Local lattice dynamics and the origin of the relaxor ferroelectric behavior

Relaxor ferroelectricity is observed in many strongly disordered ferroelectric solids. However, the atomistic mechanism of the phenomenon, particularly at high temperatures, is not well understood. In this Letter we show the local lattice dynamics as the origin of relaxor ferroelectricity through the first use of the dynamic pair-density function determined by pulsed neutron inelastic scattering. For a prototypical relaxor ferroelectric, Pb(Mg(1/3)Nb(2/3))O(3), we demonstrate that the dynamic local polarization sets in around the so-called Burns temperature through the interaction of off-centered Pb ions with soft phonons, and the slowing down of local polarization with decreasing temperature produces the polar nanoregions and the relaxor behavior below room temperature.     

Trifluoromethylation of Alkenes with Concomitant Introduction of Additional Functional Groups

The trifluoromethyl group is found in many synthetic bioactive compounds, and the difunctionalization of a C?C bond, as a powerful strategy for the construction of compounds with various functional groups, has been intensively investigated. Therefore, the difunctionalizing trifluoromethylation of alkenes has attracted growing interest because of the potential of the products as building blocks for bioactive molecules. In this review, we focus on recent advances in the trifluoromethylation of alkenes with concomitant introduction of additional functional groups.     

The magnetic phase transition in amorphous ferromagnets and in spin glasses

The magnetic phase transition in materials with exchange disorder (amorphous ferromagnets, spin glasses) is discussed. In the critical temperature range the behavior of amorphous ferromagnetic transition metal-metalloid glasses is found to be similar to the one derived for a three-dimensional homogeneous Heisenberg ferromagnet. The most prominent difference between disordered and homogeneous materials is manifested in a large temperature range of deviations from the mean field behavior beyond the critical region, as observed experimentally for the temperature dependence of the linear susceptibility of amorphous ferromagnets and of the nonlinear susceptibility of spin glasses. A molecular field theory with correlations in space and time is developed, which relates the deviations from the mean field behavior to the interplay between the temperature dependent thermal correlations in the spin system and the spatial fluctuations of the material. Application to dynamical processes (kinetic critical slowing down) is discussed.     

Ruthenium(salen)-catalyzed aerobic oxidative desymmetrization of meso-diols and its kinetics

Chiral (nitrosyl)ruthenium(salen) complexes were found to be efficient catalysts for aerobic oxidative desymmetrization of meso-diols under photoirradiation to give optically active lactols. The scope of the applicability of this reaction ranges widely from acyclic diols to mono-cyclic diols, although fine ligand-tuning of the ruthenium(salen) complexes was required to attain high enantioselectivity (up to 93% ee). In particular, the nature of the apical ligand was found to affect not only enantioselectivity but also kinetics of the desymmetrization reaction. Spectroscopic analysis of the oxidation disclosed that irradiation of visible light is indispensable not only for dissociation of the nitrosyl ligand but also for single electron transfer from the alcohol-bound ruthenium ion to dioxygen.     

Self-adaptive spatial filtering by use of azo chromophores doped in low glass-transition-temperature polymers

We report on self-adaptive spatial filtering by combination of the self-adaptive polarization-rotation property of Disperse Red1-doped polymers with low glass-transition-temperature and Fourier-transform operation. Our system can be operated with only an action beam with object information and without a probe beam for image readout. Edge enhancement by the action beam-probe beam is demonstrated as an example of the system's application to spatial filtering.     

Investigation into the evolution of the structure of K1−x LixTa1−y NbyO3 single crystals under variations in temperature

The evolution of the structure of K_1?x Li_xTa_1?y Nb_yO₃ single crystals with x = 0.001, y = 0.026, and 1900 ppm Cu (KLTN277) and with x = 0.0014 and y = 0.024 (KLTN123), which exhibit an extremely high permittivity (up to 4 × 10⁵ in the quasi-static regime for the KLTN277 crystal), is investigated in the range from room temperature to 20 K. It is demonstrated that, upon cooling to the lowest temperatures, both crystals retain their cubic structure, but the lattice parameters pass through a minimum at the temperature of the observed anomalies of the dielectric response (～50 K). In the neutron diffraction pattern of the KLTN123 sample, satellites appear in the vicinity of the (hhh) reflections at temperatures below ～50 K. These satellites can be associated with the nucleation of the rhombohedral phase.     

Asymmetric Dearomative Fluorination of 2-Naphthols with a Dicarboxylate Phase-Transfer Catalyst

A linked dicarboxylate phase-transfer catalyst enables smooth asymmetric dearomative fluorination of 2-naphthols with Selectfluor under mild conditions to give the corresponding 1-fluoronaphthalenone derivatives in a highly enantioselective manner. This reaction, which is compatible with a range of functional groups, is the first example of catalytic asymmetric fluorination of 2-naphthols, and is expected to be useful in the synthesis of bioactive molecules.