Experimental assessment of quasi-binary picture of thermotropics: induced smectic A phase in 7CB-n-heptane system.

Quasi-binary (QB) picture of thermotropics, which regards a neat thermotropic liquid crystal as a binary system consisting of (semi)rigid core and molten alkyl chain, was assessed experimentally for the most famous (and representative) thermotropic mesogenic series nCB. By adding n-heptane as solvent, the smectic A phase was induced in 7CB-n-heptane system. Small angle x-ray diffraction showed that the QB picture holds not only in the phase behavior but also in the structure. It is suggested that the melting of 8CB and 9CB to isotropic liquid via smectic and nematic liquid crystals can be understood as a thermotropic-lyotropic crossover.

Negative thermal expansion emerging upon structural phase transition in ZrV2O7 and HfV2O7.

ZrV(2)O(7) and HfV(2)O(7), which show negative thermal expansion (NTE) in the high-temperature phase, were investigated using X-ray diffraction and heat capacity calorimetry. Two sharp anomalies due to successive phase transitions were observed in the temperature dependence of heat capacity at 345.5 K and 373.4 K for ZrV(2)O(7) and 341.8 K and 370.3 K for HfV(2)O(7). The smallness of their combined entropies of transition suggested that the phase transitions are of displacive type. Effective phonon densities of states (DOS) described by a simple model, and mode-Grüneisen parameters of the low-temperature phase were obtained through the spectrum analyses of heat capacities of ZrV(2)O(7) and HfV(2)O(7). Their effective phonon DOS's show the three features common to NTE compounds: low-energy phonon mode, high-energy phonon mode, and a wide phonon gap in between. The mode-Grüneisen parameter of low-energy modes corresponding to translational and librational vibrations of the constituent polyhedra is negative but with a small absolute value due to the distortion of V(2)O(7) group in the low-temperature phase, resulting in positive thermal expansion. It is revealed that the release of the structural distortion upon the successive phase transitions with large volume increase leads to the NTE of ZrV(2)O(7) and HfV(2)O(7) in the high-temperature phase.

Neat liquid consisting of hydrogen-bonded tetramers: dicyclohexylmethanol.

Nonmonotonous temperature dependence was detected in the heat capacity and dielectric constant of the title compound in the liquid state. A coherent analysis of FT-IR spectra, heat capacity, and dielectric constants shows that the neat liquid at low temperatures consists of closed (square) tetramers via H-bonds.

Calorimetric and dielectric study of organic ferroelectrics, phenazine-chloranilic acid, and its bromo analog.

The heat capacities of single crystals of organic ferroelectric complexes phenazine-chloranilic acid (Phz-H(2)ca) and phenazine-bromanilic acid (Phz-H(2)ba) were measured. At temperatures below those of the reported ferroelectric phase transitions, heat capacity anomalies due to successive phase transitions were found in both complexes. Excess entropies involved in the low-temperature successive phase transitions are much larger than those due to the ferroelectric phase transitions. The temperature dependence of the complex dielectric constants showed the existence of multiple dielectric relaxation modes in both complexes and their deuterated analogs (Phz-D(2)ca and Phz-D(2)ba). We discuss the possibility of concerted hopping of neighboring protons within a hydrogen-bonded chain while taking into account the one-dimensional nature of the chain.

Recent progress in high-pressure studies on organic conductors.

Recent high-pressure studies of organic conductors and superconductors are reviewed. The discovery of the highest Tc superconductivity among organics under high pressure has triggered the further progress of the high-pressure research. Owing to this finding, various organic conductors with the strong electron correlation were investigated under high pressures. This review includes the pressure techniques using the cubic anvil apparatus, as well as high-pressure studies of the organic conductors up to 10 GPa showing extraordinary temperature and pressure dependent transport phenomena.

Coexistence of two aggregation modes in exotic liquid-crystalline superstructure: systematic maximum entropy analysis for cubic mesogen, 1,2-bis(4'-n-alkoxybenzoyl)hydrazine [BABH(n)].

Structure of a complex superstructure self-organized by thermotropic mesogen, 1,2-bis(4'- n-alkoxybenzoyl)hydrazine [BABH(n), where n is the number of carbon atoms in an alkoxy chain] was studied while paying special attention to the structure at the molecular level. Maximum entropy (MEM) analysis revealed that the molecular cores form two kinds of aggregates: Jungle gym with 3-fold junctions roughly on P minimal surface and spherical shells.

Calorimetric study of correlated disordering in [Hdamel]2[Cu(II)(tdpd)2] x 2 THF crystal.

The heat capacity of [Hdamel]2[Cu(II)(tdpd)2] x 2 THF was measured from 6 to 250 K by adiabatic calorimetry. There are four heat anomalies around 150 K associated with disordering in the orientation of the uncoordinated THF molecules and in the conformation of the out-of-plane allyl groups of [Hdamel](+) units. The total entropy of transition was determined to be 19.8 J K(-1) mol(-1), less than the 4R ln 2 (R = gas constant) expected from the crystal structure at room temperature. The smallness of the total entropy change on phase transitions proves the presence of the strong motional correlation between the adjacent allyl groups. The calorimetric conclusion agreed with the crystal structure at 200 K re-examined in this study.

A metallic (EDT-DSDTFVSDS)2.FeBr4 salt: antiferromagnetic ordering of d spins of FeBr4- ions and anomalous magnetoresistance due to preferential pi-d interaction.

The 2:1 salt of a new donor molecule, EDT-DSDTFVSDS with FeBr4- ion, (EDT-DSDTFVSDS)2.FeBr4 showed an essentially metallic behavior despite a small upturn in the electrical resistance below ca. 30 K (electrical conductivities at 290 and 4.2 K are 200 and 170 S cm-1, respectively). The Fe(III) d spins of the FeBr4- ions in this salt were subject to antiferromagnetic ordering at 3.3 K by virtue of a strong pi-d interaction (Jpid) which is comparable to that in a molecular metallic conductor, lambda-(BETS)2.FeCl4, and of a very weak d-d interaction (Jdd). This strong pi-d interaction was evidenced by a large and negative magnetoresistance effect (ca. 20% at 5 T) as well as by the appearance of a large dip in the resistance at the magnetic field (ca. 2.0 T) parallel to the easy axis for the spin-flop transition of the Fe(III) d spins.

Magnetoresistance effects evidencing the pi-d interaction in metallic organic conductors, (EDT-DSDTFVO)2*MX4 (M = Fe, Ga; X = Cl, Br).

The 2:1 salts of a new donor molecule, EDT-DSDTFVO with MX4- (M = Fe, Ga; X = Cl, Br) ions, were prepared. The crystal structures of the donor molecules had a beta-type packing motif. All the salts essentially exhibited metallic behaviors despite the small upturns in the resistances below 30-70 K. A large negative magnetoresistance (MR) effect [-14.7% (rho(perpendicular)) at 4.0 K and 5 T] was observed in the FeCl4- salt, while a positive MR effect [+4.0% (rho(perpendicular)) at 4.0 K and 5 T] was observed in the GaCl4- salt, suggesting that there is a pi-d interaction in the FeCl4- salt. The pressure application suppressed the resistivity upturns, increased the negative MR effect (-17.7% at 9.5 kbar) in the FeCl4- salt, and decreased the positive MR effect (+3.3% at 15 kbar) in the GaCl4- salt.

Stable metallic behavior and antiferromagnetic ordering of Fe(III) d spins in (EDO-TTFVO)2.FeCl4.

We report the crystal structure and physical properties of the 2:1 FeCl4- salt of a new donor molecule, EDO-TTFVO. Crystal structure analysis of this salt revealed that the donor molecules formed a beta' '-type two-dimensional conducting layer, and there is a short S...Cl contact between the donor molecules and the FeCl4- ions, which is expected to mediate a strong pi-d interaction. This salt showed a stable metallic conducting behavior down to 0.3 K and an antiferromagnetic ordering at TN approximately 3.0 K, indicating that this salt becomes a new antiferromagnetic molecular metal at ambient pressure. The appearance of the magnetic ordering is considered to originate from the strong pi-d interactions between the donor molecules and the FeCl4- ions because the field dependence of magnetoresistances was remarkably affected below the antiferromagnetic transition temperature.

Observation of three-dimensional fermi surfaces in a single-component molecular metal, [Ni(tmdt)2].

Rigorous evidence of metallicity of a molecular crystal consisting of single-component neutral molecules is disclosed by observing the Fermi surface through magnetic quantum oscillations. Torque magnetometry measurements of de Haas-van Alphen oscillatory signals in a single crystal of [Ni(tmdt)2] molecules (tmdt = trimethylenetetrathiafulvalenedithiolate) were performed by using a sensitive microcantilever at low temperatures in high magnetic fields to 45 T. The observed signals for all directions of magnetic field revealed unambiguously the presence of three-dimensional Fermi surfaces for both holes and electrons. The results are consistent with electronic band structure calculations for [Ni(tmdt)2].