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Ferroelectric nematic liquid crystals are fluids exhibiting spontaneous electric polarization, which is coupled to their long range orientational order. Due to their inherent property of making bound and surface charges, the free surface of ferroelectric nematics becomes unstable in electric fields. Here we show that ferroelectric liquid bridges between two electrode plates undergo distinct interfacial instabilities. In a specific range of frequency and voltage, the ferroelectric fluid bridges move as active interacting particles resembling living organisms like swarming insects, microbes or microrobots. The motion is accompanied by sound emission, as a consequence of piezoelectricity and electrostriction. Statistical analysis of the active particles reveals that the movement can be controlled by the applied voltage, which implies the possible application of the system in new types of microfluidic devices.
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Ferroelectric nematic liquid crystals (NFLCs) are distinguished by their remarkable polarization characteristics and diverse physical phenomena, sparking significant interest and excitement within the scientific community. To date, over 150 NFLC molecules are developed; however, there are no reports regarding straight linear polar molecules with a parallel alignment of the permanent dipole moment and the molecular axis. The straight polar mesogen nBOE exhibits an enantiotropic NF phase with a wide temperature window (up to 100 K) despite having a longer alkyl chain (up to n = 6) than the critical alkyl chain length of conventional models. Interestingly, nBOE with a medium-length alkyl chain displays an exotic phase sequence of NF-HCNF-SmXF during the elimination of positional displacement among adjacent molecules. Furthermore, the reflective color modulation of the HCNFLC over the entire VIS-NIR spectral regime by ultralow E-field (up to 0.14 V µm-1) is demonstrated.
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The study has demonstrated a novel microcavity-based flexible photon up-conversion system using second harmonic generation (SHG) from a polar nematic fluidic medium doped with a laser dye. The idea is based on coherent light generation via stimulated emission (lasing) and simultaneous frequency doubling inside a microcavity. The polar nematic fluid equips very high even-order optical nonlinearity due to its polar symmetry and large dipole moment along the molecular long axis. At the same time, its inherent fluidic nature allows to easily functionalize the media just by doping, in the present case, with an emissive laser dye. The demonstrated system exhibits a giant nonlinear optical response to input light, while enabling spectral narrowing and multiple-signal output of up-converted light, which is not attainable through the simple SH-conversion of input light. Furthermore, the susceptibility of the liquid crystal offers dynamic modulation capabilities by an external stimulus, such as signal switching by the application of electric field or wavelength tuning through temperature variation. Such a brand-new type of simple coherent flexible up-conversion system must be promising as a new principle for easily accessible and down-scalable wavelength conversion devices.
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Light-matter strong coupling (LMSC) is an intriguing state in which light and matter are hybridized inside a cavity. It is increasingly recognized as an excellent way to control material properties without any chemical modification. Here, we show that the LMSC is a powerful state for manipulating chiral nonlinear optical (NLO) effects through the investigation of second harmonic generation (SHG) circular dichroism. At the upper polariton band in LMSC, in addition to the enhancement of SHG by more than 1 order of magnitude, the responsivity to the handedness of circularly polarized light was largely modified, where sign inversion and increase of the dissymmetry factor were achieved. Quarter waveplate rotation analysis revealed that the LMSC clearly influenced the coefficients associated with chirality in the NLO process and also contributed to the enhancement of nonlinear magnetic dipole interactions. This study demonstrated that LMSC serves as a great platform for controlling chiral and magneto-optics.
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The chiral organic-inorganic halide perovskites (OIHPs) are vital candidates for superior nonlinear optical (NLO) effects associated with circularly polarized (CP) light. NLO in chiral materials often couples with magnetic dipole (MD) transition, as well as the conventional electric dipole (ED) transition. However, the importance of MD transition in NLO process of chiral OIHPs has not yet been well recognized. Here, the circular polarized probe analysis of second harmonic generation circular dichroism (SHG-CD) provides the direct evidence that the contribution of MD leads to a large anisotropic response to CP lights in chiral OIHPs, (R-/S-MBACl)2PbI4. The thin films exhibit great sensitivity to CP lights over a wide wavelength range, and the g-value reaches up to 1.57 at the wavelength where the contribution of MD is maximized. Furthermore, it is also effective as CP light generator, outputting CP-SHG with maximum g-factor of 1.76 upon the stimulation of linearly polarized light. This study deepens the understanding of relation between chirality and magneto-optical effect, and such an efficient discrimination and generation of CP light signal is highly applicable for chirality-based sensor and optical communication devices.
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Chiral perovskites have garnered significant attention, owing to their chiroptical properties and emerging applications. Current fabrication methods often involve complex chemical synthesis routes. Herein, an alternative approach for introducing chirality into nonchiral hybrid organic-inorganic perovskites (HOIPs) using nanotemplates composed of cholesteric polymeric networks is proposed. This method eliminates the need for additional molecular design. In this process, HOIP precursors are incorporated into a porous cholesteric polymer film, and two-dimensional (2D) HOIPs grow inside the nanopores. Circularly polarized light emission (CPLE) was observed even though the selective reflection band of the cholesteric polymer films containing a representative HOIP deviated from the emission wavelength of the 2D HOIP. This effect was confirmed by the induced circular dichroism (CD) observed in the absorbance band of the HOIP. The observed CPLE and CD are attributed to the chirality induced by the template in the originally nonchiral 2D HOIP. Additionally, the developed 2D HOIP exhibited a long exciton lifetime and good stability under harsh conditions. These findings provide valuable insights into the development and design of innovative optoelectronic materials.
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Unlike absorption-based colors of dyes and pigments, reflection-based colors of photonic crystals, so called "structural colors", are responsive to external stimuli, but can remain unfaded for over ten million years, and therefore regarded as a next-generation coloring mechanism. However, it is a challenge to rationally design the spectra of structural colors, where one structure gives only one reflection peak defined by Bragg's law, unlike those of absorption-based colors. Here, we report a reconfigurable photonic crystal that exhibits single-peak and double-peak structural colors. This photonic crystal is composed of a colloidal nanosheet in water, which spontaneously adopts a layered structure with single periodicity (407â nm). After a temperature-gradient treatment, the photonic crystal segregates into two regions with shrunken (385â nm) and expanded (448â nm) periodicities, and thus exhibits double reflection peaks that are blue- and red-shifted from the original one, respectively. Notably, the transition between the single-peak and double-peak states is reversible.
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In this paper, chiral intermediate phases composed of two achiral molecules are fabricated by utilizing nanophase separation and molecular hierarchical self-organization. An achiral bent-core guest molecule, exhibiting a calamitic nematic and a dark conglomerate phase according to the temperature, is mixed with another achiral bent-core host molecule possessing a helical nanofilament to separate the phases between them. Two nanosegregated phases are identified, and considerable chiroptical changes, such as circular dichroism and circularly polarized luminescence, are detected at the transition temperatures between the different nanophase-separated states. The nanosegregated chiral phase-wherein the helical nanofilament and dark conglomerate phases are phase-separated-exhibits the highest chiroptical intensities. The luminescence dissymmetry factor, |glum|, in this phase is amplified by an order of magnitude compared with that of another nanosegregated phase, wherein the helical nanofilament and nematic phases are phase-separated.
Assuntos
Luminescência , Dicroísmo Circular , Temperatura , Temperatura de TransiçãoRESUMO
We studied the structure of a helical nano-filament of the B4 phase in mixtures of a cholesteric liquid crystal mixture and a bent-core molecule using a resonant soft X-ray scattering (RSoXS) technique. In this system, nanophase separation occurs and it was already found that an unexpected new functional chiral smectic structure in the rod-like molecule rich region is constructed by the strong interaction between bent-core and rod-like molecules. In this paper, we focused on the structure of the helical filament in the bent-core liquid crystalline molecule rich region in this mixing system, and it was found that the pitch of the helical filament decreases and the coherence of the helical structure increases.
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Hund's multiplicity rule states that a higher spin state has a lower energy for a given electronic configuration1. Rephrasing this rule for molecular excited states predicts a positive energy gap between spin-singlet and spin-triplet excited states, as has been consistent with numerous experimental observations over almost a century. Here we report a fluorescent molecule that disobeys Hund's rule and has a negative singlet-triplet energy gap of -11 ± 2 meV. The energy inversion of the singlet and triplet excited states results in delayed fluorescence with short time constants of 0.2 µs, which anomalously decrease with decreasing temperature owing to the emissive singlet character of the lowest-energy excited state. Organic light-emitting diodes (OLEDs) using this molecule exhibited a fast transient electroluminescence decay with a peak external quantum efficiency of 17%, demonstrating its potential implications for optoelectronic devices, including displays, lighting and lasers.
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Chirality-induced current-perpendicular-to-plane magnetoresistance (CPP-MR) originates from current-induced spin polarization in molecules. The current-induced spin polarization is widely recognized as a fundamental principle of chiral-induced spin selectivity (CISS). In this study, we investigate chirality-induced current-in-plane magnetoresistance (CIP-MR) in a chiral molecule/ferromagnetic metal bilayer at room temperature. In contrast to CPP-MR, CIP-MR observed in the present study requires no bias charge current through the molecule. The temperature dependence of CIP-MR suggests that thermally driven spontaneous spin polarization in chiral molecules is the key to the observed MR. The novel MR is consistent with recent CISS-related studies, that is, chiral molecules in contact with a metallic surface possess a finite spin polarization.
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Here, we report a medium-to-polymer anomalous chiral transfer in the supramolecular polymerization of a tetraphenylporphyrin-based achiral hydrogen-bonding monomer (TPP) in a chiral medium of 5-cyanobiphenyl CB*. A mixture of TPP in (R)-CB* ([TPP]=7.7â mol %) at 40 °C gave a columnar oblique LC mesophase, where the individual columns were composed of an optically active helical supramolecular polymer of TPP as a consequence of a successful medium-to-polymer chiral transfer. Meanwhile, upon dilution of CB* with achiral 5-cyanobiphenyl CB, the optical activity of the system showed an anomalous bell-shaped dependency on the composition of CB*/CB, where the gabs value of 0.049 at CB*/CB=50/50 was 6.0â times larger than the gabs value of CB* alone. Such anomalous chiroptical amplification in CD is most likely due to a change in the stacking geometry of TPP in the oblique columnar LC upon lateral compression.
Assuntos
Polímeros , Ligação de Hidrogênio , PolimerizaçãoRESUMO
Dielectric permittivity, a measure of polarisability, is a fundamental parameter that dominates various physical phenomena and properties of materials. However, it remains a challenge to control the dielectric permittivity of materials reversibly over a large range. Herein, we report an anisotropic fluid with photoresponsive dielectric permittivity (200 < ε < 18,000) consisting of a fluorinated liquid-crystalline molecule (96 wt%) and an azobenzene-tethered phototrigger (4 wt%). The reversible trans-cis isomerisation of the phototrigger under blue and green light irradiation causes a switch between two liquid-crystalline phases that exhibit different dielectric permittivities, with a rapid response time (<30 s) and excellent reversibility (~100 cycles). This anisotropic fluid can be used as a flexible photovariable capacitor that, for example, allows the reversible modulation of the sound frequency over a wide range (100 < f < 8500 Hz) in a remote manner using blue and green wavelengths.
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Combinations of different geometries and surface anchoring conditions give rise to the diversity of topological structures in nematic colloid systems. Tuning these parameters in a single system offers possibilities for observing the evolution of the topological transformation and for manipulating colloids through topological forces. Here we investigate the nontrivial topological properties of micro-rods dispersed in nematic liquid crystals through experimental observation and computer simulation. The topological variation is driven by photodynamically changing the surface anchoring using azobenzene-based surface-commander molecules, the majority of which are localized on both the substrates and the surface of micro-rods. By comparing experimental and simulation results, we show previously unidentified topological properties of the two-body LC-rod-colloid system. Moreover, unlike the traditional photoresponsive liquid crystal systems, the localization of azobenzene molecules on the surfaces makes it possible to change only the direction of the surface orientation, not disordering of the bulk structures. The results assist in the development of photo-driven micro-robotics in fluids.
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Just like in living organisms, if precise coherent operation of tiny movable components is possible, one may generate a macroscopic mechanical motion. Here we report that ~1010 pieces of colloidally dispersed nanosheets in aqueous media can be made to operate coherently to generate a propagating macroscopic wave under a non-equilibrium state. The nanosheets are initially forced to adopt a monodomain cofacial geometry with a large and uniform plane-to-plane distance of ~420 nm, where they are strongly correlated by competitive electrostatic repulsion and van der Waals attraction. When the electrostatic repulsion is progressively attenuated by the addition of ionic species, the nanosheets sequentially undergo coherent motions, generating a propagating wave. This elaborate wave in time and space can transport microparticles over a long distance in uniform direction and velocity. The present discovery may provide a general principle for the design of macroscopically movable devices from huge numbers of tiny components.
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Shape-transformable molecular additives with photoresponsivity, such as azobenzene or spiropyran, in matter are known to decrease the local order parameter and lead to drastic state variations under light irradiation. For example, a liquid crystalline state can be transformed to an isotropic liquid state by photo-exciting a tiny amount of azobenzene additives from trans- to cis-conformers. On the other hand, structural or shape transformation without changing the phase state is also intriguing since it offers an opportunity for manipulating specific structures. Here, we demonstrate an active control of the topology of chiral particle-like twisting structures, dubbed toron, by light. Interestingly, the individual twisting structure is fully reconfigurable between spherical and unique branched topological states. We reveal that the shape transformation is driven by the free-energy competition between the variation of surface anchoring strength and the elastic energy stored in the twisting structure. The mean-field simulation based on the Landau-de Gennes framework shows that the elastic anisotropy plays the dominant role in modifying the toron topology upon weak anchoring. The results offer a new path for understanding the process of topology-involved shape transformation and fabrication of novel functional materials.
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A novel chiral nematic phase with a polar helical order is realized via the introduction of helical twisting power into a polar nematogen. The properties of the induced polar nematic (polar cholesteric: Np*) phase differ from those of the conventional cholesteric (N*) phases existing thus far. Np*, which is a new class of N* structures, is characterized not only by its helically twisted nematic director, but also by a continuously twisted polarization. Transmission spectroscopy and helical pitch measurements in a wedge cell revealed that the half-helical pitch in the Np* phase vanished because of the polar response in the Np* helix. The inner polar director in the Np* phase is confirmed in dielectric and second-harmonic-generation studies. Furthermore, this unique Np*LC, which corresponds to a half-/full-pitch helix, enables ultrafast electro-optic switching (τ < 20 µs), and proposes new potential applications for electrically interchangeable photonic bandgaps.
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This study focused on the use of nonconventional bent-core π-electronic systems, 2,2'-bipyrroles substituted with modified benzoyl units, as building units of stimuli-responsive assemblies. Electric-field-responsive mesophase behaviors were observed in homochiral synclinic ferroelectric smectic C structures comprising the syn conformations. Electric-field application induced changes in the polarized optical microscopy textures with dynamic behaviors derived from the conversion from twisted to untwisted states.
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Steady rotation is induced in cholesteric droplets dispersed in a specific liquid solvent under a temperature gradient. In this phenomenon, two rotational modes have been considered: (1) collective rotation of the local director field and (2) rigid-body rotation of the whole droplet structure. However, here we present another rotational mode induced in a pillar-shaped cholesteric droplet confined between substrates under a temperature gradient, that is, a differential rotation where the angular velocity varies as a function of the radial coordinate in the pillar. A detailed flow field analysis revealed that every pillar under a temperature gradient involves a double convection roll. These results suggested that the differential rotation in the cholesteric pillars was driven by the inhomogeneous material flow induced by a temperature gradient. The present experimental study indicates that the coupling between the flow and the director motion plays a key role in the rotation of the cholesteric droplets under the temperature gradient.