Delayed fluorescence from inverted singlet and triplet excited states.

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.

Manipulation of Chiral Nonlinear Optical Effect by Light-Matter Strong Coupling.

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.

Magneto-chiral Nonlinear Optical Effect with Large Anisotropic Response in Two-Dimensional Halide Perovskite.

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.

Reconfigurable Photonic Crystal Reversibly Exhibiting Single and Double Structural Colors.

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 (407 nm). After a temperature-gradient treatment, the photonic crystal segregates into two regions with shrunken (385 nm) and expanded (448 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.

Chirality-Induced Magnetoresistance Due to Thermally Driven Spin Polarization.

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.

Nontrivial topological defects of micro-rods immersed in nematics and their phototuning.

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.

Chiroptical Performances in Self-Assembled Hierarchical Nanosegregated Chiral Intermediate Phases Composed of Two Different Achiral Bent-Core Molecules.

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.

Photo-reconfigurable twisting structure in chiral liquid crystals triggered by photoresponsive surface.

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.

Noncentrosymmetric Columnar Liquid Crystals with the Bulk Photovoltaic Effect for Organic Photodetectors.

The bulk photovoltaic effect (BPVE) has drawn intensive attention due to its unique features that cannot be accessed with the conventional photovoltaic effect. However, the BPVE is observed in noncentrosymmetric materials and has been studied mainly for inorganic materials. Here, we report a simple subphthalocyanine (SubPc) derivative that assembles into a noncentrosymmetric columnar liquid crystal with the help of a DC E-field. These columnar assemblies exhibit the BPVE over a wide range of wavelengths up to 650 nm. Furthermore, just by sandwiching this columnar assembly between two ITO electrodes, the resultant device reaches a light-on/off ratio, Ilight/Idark, as high as 6.6 × 103, indicating that the polar columnar assemblies with SubPcs are promising for photodetectors.

Supramolecular Polymerization in Liquid Crystalline Media: Toward Modular Synthesis of Multifunctional Core-Shell Columnar Liquid Crystals.

Recently, we discovered a modular synthetic approach for constructing core-shell columnar liquid crystals (LCs) by supramolecular polymerization in LC media. In the present work, we successfully confirmed that our modular synthetic approach has the potential to be widely extended to the development of multifunctional columnar LCs. Herein, we constructed the first core-shell columnar LC that was proved to be orientable by both electric and magnetic fields by the supramolecular polymerization of NODiskNH* in a nematic LC medium of 4-cyano-4'-pentyloxybiphenyl (5OCB). NODiskNH* is a chiral benzenetricarboxamide derivative bearing 2,2,6,6-tetramethylpiperidine 1-oxyl termini, which is known to form a helical supramolecular polymer via a triple hydrogen-bonding array. NODiskNH* alone formed a hydrogen-bonded liquid phase without any long-range structural ordering. However, a nematic LC medium of 5OCB, when mixed with NODiskNH* at a molar ratio of 1:3, underwent a "structural order-increasing" mesophase transition, affording an optically active single LC phase with a hexagonally arranged core-shell columnar geometry in a temperature range from 113 to 51 °C. Unprecedentedly, this core-shell columnar LC can orient its columns both electrically and magnetically, resulting in unidirectional columnar ordering.

Spherical-cap droplets of a photo-responsive bent liquid crystal dimer.

Using a photo-responsive dimer exhibiting the transition between nematic (N) and twist-bend nematic (NTB) phases, we prepared spherical cap-shaped droplets on solid substrates exposed to air. The internal director structures of these droplets vary depending on the phase and on the imposed boundary conditions. The structural switching between the N and NTB phases was successfully performed either by temperature control or by UV light-irradiation. The N phase is characterized by an extremely small bend elastic constant K3, and surprisingly, we found that the droplet-air interface induces a planar alignment, in contrast to that seen for typical calamitic liquid crystals. As a consequence, the director configuration was stabilized in a structure substantially different from that normally found in conventional nematic liquid crystalline droplets. In the twist-bend nematic droplets characteristic structures with macroscopic length scales were formed, and they were well controlled by the droplet size. These results indicated that a continuum theory is effective in describing the stabilization mechanism of the macroscopic structure even in the twist-bend nematic liquid crystal droplets exhibiting director modulations on a scale of several molecular lengths.

The role of structural anisotropy in the magnetooptical response of an organoferrogel with mobile magnetic nanoparticles.

We investigate the structure and the magnetooptical response of isotropic and anisotropic fibrillous organoferrogels with mobile magnetic nanoparticles (MNPs). We demonstrate that the presence of the gel network restricts the magnetooptical response of the ferrogel. Even though the ferrogel exhibits no magnetic hysteresis, an optical hysteresis has been found. This suggests that the magnetooptical response is primarily determined by the dynamics of self-assembly of the MNPs into shape-anisotropic agglomerates. Furthermore, we show that the optical anisotropy of the system can be fine-tuned by varying the concentration of the gelator and the MNPs, respectively. The optical response in structurally anisotropic gels becomes orientation-dependent, revealing an intricate interplay between the gel mesh and the MNPs.

Redox-Responsive Chiral Dopant for Quick Electrochemical Color Modulation of Cholesteric Liquid Crystal.

Here, we report the first redox-active chiral dopant FcD, which electrically alters its helical twisting power (HTP) for a cholesteric liquid crystalline (LC) medium and quickly changes the reflection color. FcD is composed of an axially chiral binaphthyl unit in conjunction with a redox-active ferrocene unit. A cholesteric LC phase of 4'-pentyloxy-4-cyanobiphenyl, doped with FcD (3.0 mol %), developed a blue reflection color. When nitrosyl tetrafluoroborate, a one-electron oxidant, was added to this cholesteric LC phase, FcD was oxidized to decrease its original HTP value by 13%, so that a green reflection color was developed. In the presence of a supporting electrolyte, the reflection color was electrochemically modulated using a sandwich-type glass cell with indium tin oxide electrodes. In quick response to the applied voltage of +1.5 V, the reflection color changed from blue to green within 0.4 s. When 0 V was applied, the reflection color returned to its original blue color. The FcD-doped cholesteric LC is characterized by its fastest electrochemical response and lowest operating voltage among those reported for electrically driven cholesteric LC devices.

Reversible Switching of the Magnetic Orientation of Titanate Nanosheets by Photochemical Reduction and Autoxidation.

Optical properties of aqueous colloidal dispersions of 2D electrolytes, if their aspect ratios are extra-large, can be determined by their orientation preferences. Recently, we reported that a colloidal dispersion of diamagnetic titanate(IV) nanosheets (TiIVNSs), when placed in a magnetic field, is highly anisotropic because TiIVNS anomalously orients its 2D plane orthogonal to the magnetic flux lines due to its large anisotropic magnetic susceptibility. Herein, we report a serendipitous finding that TiIVNSs can be in situ photochemically reduced into a paramagnetic species (TiIV/IIINSs), so that their preference of magnetic orientation changes from orthogonal to parallel. This transition distinctly alters the structural anisotropy and therefore optical appearance of the colloidal dispersion in a magnetic field. We also found that TiIV/IIINSs is autoxidized back to TiIVNSs under non-deaerated conditions. By using an elaborate setup, the dispersion of TiIVNSs serves as an optical switch remotely operable by magnet and light.

An Anisotropic Hydrogel Actuator Enabling Earthworm-Like Directed Peristaltic Crawling.

Peristaltic crawling, which is the moving mechanism of earthworm-like limbless creatures in narrow spaces, is a challenging target to mimic by using soft materials. Here we report an unprecedented hydrogel actuator that enables not only a peristaltic crawling motion but also reversing its direction. Our cylindrically processed hydrogel contains gold nanoparticles for photothermal conversion, a thermoresponsive polymer network for switching the electrical permittivity of the gel interior, and cofacially oriented 2D electrolytes (titanate nanosheets; TiNSs) to synchronously change their anisotropic electrostatic repulsion. When a hydrogel, which was designed to include cofacially oriented TiNSs along the cylindrical gel axis, is pointwisely photoirradiated with a visible-light laser, it spatiotemporally expands immediately (<0.5 s) and largely (80 % of its original length) in an isovolumetric manner. When the irradiation spot is moved along the cylindrical gel axis, the hydrogel undergoes peristaltic crawling due to quick and sequential elongation/contraction events and moves oppositely toward the laser scanning direction. Thus, when the scanning direction is switched, the crawling direction is reversed. When gold nanorods are used in place of gold nanoparticles, the hydrogel becomes responsive to a near-infrared light, which can deeply penetrate into bio tissues.

An autonomous actuator driven by fluctuations in ambient humidity.

Devices that respond to negligibly small fluctuations in environmental conditions will be of great value for the realization of more sustainable, low-power-consumption actuators and electronic systems. Herein we report an unprecedented film actuator that seemingly operates autonomously, because it responds to the adsorption and desorption of a minute amount of water (several hundred nanograms per 10 mm(2)) possibly induced by fluctuations in the ambient humidity. The actuation is extremely rapid (50 ms for one curl) and can be repeated >10,000 times without deterioration. On heating or light irradiation, the film loses adsorbed water and bends quickly, so that it can jump vertically up to 10 mm from a surface or hit a glass bead. The film consists of a π-stacked carbon nitride polymer, formed by one-pot vapour-deposition polymerization of guanidinium carbonate, and is characterized by a tough, ultralightweight and highly anisotropic layered structure. An actuator partially protected against water adsorption is also shown to walk unidirectionally.

Nanosegregated Chiral Materials with Self-Assembled Hierarchical Mesophases: Effect of Thermotropic and Photoinduced Polymorphism in Rodlike Molecules.

Supramolecular chirality in a binary mixture of achiral bent-core (BC) and achiral rodlike mesogens was observed. Three different nanosegregated mesophases were determined in the binary system, and meaningful changes in circular dichroism (CD) were detected near the phase-transition temperatures of the rodlike mesogens. The highest CD intensity in the binary system was noted in the nanosegregated mesophase, in which the BC mesogens were in the helical nanofilament (HNF) phase and the rodlike mesogens were in the smectic A phase. The supramolecular chirality in the binary mixture was attributed to the self-assembled hierarchical chiral superstructures. Based on the experimental results, plausible scenarios for the chiral superstructures of the rodlike molecules embedded in the HNF networks are suggested. In addition, a system comprising BC and rodlike molecules doped with a photoresponsive compound exhibited remarkable photoswitching of CD intensity. According to the isothermal photoinduced phase transition of the embedded molecules in BC molecular HNFs, the observed CD intensities can be dynamically and reversibly modulated. Such a material with easily controllable functionality is of considerable interest in the field of materials science.

Photomanipulation of the anchoring strength using a spontaneously adsorbed layer of azo dendrimers.

We systematically studied the photoinduced anchoring transition in a nematic liquid crystal containing azo dendrimers. Because the azo dendrimers in the trans-isomer state were spontaneously adsorbed at substrate surfaces, which was confirmed by optical second-harmonic generation (SHG), a homeotropic orientation was established at the first stage. Ultraviolet (UV) light irradiation triggered a transition into a planar state which was accompanied by a suppression of the SH generation. The monotonic decrease of the effective scalar order parameter with increasing UV light intensity was determined by polarized attenuated total reflection infrared (ATR-IR) spectroscopy. The variation of anchoring strength and extrapolation length was evaluated by observing the Fréedericksz transition as a function of UV light intensity at a certain visible (VIS) light intensity. Such a photoinduced variation can be interpreted as a variation of the anchoring strength depending on the trans/cis ratio at the surfaces based on a modified Rapini-Papoular model. Thus, this system provides the opportunity for a controlled change in the anchoring strength.

Lasing properties of polymerized chiral nematic Bragg onion microlasers.

Dye doped photocurable cholesteric liquid crystal was used to produce solid Bragg onion omnidirectional lasers. The lasers were produced by dispersing and polymerizing chiral nematic LC with parallel surface anchoring of LC molecules at the interface, extracted and transferred into another medium. Lasing characteristics were studied in carrier medium with different refractive index. The lasing in spherical cholesteric liquid crystal was attributed to two mechanisms, photonic bandedge lasing and lasing of whispering-gallery modes. The latter can be suppressed by using a higher index carrier fluid to prevent total internal reflection on the interface of the spheres. Pulse-to-pulse stability and threshold characteristics were also studied and compared to non-polymerized lasers. The polymerization process greatly increases the lasing stability.