of caffeine is in a state of dynamically orientationally disordered crystalline state (so-called "plastic, or rotator, phase"). (2) This high-symmetry hexagonal phase can be maintained at low temperature in a metastable situation. (3) Under deep undercooling of form I a glass transition occurs in the disordered crystalline state near room temperature. It is associated with the orientational freezing in of the molecular motions. Otherwise stated, the metastable state I enters into a nonergodic unstable state, so-called "glassy crystal" state. These findings rationalize the difficulties seen with caffeine in pharmaceutical science.     

What does pressure decide to cook with orientationally disordered plastic phase of cubane: an orientational glass or crystal?

The effect of pressure on the structure and reorientational motion of molecules in orientationally disordered (OD) crystalline phase of cubane has been investigated in detail using variable shape molecular simulations in constant-pressure constant-temperature ensemble. Complete orientational ordering occurs at a pressure of 1.0 GPa and the OD phase transforms to an orientationally ordered phase at this pressure. The transition is associated with a kink in the variation of structural parameters such as cell parameters, unit-cell volume, and interaction energy. This transition is also associated with an anomaly in specific heat. Above this transition pressure, the structural quantities display only smaller changes with further increase in pressure. The structure of high-pressure orientationally ordered (HPOO) phase has been characterized using radial distribution functions and orientational distribution function. From detailed analysis of the structure of HPOO phase we conclude that it is isostructural with low-temperature orientationally ordered phase. The OD phase has four times larger compressibility than the HPOO phase.     

Plastic and glassy crystalline states of methane: A Monte Carlo simulation study

A Monte Carlo simulation study has been carried out on the glassy crystalline phases of methane obtained by annealing or quenching the plastic (orientationally disordered) phase. Different cooling rates lead to different states of the glass. Temperature variation of the reorientational parameter suggests the presence of a transition between the plastic and glassy crystalline phases.     

Studies on structures of lipid A-monophosphate clusters

Single crystalline clusters of lipid A-monophosphate were grown from organic dispersions containing 5-15% (v/v) water at various volume fractions, φ, and temperatures. The morphology of the single lipid A-monophosphate crystals was either rhombohedral or hexagonal. The hexagonal crystals were needlelike or cylindrical in shape, with the long dimension parallel to the c axis of the unit cell. The crystalline clusters were studied using electron microscopy and x-ray powder diffraction. Employing molecular location methods following a Rietveld refinement and whole-pattern refinement revealed two monoclinic crystal structures in the space groups P2(1) and C2, both converged with R(F) = 0.179. The two monoclinic crystal structures were packing (hydrocarbon chains) and conformational (sugar) polymorphs. Neither of these two structures had been encountered previously. Only intramolecular hydrogen bonding was observed for the polymorphs, which were located between the amide and the carboxyl groups. Another crystalline structure was found in the volume-fraction range 2.00 × 10(-3) ≤ φ ≤ 2.50 × 10(-3), which displayed hexagonal symmetry. The hexagonal symmetry of the self-assembled lipid A-monophosphate crystalline phase might be reconciled with the monoclinic symmetry found at low-volume-fractions. Therefore, lowering the symmetry from cubic, i.e., Ia 3d, to rhombohedral R 3 m, and finally to the monoclinic space group C2 was acceptable if the lipid A-monophosphate anion was completely orientationally ordered.     

高压下C60晶体玻璃化行为的理论研究

通过构造C_(60)分子间的相互作用，研究了在不同压力下C_(60)晶体中的取向有序结构．利用计算出来的两个取向之间的能量差和相隔势驿，研究了热平衡时取向占有几率和玻璃化转变温度的压力相关性．结果与实验符合．     

New mesomorphic organocyclosiloxanes II. Thermal behaviour and mesophase structure of organocyclohexasiloxanes

Investigations of thermotropic phase transitions performed on organocyclosiloxanes [PhSi(O)OSiR]₆, where R is Me₃, Me₂(CH₂Cl) or Me₂(CH≃CH₂), have revealed that all these hexamers are mesomorphic compounds. The hexamers exhibit uncommon polymesomorphic behaviour forming two quite different mesomorphic structures. The molecular arrangement in the low temperature (LT) modification is characterized by two-dimensional (2D) long-range order with hexagonal packing. The X-ray diffraction pattern and peculiarities of molecular packing in the crystal lead us to suggest that the LT-mesophase is columnar, presumably of the Col_hd type. The LT-mesophase is formed by dimeric moieties, which associate with each other in column-like substructures, the ring planes not orthogonal to the stack axis. The high temperature (HT) mesophase is a plastic crystal (3D-order), where molecules take up positions in a face-centred cubic lattice. This is a very uncommon example of thermal behaviour for plastic crystals that provides a unique opportunity to bridge the gap between plastic crystalline and liquid crystalline mesomorphic behaviour. The thermal and structural properties of the mesophases depend upon the type of side groups of the hexamers. The size of the ring also affects the phase behaviour and the mesomorphic structure. This conclusion is consistent with data obtained by us earlier for cyclotetrasiloxanes.     

EPR studies on molecular orientation in a surface-stabilized paramagnetic liquid crystal cell

By EPR spectroscopy, we have developed a new method for determining the molecular orientation in a surface-stabilized liquid crystal (LC) cell, which includes a paramagnetic LC, (2S,5S)-2,5-dimethyl-2-heptyloxyphenyl-5-[4-(4-octyloxybenzenecarbonyloxy)phenyl]pyrrolidine-1-oxy (1), whose spin source is fixed in the rigid core. For each phase of racemic [(+/-)] and enantiomerically enriched [(S,S)] 1 in a surface-stabilized LC cell (4 microm thickness), the observed g-value profiles depending on the angle between the applied magnetic field and the cell plane were successfully simulated by the orientation models: (i) the LC molecule in the nematic (N) phase of (+/-)-1 freely rotates around the long axis, which is always parallel to the rubbing direction; (ii) the long axis of the freely rotating LC molecule in the chiral nematic (N*) phase of (S,S)-1 is always parallel to the cell plane but rotates in the plane to form a helical superstructure; and (iii) in the crystalline phase of (S,S)-1, the molecular long axis forms a helical superstructure similar to that of the N* phase, but the molecule is fixed around the long axis so that the NO bond lies in the cell plane. Fitting the temperature profile of the g-value in the N phase of (+/-)-1 by use of the Haller equation, we determined the molecular g-values along the molecular long axis (g(parallelM)) and short axis (g(perpendicularM)), which were successfully reproduced by the use of the set of principal g-values of a similar nitroxide with consideration of the structure of the LC molecule optimized by Molecular Mechanics 3 (MM3).     

Molecular dynamics simulation on devitrification: isothermal devitrification and thermodynamics of PbF2 glasses

The vitrification and devitrification features of lead fluoride are investigated by means of molecular dynamic simulations. The influence of heating rate on the devitrification temperature as well as the dependence of the glass properties on its thermal history, i.e., the cooling rate employed, is identified. As expected, different glasses are obtained when the cooling rates differ. Diffusion coefficient analysis during heating of glass and crystal, indicates that the presence of defects on the glassy matrix favors the transition processes from the ionic to a superionic state, with high mobility of fluorine atoms, responsible for the high anionic conduction of lead fluoride. Nonisothermal and isothermal devitrification processes are simulated in glasses obtained at different cooling rates and structural organizations occurring during the heat treatments are clearly observed. When a fast cooling rate is employed during the glass formation, the devitrification of a single crystal (limited by the cell dimensions) is observed, while the glass obtained with slower cooling rate, allowing relaxations and organization of various regions on the glass bulk during the cooling process, devitrifies in more than one crystalline plane.     

Radiation-induced polymerization of cyclohexene sulfide in the solid state

Radiation-induced solid-state polymerization of cyclohexene sulfide has been investigated. Differential thermal analysis shows that this compound has a phase transition point at ?74°C and behaves as a plastic crystal in the temperature range from ?74 to ?20°C (melting point). By rapid cooling, this plastic crystal was easily supercooled, and below ?166°C a glassy crystal, i.e., a supercooled nonequilibrium state of plastic crystal, was obtained. In-source polymerization proceeded in the plastic crystalline state. Postpolymerization of glassy crystalline monomer irradiated at ?196°C occurred above ?166°C (glass transition point) during subsequent heating.     

Glass Formation of a Coordination Polymer Crystal for Enhanced Proton Conductivity and Material Flexibility

The glassy state of a two‐dimensional (2D) Cd²⁺ coordination polymer crystal was prepared by a solvent‐free mechanical milling process. The glassy state retains the 2D structure of the crystalline material, albeit with significant distortion, as characterized by synchrotron X‐ray analyses and solid‐state multinuclear NMR spectroscopy. It transforms to its original crystal structure upon heating. Thus, reversible crystal‐to‐glass transformation is possible using our new processes. The glass state displays superior properties compared to the crystalline state; specifically, it shows anhydrous proton conductivity and a dielectric constant two orders of magnitude greater than the crystalline material. It also shows material flexibility and transparency.     

Dielectric behaviour of H-bonded liquids and amorphous and crystalline solids

Three aspects of dielectric behaviour and H-bonding in amorphous and crystalline materials are reviewed: (i) where intermolecular H-bond formation on cooling decreases the orientation polarization and renders a substance apparently non-polar and compression tends to restore the original polarization; (ii) where supercooled water imbibed in a synthetic linear and network polymer matrix shows relaxation characteristics of free and bound states of water molecules and a persistence of molecular motions in the glassy state; and (iii) where water molecules included as guests in a macrocyclic conformation of a molecule stabilize its crystal structure, remain orientationally and positionally disordered within the constraint of tetrahedral bonding, and gradually undergo proton-ordering with decrease in temperature. Examples of the first are long-chain isomeric alcohols, of the second hydrophilic polymers and hydrogels, and of the third cyclodextrins.     

Direct crystallization of silicate–phosphate glasses of NaCaPO4–SiO2 system

The subject of the study was silicate–phosphate glasses of NaCaPO₄–SiO₂ system which are precursors of glass–crystalline materials. Glass–crystalline materials of NaCaPO₄–SiO₂ system obtained via crystallization of glasses belong to a group of the so-called bioactive materials. In order to obtain glass–crystalline materials with pre-established parameters, it is necessary to conduct crystallization of glasses at specific conditions. In order to design direct crystallization process properly, it is necessary to know the structure and microstructure of the glassy precursor. Microscopic investigation showed that liquation takes place in all the studied glasses. Based on DSC examinations, it has been found out that crystallization of the glasses of NaCaPO₄–SiO₂ system is a multistep process. The presence of several clearly separated exothermic peaks in DSC curves of investigated glasses makes it possible to crystallize only the separated phase with the matrix remaining amorphous or vice versa. Conducted detailed X-ray and spectroscopic studies of the materials obtained by heating in a gradient furnace (in the temperature specified on the basis of DSC) showed that separated phase and matrix crystallizes separately. Therefore, bioactive glass–crystalline materials can be obtained due to the existence of the phase separation phenomenon and pre-established sizes of the crystalline phase.     

Anisotropic pseudorotation of the photoexcited triplet state of fullerene C60 in molecular glasses studied by pulse EPR

Spin-polarized echo-detected electron paramagnetic resonance (EPR) spectra and the transversal relaxation rate T2(-1) of the photoexcited triplet state of fullerene C60 molecules were studied in o-terphenyl, 1-methylnaphthalene, and decalin glassy matrices. The model is composed of a fast (correlation time approximately 10(-12) s) pseudorotation of (3)C60 in a local anisotropic potential created by interaction of the fullerene molecule with the surrounding matrix molecules. In simulations, this potential is assumed to be axially symmetric around some axis of a preferable orientation in a matrix cage. The fitted value of the potential was found to depend on the type of glass and to decrease monotonically with a temperature increase. A sharp increase of the T2(-1) temperature dependence was found near 240 K in glassy o-terphenyl and near 100 K in glassy 1-methylnaphthalene and decalin. This increase probably is related to the influence on the pseudorotation of the onset of large-amplitude vibrational molecular motions (dynamical transition in glass) that are known for glasses from neutron scattering and molecular dynamics studies. The obtained results suggest that molecular and spin dynamics of the triplet fullerene are extremely sensitive to molecular motions in glassy materials.     

Columnar phases of achiral vanadyl liquid crystalline complexes

Two liquid crystalline vanadyl complexes have been studied by frequency domain dielectric spectroscopy over the range 10 mHz to 13 MHz. The materials exhibit two or three columnar phases denoted Col_ro, Col_rd, and Col_hd that were identified by X-ray diffraction. In the higher temperature Col_rd phase, a relaxation process in the kHz range is observed that is attributed to the reorientation about the molecular short axis. A pronounced dielectric relaxation process shows up in the low temperature Col_ro phase at hertz and sub-hertz frequencies. This slow relaxation is assigned to reorientation of the molecular dipoles within the polar linear chains, which are aligned along the column's axis. Triangular wave switching studies at low frequency reveal processes inside the Col_ro phase which are most probably due to ionic/charges relaxations but a ferroelectric switching for an achiral discotic system cannot be ruled out completely. Below the Col_ro phase there is an orientationally disordered crystalline Cr_x phase with disordered side chain dipoles. A dielectric relaxation process connected with the intramolecular relaxation of the alkoxy side chains, similar to the beta-process of polymers, has been found in the lower temperature Cr_x phase.     

Two-dimensional chiral model for liquid crystals, bent hard needles: a Monte Carlo simulation

The liquid crystalline behavior of a two dimensional (2D) model of hard needles bent into a "zigzag shape" is studied. This model, originally designed to study two dimensional chiral segregation, also shows liquid crystalline behavior and has some anomalous features which are contrasted in relation to the following: (i) Most of the microscopical models used to study liquid crystals have a symmetry axis that coincides with a molecular axis; (ii) in three-dimensions, chiral molecules can form cholesteric instead of nematic phases; (iii) the smectic phase is usually found when attractions are present or at least when the molecules have finite volume. Despite the fact that the present 2D model does not have any of these characteristics, numerical evidence is found for the occurrence of nematic and smectic phases. Since these molecules are athermal, infinitely repulsive, and infinitesimally thin, the liquid crystalline characteristics are attributed to excluded volume effects. To determine the mesophases of the model, both nematic and smectic order parameters as well as distribution functions are computed.     

Thermodynamics of soft anisotropic contact lines

Contact lines arising from the intersection of interfaces between liquids and nematic liquid crystals are representative models of soft anisotropic contact lines. This paper presents the thermodynamics of soft anisotropic contact lines and the derivation of the one dimensional (1D) Gibbs-Duhem adsorption equation. Consistency between the 1D Gibbs-Duhem equation and the classical equations of lineal nematostatics is shown. Using a phase space that takes into account thermodynamics, liquid crystalline order, and geometric variables, the generalized nematic line Gibbs-Duhem equation reveals the presence of couplings between curvature, torsion, adsorption, temperature, and average molecular orientation. Merging the thermodynamic analysis with nematostatics results in a model for contact line shape and orientation selection. The ability of an adsorbed solute to orient the director and to bend and twist the contact line is predicted. The thermodynamic origin of preferred orientation at a straight contact line is established.     

Anisotropic Change in the Magnetic Susceptibility of a Dynamic Single Crystal of a Cobalt(II) Complex

Atypically anisotropic and large changes in magnetic susceptibility, along with a change in crystalline shape, were observed in a Co^II complex at near room temperature. This was achieved by combining oxalate molecules, acting as rotor, and a Co^II ion with unquenched orbital angular momentum. A thermally controlled 90° rotation of the oxalate counter anion triggered a symmetry‐breaking ferroelastic phase transition, accompanied by contraction–expansion behavior (ca. 4.5 %) along the long axis of a rod‐like single crystal. The molecular rotation induced a minute variation in the coordination geometry around the Co^II ion, resulting in an abrupt decrease and a remarkable increase in magnetic susceptibility along the direction perpendicular and parallel to the long axis of the crystal, respectively. Theoretical calculations suggested that such an unusual anisotropic change in magnetic susceptibility was due to a substantial reorientation of magnetic anisotropy induced by slight disruption in the ideal D ₃ coordination environment of the complex cation.     

Ordering of some liquid crystals containing the 2-phenylindazole core

Molecules containing the 2-phenylindazole core present liquid crystalline properties even if the two terminal chains do not point along the same axis. ¹³CNMR in the liquid crystalline phase shows that the molecular long axis is nearly aligned with the para-axis of the phenyl moiety of the 2-phenylindazole core. This implies that the first fragments of the chain belonging to the indazole moiety do not lie along the molecular long axis. To promote liquid crystal properties, this chain needs to possess at least six carbon atoms.