ABSTRACT
A novel organo sulfur and selenium-controlled emission behavior in discrete copper(I) clusters has been demonstrated for the first time. The pentanuclear [Cu5Br5(L1)2] (1), trinuclear [Cu3Br3(L2)2] (2), dinuclear [Cu2I2(L1)2] (3), and tetranuclear [Cu4I4(L2)2CH3CN] (4) copper(I) discrete clusters have been synthesized from the reaction between L1 [L1 = 1-isopropyl-3-(pyridin-2-yl)-imidazol-2-thione] or L2 [L2 = 1-isopropyl-3-(pyridin-2-yl)-imidazol-2-selone] chelating ligands and corresponding copper(I) halide salts. These new clusters have been characterized by FT-IR, UV-visible, thermogravimetric analysis, and fluorescence spectroscopy techniques. Single-crystal X-ray diffraction studies reveal that 1-4 consists of abundant d10-d10 interactions. The structural and bonding features of clusters have been investigated using density functional theory calculations. Notably, the L2-ligated 2 and 4 are poorly emissive, while L1-ligated 1 and 3 showed strong emission in the orange and green regions, respectively. The time-dependent density functional theory natural transition orbital calculations of 1 and 3 reveal the nature of the transitions contributed by 3MLCT/3LLCT/3ILCT. Photoluminescence quantum yields of 1 and 3 are 19 and 11%, with average lifetimes of 21.55 and 6.57 µs, respectively. 1 and 3 were coated on prototype LED bulbs for light-emitting performance.
ABSTRACT
Micro-sized chiral-nematic liquid crystal (N* LC) polymer particles have attracted considerable interest as versatile reflective colorants with selective circularly polarized light (CPL) properties. However, challenges in achieving the desired size distribution of N* LC particles have led to an incomplete understanding of their reflective characteristics. In this study, we successfully synthesized N* LC particles via dispersion polymerization, enabling precise control over size polydispersity by manipulating the composition of the polymerization solvent. Our investigation revealed that monodisperse N* LC particles displayed distinct reflection bands with high CPL selectivity, while polydisperse particles exhibited broader reflection with lower CPL selectivity. These findings underscore the potential to synthesize N* LC particles with tailored reflective properties using identical monomeric compounds. Furthermore, we demonstrated the production of multifunctional reflective colorants by blending N* LC particles with varying reflection colors. These discoveries hold significant promise for advancing the development of reflective colorants and anti-counterfeiting printing techniques utilizing micro-sized N* LC particles.
ABSTRACT
The optical Freedericksz transition (OFT) can reversibly control the molecular orientation of liquid crystals (LCs) only by light irradiation, leading to the development of all-optical devices, such as smart windows. In particular, oligothiophene-doped LCs show the highly sensitive OFT due to the interaction between dyes and an optical-electric field. However, the sensitivity is still low for the application to optical devices. It is necessary to understand the factors in LCs affecting the OFT behavior to reduce the sensitivity. In this study, we investigated the effect of the host LC structure on the OFT in oligothiophene-doped LCs. The threshold light intensity for the OFT in trifluorinated LCs was 42% lower than that in LCs without fluorine substituents. This result contributes to the material design for the low-threshold optical devices utilizing the OFT of dye-doped LCs.
ABSTRACT
Inorganic nanomaterials such as nanotubes and nanorods have attracted great attention due to their anisotropic properties. Although the alignment control of inorganic nanomaterials is key to the development of functional devices utilizing their fascinating properties, there is still difficulty in achieving uniform alignment over a large area with a micrometer thickness. To overcome this problem, we focused on liquid crystals (LCs) to promote the alignment of anisotropic nanomaterials, taking advantage of the cooperative motion of LCs. We present the uniform, one-dimensional alignment of ZnO nanorods along the direction of LCs in micrometer-thick cells by grafting nematic LC polymers from the nanorod surfaces to provide miscibility with the host LCs. Polarized optical microscopy and polarized UV-visible absorption spectroscopy revealed the unidirectional alignment of nematic LC polymer-grafted ZnO nanorods parallel to the nematic host LCs.
ABSTRACT
Optical limiting is a phenomenon widely recognized as the potential application for a protector of human eyes and optical sensors from irradiation with lasers. However, a high optical limiting threshold and low flexibility have restricted such applications. Here, we report that oligothiophene-doped liquid crystals (LCs) function as a low-threshold optical limiter with deformability. Irradiation of dye-doped LCs with a continuous wave (CW) laser beam brings about the formation of diffraction rings, and the number of rings changes depending on the incident light intensity due to their photoinduced molecular reorientation. Utilizing such reorientation enables reversible optical limiting without additional multilayered optical components. In particular, an electric field application to a LC-based optical limiter decreases their optical limiting threshold from 2100 to 25 mW/cm2, and the threshold can be tuned by adjusting the applied voltage. Furthermore, the softness of LCs allows for the fabrication of the deformable optical limiter; optical limiting due to the molecular reorientation occurs even in largely bent states. The low-threshold and deformable optical limiter based on oligothiophene-doped LCs thus will enable one to develop the protector of eyes and optical sensors from glaring light-induced damage.
