Project description:Chiral molecules with low enantiomer interconversion barriers racemize even at cryogenic temperatures due to quantum tunneling, forming a racemic mixture that is impossible to separate using conventional chemical methods. Here we both experimentally and theoretically demonstrate a method to create and probe a state-specific enantiomeric enrichment for such molecular systems. The coherent, non-linear, and resonant approach is based on a microwave six-wave mixing scheme and consists of five phase-controlled microwave pulses. The first three pulses induce a chiral wavepacket in a chosen rotational state, while the consecutive two pulses induce a polarization for a particular rotational transition (listen transition) with a magnitude proportional to the enantiomeric excess created. The experiments are performed with the transiently chiral molecule benzyl alcohol, where a chiral molecular response was successfully obtained. This signal demonstrates that enantiomeric excess can be induced in a quantum racemic mixture of a transiently chiral molecule using the developed microwave six-wave mixing scheme, which is an important step towards controlling non-rigid chiral molecular systems.
Project description:Ferroelectricity and antiferroelectricity are widely seen in various types of condensed matter and are of technological significance not only due to their electrical switchability but also due to intriguing cross-coupling effects such as electro-mechanical and electro-caloric effects. The control of the two types of dipolar order has practically been made by changing the ionic radius of a constituent atom or externally applying strain for inorganic crystals and by changing the shape of a molecule for organic crystals. However, the basic physical principle behind such controllability involving crystal-lattice organization is still unknown. On the basis of a physical picture that a competition of dipolar order with another type of order is essential to understand this phenomenon, here we develop a simple model system composed of spheroid-like particles with a permanent dipole, which may capture an essence of this important structural transition in organic systems. In this model, we reveal that energetic frustration between the two types of anisotropic interactions, dipolar and steric interactions, is a key to control not only the phase transition but also the coupling between polarization and strain. Our finding provides a fundamental physical principle for self-organization to a crystal with desired dipolar order and realization of large electro-mechanical effects.
Project description:Flexible organic materials possessing useful electrical properties, such as ferroelectricity, are of crucial importance in the engineering of electronic devices. Up until now, however, only ferroelectric polymers have intrinsically met this flexibility requirement, leaving small-molecule organic ferroelectrics with room for improvement. Since both flexibility and ferroelectricity are rare properties on their own, combining them in one crystalline organic material is challenging. Herein, we report that trisubstituted haloimidazoles not only display ferroelectricity and piezoelectricity-the properties that originate from their non-centrosymmetric crystal lattice-but also lend their crystalline mechanical properties to fine-tuning in a controllable manner by disrupting the weak halogen bonds between the molecules. This element of control makes it possible to deliver another unique and highly desirable property, namely crystal flexibility. Moreover, the electrical properties are maintained in the flexible crystals.
Project description:Using quantum mechanics (QM, Density Functional Theory) we show that all four phases of barium titanate (BaTiO(3)) have local Ti distortions toward 111 (an octahedral face). The stable rhombohedral phase has all distortions in phase (ferroelectric, FE), whereas higher temperature phases have antiferroelectric coupling (AFE) in one, two, or three dimensions (orthorhombic, tetragonal, cubic). This FE-AFE model from QM explains such puzzling aspects of these systems as the allowed Raman excitation observed for the cubic phase, the distortions toward 111 observed in the cubic phase using x-ray fine structure, the small transition entropies, the heavily damped soft phonon modes, and the strong diffuse x-ray scattering in all but the rhombohedral phase. In addition, we expect to see additional weak Bragg peaks at the face centers of the reciprocal lattice for the cubic phase. Similar FE-AFE descriptions are expected to occur for other FE materials. Accounting for this FE-AFE nature of these phases is expected to be important in accurately simulating the domain wall structures, energetics, and dynamics, which in turn may lead to the design of improved materials.
Project description:AFE crystals could also crystallize in polar point groups. If the dipole moment is reversible along the anti-polar axis under an external electric field, the polar crystal is an AFE crystal. Symmetry is an essential concept in physics, chemistry and materials science. Comprehensive, authoritative and accessible symmetry theory can provide a strong impetus for the development of related materials science. Through the sustained efforts of physicists and crystallographers, researchers have mastered the relationship between structural symmetry and ferroelectricity, which demands crystallization in the 10 polar point groups. However, the symmetry requirement for antiferroelectricity is still ambiguous, and polar crystals possessing antiferroelectricity seem contradictory. This work systematically and comprehensively studies the transformation of dipole moments under symmetry operations, using accessible geometric methods and group theory. The results indicate crystals that crystallize in polar point groups 2 (C2), m (C1h), mm2 (C2v), 4 (C4), 4mm (C4v), 3m (C3v), 6 (C6) and 6mm (C6v) also possess anti-polar structure and are capable of Kittel-type antiferroelectricity. The anti-polar direction of each point group is also highlighted, which could provide a straightforward guide for antiferroelectric property measurement. Like ferroelectric crystals, antiferroelectric crystals belonging to polar point groups have great potential to become a family of important multifunctional electroactive and optical materials. This contribution refines antiferroelectric theory, will help facilitate and stimulate the discovery and rational design of novel antiferroelectric crystals, and enrich the potential functional applications of antiferroelectric materials.
Project description:Racemic-metal complexes were used to determine identity, enantiomeric excess, and concentration of chiral diamines using metal-to-ligand charge transfer bands in circular dichroism spectroscopy. It takes under just 2 min per sample to determine [G]t and %R with tolerable errors (19% and 4%, respectively). The simplicity of the achiral receptors employed confers to this technique great potential for high-throughput screening.
Project description:Plasmonic lattice nanostructures are of technological interest because of their capacity to manipulate light below the diffraction limit. Here, we present a detailed study of dark and bright modes in the visible and near-infrared energy regime of an inverted plasmonic honeycomb lattice by a combination of Au+ focused ion beam lithography with nanometric resolution, optical and electron spectroscopy, and finite-difference time-domain simulations. The lattice consists of slits carved in a gold thin film, exhibiting hotspots and a set of bright and dark modes. We proposed that some of the dark modes detected by electron energy-loss spectroscopy are caused by antiferroelectric arrangements of the slit polarizations with two times the size of the hexagonal unit cell. The plasmonic resonances take place within the 0.5-2 eV energy range, indicating that they could be suitable for a synergistic coupling with excitons in two-dimensional transition metal dichalcogenides materials or for designing nanoscale sensing platforms based on near-field enhancement over a metallic surface.
Project description:We report two new series of compounds that show the ferroelectric nematic, NF, phase in which the terminal chain length is varied. The longer the terminal chain, the weaker the dipole-dipole interactions of the molecules are along the director and thus the lower the temperature at which the axially polar NF phase is formed. For homologues of intermediate chain lengths, between the non-polar and ferroelectric nematic phases, a wide temperature range nematic phase emerges with antiferroelectric character. The size of the antiparallel ferroelectric domains critically increases upon transition to the NF phase. In dielectric studies, both collective ("ferroelectric") and non-collective fluctuations are present, and the "ferroelectric" mode softens weakly at the N-NX phase transition because the polar order in this phase is weak. The transition to the NF phase is characterized by a much stronger lowering of the mode relaxation frequency and an increase in its strength, and a typical critical behavior is observed.
Project description:Growing crystallographically incommensurate and dissimilar organic materials is fundamentally intriguing but challenging for the prominent cross-correlation phenomenon enabling unique magnetic, electronic, and optical functionalities. Here, we report the growth of molecular layered magnet-in-ferroelectric crystals, demonstrating photomanipulation of interfacial ferroic coupling. The heterocrystals exhibit striking photomagnetization and magnetoelectricity, resulting in photomultiferroic coupling and complete change of their color while inheriting ferroelectricity and magnetism from the parent phases. Under a light illumination, ferromagnetic resonance shifts of 910 Oe are observed in heterocrystals while showing a magnetization change of 0.015 emu/g. In addition, a noticeable magnetization change (8% of magnetization at a 1,000 Oe external field) in the vicinity of ferro-to-paraelectric transition is observed. The mechanistic electric-field-dependent studies suggest the photoinduced ferroelectric field effect responsible for the tailoring of photo-piezo-magnetism. The crystallographic analyses further evidence the lattice coupling of a magnet-in-ferroelectric heterocrystal system.
Project description:1,4-Dihydropyridine (DHP) scaffold holds an outstanding position with its versatile pharmacological properties among all heterocyclic compounds. Although most of the commercially available DHPs are marketed as a racemic mixture, the chiral center at C-4 can lead to even opposite pharmacological activities between the enantiomers. In the present study, enantioseparation of seventeen DHP structural analogues, consisting of either pharmacologically active or newly synthesized derivatives, (M2-4, MD5, HM2, HM10, CE5, N11, N10, N7, M11, MC6-8, MC13, MD23, and 42IIP) by high-performance liquid chromatography was investigated using immobilized polysaccharide-based chiral stationary phase, Chiralpak IC column. Due to the solvent versatility of the covalently immobilized chiral stationary phase in enantiomer separation, multiple elution modes including standard normal phase, nonstandard mobile phase, and reversed phase were used to expand the possibility to find the optimum enantioselective conditions for the tested analytes. Under appropriate separation conditions, complete enantiomeric separation was obtained for nearly all compounds except MC6-8 and MC13 which contained two chiral centers. Additionally, the effects of the polar modifier, the additive, and column temperature on the chiral recognition were evaluated. The thermodynamic parameters calculated according to the linear van't Hoff equation indicated that the chiral separations in this study were enthalpy-driven or entropy-driven. Some parameters of method validation such as linearity, limit of quantitation, and repeatability were also measured for all studied compounds to prove the reliability of the method.