Chiral Crystals Research Articles

Chiral Spinodal-like Ordering of Homoimmiscible Water at Interface between Water and Chiral Ice III.

Diversity in structures of water endowed by a hydrogen-bonding network plays crucial roles in wide varieties of phenomena in nature. Chiral ordering of water molecules is an intriguing phenomenon from the viewpoint of bimolecular functions. However, experimental reports on chiral ordering have been limited to the water molecules interacting with biomolecules on the molecular scale. It remains unclear whether pure liquid water forms long-range chiral ordering without any interaction with biomolecules. Here, we show that chiral anisotropy can be observed in the macro/mesoscopic network pattern of an unknown water layer formed via spinodal phase separation-like dynamics at the interface between water and ice III with a chiral crystal structure. We named this unknown water homoimmiscible water. Our observations infer that the unknown water is a chiral liquid crystal. This possibility opens new avenues for a wide variety of research fields such as liquid polymorphism, biology, earth and planetary science, and so forth from the perspective of chirality.

Design of High-Efficiency Hydrogen Evolution Catalysts in a Chiral Crystal

Design of High-Efficiency Hydrogen Evolution Catalysts in a Chiral Crystal

An Electrically Tunable Dual‐Mode Laser Based on Self‐Assembled Soft Photonic Liquid Crystals

AbstractSoft photonic liquid crystals with electrically responsive properties are among the most promising intelligent materials for optoelectronic applications. This work demonstrates an ultra‐fast electrically tunable dual‐mode laser by introducing dye‐doped chiral liquid crystals. Due to the strong chirality of the chiral liquid crystal, two self‐assembled structures form depending on the temperatures. One is the chiral nematic phase (N*) with a 1D helical structure; the other is the blue phases (BPs) with 3D cubic structures. By tuning the strength of an electric field, the dye‐doped chiral liquid crystals are operated in two different modes: a band‐edge laser and a random laser. In the band‐edge mode, due to the electrostriction effect of the BPs, the electric‐tuning range of the laser emission is from 537 to 645 nm, and the switching times are less than 20 ms. When the electric field goes beyond a threshold value to force the occurrence of the BPs‐chiral‐nematic transition, the band‐edge laser with elliptical polarization emission is switched to a random laser with an immediate unpolarization emission (0.9 ms). Furthermore, the reversibility of the effects mentioned above points out the potential applications of self‐assembled soft photonic materials, spanning from solid‐state lighting to bio‐imaging.

Chiral amino acid-templated tin fluorides tailoring nonlinear optical properties, birefringence, and photoluminescence.

In this study, we successfully synthesized two types of new chiral amino acid-templated tin fluoride crystals: (R)-[(C8H10NO3)2]Sn(IV)F6, (S)-[(C8H10NO3)2]Sn(IV)F6, (R)-[C8H10NO3]Sn(II)F3, and (S)-[C8H10NO3]Sn(II)F3, employing a slow evaporation method. The crystal structures of Sn(IV)-compounds were determined to belong to the noncentrosymmetric (NCS) nonpolar space group, P21212. Conversely, the structures of Sn(II)-compounds were found to crystallize in the NCS polar space group, P21, as revealed by single-crystal X-ray diffraction analysis. Remarkably, Sn(IV)-compounds exhibited a larger birefringence (0.328@546.1 nm), attributed to the well-stacked arrangement of planar π-conjugated benzene rings along the b-axis. The ability of tin(IV) fluorides to form more hydrogen bonds with ligands increased the probability of π-π interactions between benzene rings, enabling the growth of centimeter-sized crystals in Sn(IV)-compounds. In contrast, Sn(II)-compounds displayed a stronger second-harmonic generation (SHG) response (0.85 × KDP) than Sn(IV)-compounds (0.46 × KDP). This enhanced SHG response in Sn(II)-compounds was attributed to the increased dipole moments resulting from the presence of lone pairs. Additionally, Sn(II)-compounds exhibited photoluminescent properties due to the transition from the metal-to-ligand charge transfer state, facilitated by the presence of the lone pairs.

Stability of the chiral crystal phase and breakdown of the cholesteric phase in mixtures of active-passive chiral rods.

In this study, we aim to explore the effect of chirality on the phase behavior of active helical particles driven by two-temperature scalar activity. We first calculate the equation of state of soft helical particles of various intrinsic chiralities using molecular dynamics (MD) simulation. In equilibrium, the emergence of various liquid crystal (LC) phases such as nematic (N), cholesteric , smectic (Sm) and crystal (K) crucially depends on the presence of walls that induce planar alignment. Next, we introduce activity through the two-temperature model: keep increasing the temperature of half of the helical particles (labeled as 'hot' particles) while maintaining the temperature of the other half at a lower value (labeled as 'cold' particles). Starting from a homogeneous isotropic (I) phase, we find the emergence of 2-TIPS: two temperature-induced phase separations between the hot and cold particles. We also observe that the cold particles undergo an ordering transition to various LC phases even in the absence of a wall. This observation reveals that the hot-cold interface in the active system plays the role of a wall in the equilibrium system by inducing an alignment direction for the cold particles. However, in the case of a cholesteric phase, we observe that activity destabilizes the phase by inducing smectic ordering in the cold zone while an isotropic structure in the hot zone. The smectic ordering in the cold zone eventually transforms to a chiral crystal phase with high enough activity.

Light-controllable liquid crystal platform for microparticle oscillations and transport.

Liquid crystal colloids manifest complex motion caused by external stimuli, but tunable and addressable control of microsized objects remains a challenge. This study aims to demonstrate light-driven trapping, transport, and sustained periodic motions of microparticles by employing liquid crystal films as a light-controllable colloidal platform. The diverse motions of microscopic particles result from Marangoni convection coupled with elastic deformations in free-surface liquid crystal films subjected to light beam heating. The specific mode of particle motion, including damped and sustained oscillations, also combined with sustained rotation, is defined by the liquid crystal chirality, particle surface treatment, film thickness, and the power of the tightly focused light beam. The results reveal that free-surface liquid crystals provide a unique platform for the indirect optical manipulation of microscopic objects, paving the way for novel applications in microfluidic tools, particle sorting and transport, micropatterning, and various micromachines.

Tuning organic crystal chirality by enantiomer-specific oriented attachment

This work enriches the application of enantiomer-specific oriented attachment for chiral enantiomer enrichment.

Complete topological phase diagram and realization of minimum Weyl nodes in a sheared chiral crystal of elemental tellurium

Complete topological phase diagram and realization of minimum Weyl nodes in a sheared chiral crystal of elemental tellurium

Spin selectivity in elemental tellurium and other chiral materials

The phenomenon of chirality-induced spin selectivity (CISS), where chiral organic molecules enable the selective transmission of electrons spin-polarized along the direction of electric current, has been studied for nearly two decades. Despite its technological relevance, CISS is not fully understood. Recent studies have expanded the concept of spin selectivity to chiral inorganic crystals, offering promise for magnet-free spintronics and other applications. This Perspective reviews recent developments on spin selectivity in non-magnetic solid-state materials, whereby chirality-dependent charge-to-spin conversion is responsible for transforming electric currents into spin signals, and spin transport within devices. Notably, chiral systems often outperform non-chiral ones in terms of conversion efficiency and facilitate long-range spin transport, which makes them relevant for both fundamental and applied physics. After examining the archetypal example of the chiral crystal, elemental tellurium, and the studies of spin selectivity in Weyl semimetals, we discuss its origin in terms of the unconventional (collinear) Rashba–Edelstein effect. We also explore key factors affecting the conversion efficiency and robustness of spin transport, focusing on persistent spin textures and their influence on spin lifetime. In addition, we discuss the potential impact of band velocities and the role of orbital contributions, as well as the differences associated with reduced dimensionality, providing a roadmap for guiding future theoretical, experimental, and applied studies.

Cluster-assembled superatomic crystals for chirality-dependent charge-to-spin conversion

In chiral materials, spins and chirality are coupled via spin-orbit interaction, provoking a fast-growing field of chiral spintronics. Compared with the widely explored chiral molecules, exploration of chirality-dependent spin effects in crystals and supramolecules remain limited. Here we assemble chiral superatomic crystals MXTe4 (M = transition metal; X = Ga or Ge) using telluride tetrahedra clusters as building blocks. Distinct from atomic crystals, these assembled monolayers have tunable symmetries and electronic characteristics by tilting the tetrahedral units through the variation of inter-cluster interaction. Dresselhaus-type spin textures and anisotropic spin Hall effect with inversed sign of spin current under opposite geometrical handedness are demonstrated in these chiral monolayers by symmetry analysis and verified by ab initio calculations. These results provide an innovative paradigm for assembling superatomic crystals with designated symmetry and hierarchical structures to access the chirality-driven quantum effects.

Polychromatic Dual-Mode Imaging with Structured Chiral Photonic Crystals.

Optical spatial differentiation is a typical operation of optical analog computing and can single out the edge to accelerate the subsequent image processing, but in some cases, overall information about the object needs to be presented synchronously. Here, we propose a multifunctional optical device based on structured chiral photonic crystals for the simultaneous realization of real-time dual-mode imaging. This optical differentiator is realized by self-organized large-birefringence cholesteric liquid crystals, which are photopatterned to encode with a special integrated geometric phase. Two highly spin-selective modes of second-order spatial differentiation and bright-field imaging are exhibited in the reflected and transmitted directions, respectively. Two-dimensional edges of both amplitude and phase objects have been efficiently enhanced in high contrast and the broadband spectrum. This work extends the ingenious building of hierarchical chiral nanostructures, enriches their applications in the emerging frontiers of optical computing, and boasts considerable potential in machine vision and microscopy.

IrGe4: A Predicted Weyl-Metal with a Chiral Crystal Structure.

Polycrystalline IrGe4 was synthesized by annealing elements at 800 °C for 240 h, and the composition was confirmed by energy-dispersive X-ray spectroscopy. IrGe4 adopts a chiral crystal structure (space group P3121) instead of a polar crystal structure (P31), which was corroborated by the convergent-beam electron diffraction and Rietveld refinements using synchrotron powder X-ray diffraction data. The crystal structure features layers of IrGe8 polyhedra along the b axis, and the layers are connected by edge- and corner-sharing. Each layer consists of corner-shared [Ir3Ge20] trimers, which are formed by three IrGe8 polyhedra connected by edge-sharing. Temperature-dependent resistivity indicates metallic behavior. The magnetoresistance increases with increasing applied magnetic field, and the nonsaturating magnetoresistance reaches 11.5% at 9 T and 10 K. The Hall resistivity suggests that holes are the majority carrier type, with a carrier concentration of 4.02 × 1021 cm-3 at 300 K. Electronic band structures calculated by density functional theory reveal a Weyl point with a chiral charge of +3 above the Fermi level.

Switching of lasing direction in reconfigurable chiral photonic crystals: publisher’s note

This publisher’s note contains a correction to Opt. Mater. Express 13(6), 1555 (2023)10.1364/OME.491580.

Kinetic features of the adsorption of menthol enantiomers on o-toluylic acid and CsCuCl3 crystals with supramolecular chirality

Chirality plays a key role in modern science because it is the distinguishing feature of molecules and crystals. The spontaneous emergence of chirality in the absence of detectable chiral physical and chemical sources has recently advanced significantly due to the deracemization of conglomerates through Viedma ripening. As a result, systems based on supramolecular chirality are obtained. Of particular importance to this type of chirality is the fact that supramolecular chirality underlies the formation of life on Earth. One manifestation of supramolecular chirality is enantiomorphic crystals. Previously, we studied the mechanism of supramolecular chiral recognition for enantiomorphic crystals in the case of adsorption of optically active substances on them. However, for a more detailed study of the mechanism, it is required to study a large number of chiral crystals, which differ in their physicochemical properties. In this work, we studied the adsorption kinetics of menthol enantiomers on the surface of enantiomorphic crystals of o-toluic acid and CsCuCl3 with supramolecular chirality. The Viedma ripening method was used to obtain homochiral crystals. The crystals obtained in this way were deposited on the surface of the ASKG silica gel. The kinetics of adsorption has been studied by describing chemical models of Lagergren's pseudo-first order, Ho and McKay's pseudo-second order, and the Elovich model, simplified by Chen and Clayton. From an analysis of the adsorption curves of menthol enantiomers, it is noticeable that the curves differ on the crystals under consideration. The enantioselectivity coefficient on crystals of o-toluic acid and CsCuCl3 α, calculated as the ratio of higher adsorption to lower one, is 1.04-1.07 and 1.34-1.36 respectively. Using the t-test, the adsorption values of menthol enantiomers on enantiomorphic crystals of o-toluic acid and CsCuCl3 were processed until equilibrium was reached. The variances of all experimental data were checked for homogeneity using the F-test. It follows from the obtained data that the difference in adsorption values is statistically significant for the sample modified with both o-toluic acid and CsCuCl3. Based on the results obtained in the process of modeling the adsorption kinetics of menthol enantiomers by chemical models, the adsorption rate constants were calculated. It was found that in all methods the rate constants of D-menthol and L-menthol are different, and D-menthol is adsorbed faster than L-. From the data obtained, it is noticeable that the adsorption equilibrium in the case of both samples is shifted to the right. Thus, the difference in adsorption rate constants, as well as significant differences in the adsorption values of enantiomers in the region until adsorption–desorption equilibrium is reached, indicates that the adsorption rate of menthol enantiomers on crystals of o-toluic acid and CsCuCl3 obtained under Viedma ripening conditions is different.

Probing chirality of crystals using electron paramagnetic resonance (EPR) spectroscopy

One of the most challenging tasks in analytical chemistry is the determination of the chirality (identification of an enantiomeric composition) in solids mainly because of the strict requirements of the pharmaceutical industry for enantiomerically pure drugs. Although there are a few methods available to accomplish enantio‑differentiation in solids, for example: X-ray diffraction (XRD), Thermogravimetric analysis (TGA), CD spectroscopy, and low-frequency (LF) Raman spectroscopy, this is still very challenging. In this work, we have developed a new method to measure the chirality of crystals, based on electron paramagnetic resonance (EPR) spectroscopy of chiral crystals doped with Cu2+ as the EPR active ion. Here, we demonstrate our approach using a model system of l- and DL-Histidine crystals doped with Cu2+. We show that EPR measurements of the Cu2+-doped Histidine crystals can accurately determine the chirality and enantiomeric composition of the crystals. We present a very preliminary example of this technique, and we hope that in the future it will be possible to refine and develop this method for many other chiral organic crystal systems.

Chiral Van Der Waals Superlattices for Enhanced Spin-Selective Transport and Spin-Dependent Electrocatalytic Performance.

The emergence of the chiral-induced spin-selectivity (CISS) effect offers a new avenue for chiral organic molecules to autonomously manipulate spin configurations, thereby opening up possibilities in spintronics and spin-dependent electrochemical applications. Despite extensive exploration of various chiral systems as spin filters, one often encounters challenges in achieving simultaneously high conductivity and high spin polarization (SP). In this study, a promising chiral van der Waals superlattice, specifically the chiral TiS2 crystal, is synthesized via electrochemical intercalation of chiral molecules into a metallic TiS2 single crystal. Multiple tunneling processes within the highly ordered chiral layered structure of chiral TiS2 superlattices result in an exceptionally high SP exceeding 90%. This remarkable observation of significantly high SP within the linear transport regime is unprecedented. Furthermore, the chiral TiS2 electrode exhibits enhanced catalytic activity for oxygen evolution reaction (OER) due to its remarkable spin-selectivity for triplet oxygen evolution. The OER performance of chiral TiS2 superlattice crystals presented here exhibits superior characteristics to previously reported chiral MoS2 catalysts, with an approximately tenfold increase in current density. The combination of metallic conductivity and high SP sets the stage for the development of a new generation of CISS materials, enabling a wide range of electron spin-based applications.

Impact of Chiral Symmetry Breaking on Spin-Texture and Lone Pair Expression in Chiral Crystals of Hybrid Antimony and Bismuth Halides

Impact of Chiral Symmetry Breaking on Spin-Texture and Lone Pair Expression in Chiral Crystals of Hybrid Antimony and Bismuth Halides

Phase-change in topological chiral phononic crystal for directional coupling switch

Recently, acoustic valley Hall topological insulators have become a cutting-edge area of acoustic physics, where the topological phase transition in phononic crystals shows the presence of band inversion through the Dirac point in the momentum space. We developed a 2D hexagonal lattice chiral phononic crystal using reconfigurable construction by extending one side of the original rectangular rods. When the variation of the side length was from left to right, the topological phase transition is triggered by reopening the Dirac degeneracies beyond high-symmetry points in the first Brillouin zone. We numerically showed valley edge state’s propagation through the interface bent toward distinct chiral topological phononic crystals. Moreover, we assembled 2 × 2 cross-waveguides with a defect cavity based on double heterostructure interfaces. The simulated results verify that the phase change is achieved by the directional coupling switching. This research possibly paves the way for exploiting valley edge states to design the complex acoustic waveguide.

Observation of triple-branch valley topological edge states and abnormal refraction in elastic phononic crystal plates

Topological edge states (TES) have attracted wide interest in elastic waves, due to its backscattering immunity and directional wave transportation. In this work, the triple-branch TES and their rich refraction behaviors are investigated in one single valley chiral phononic crystal (PC) plate with double-sided symmetric pillars. The triple-branch TES emerge simultaneously in one structure, and their robust transportation against disorder, cavity, and sharp bends are demonstrated in both simulation and experiment. Furthermore, the refraction behaviors for triple-branch TES from PC plate into bare plate are unveiled both theoretically and experimentally, leading to the normal refraction for first branch TES while the abnormal refraction for the second or third branch TES. These results offer opportunity for designing mechanical device or controlling the wave propagation along phonon circuits in multiple bandwidths and with robustness.

Fused-Ring Electron-Acceptor Single Crystals with Chiral 2D Supramolecular Organization for Anisotropic Chiral Optoelectronic Devices.

Supramolecular chiral organization gives π-conjugated molecules access to fascinating specific interactions with circularly polarized light (CPL). Such a feature enables the fabrication of high-performance chiral organic electronic devices that detect or emit CPL directly. Herein, it is shown that chiral fused-ring electron-acceptor BTP-4F single-crystal-based phototransistors demonstrate distinguished CPL discrimination capability with current dissymmetry factor exceeding 1.4, one of the highest values among state-of-the-art direct CPL detectors. Theoretical calculations prove that the chirality at the supramolecular level in these enantiomeric single crystals originates from chiral exciton coupling of a unique quasi-2Dsupramolecular organization consisting of interlaced molecules with opposite helical conformation. Impressively, such supramolecular organization produces a higher dissymmetry factor along the preferred growth direction of the chiral single crystals in comparison to that of the short axis direction. Furthermore, the amplified, inverted, and also anisotropic current dissymmetry compared to optical dissymmetry is studied by finite element simulations. Therefore, a unique chiral supramolecular organization that is responsible for the excellent chiroptical response and anisotropic electronic properties is developed, which not only enables the construction of high-performance CPL detection devices but also allows a better understanding of the structure-property relationships in chiral organic optoelectronics.