Photochemically and Thermally Programmed Optical Multi-States from a Single Diacetylene-Functionalized Cyanostilbene Luminogen.

To develop advanced optical systems, many scientists have endeavored to create smart optical materials which can tune their photophysical properties by changing molecular states. However, optical multi-states are obtained usually by mixing many dyes or stacking multi-layered structures. Here, multiple molecular states are tried to be generated with a single dye. In order to achieve the goal, a diacetylene-functionalized cyanostilbene luminogen (DACSM) is newly synthesized by covalently connecting diacetylene and cyanostilbene molecular functions. Photochemical reaction of cyanostilbene and topochemical polymerization of diacetylene can change the molecular state of DACSM. By thermal stimulations and the photochemical reaction, the conformation of polymerized DACSM is further tuned. The synergetic molecular cooperation of cyanostilbene and diacetylene generates multiple molecular states of DACSM. Utilizing the optical multi-states achieved from the newly developed DACSM, switchable optical patterns and smart secret codes are successfully demonstrated.

Self-Assembled and Polymerized Hierarchical Nanostructure Films of Cyanostilbene-Based Reactive AIEgens for Smart Chemosensors.

For the development of acid-responsive advanced fluorescent films with a 2D nanostructure, a pyridyl cyanostilbene-based AIEgen (PCRM) is newly synthesized. The synthesized PCRM exhibits aggregation-induced emission (AIE) and responds reversibly to acid and base stimuli. To fabricate the nanoporous polymer-stabilized film, PCRM and 4-(octyloxy)benzoic acid (8OB) are complexed in a 1:1 ratio through hydrogen bonding. The PCRM-8OB complex with a smectic mesophase is uniaxially oriented at first and photopolymerized with a crosslinker. By subsequently removing 8OB in an alkaline solution, nanopores are generated in the self-assembled and polymerized hierarchical 2D nanostructure film. The prepared nanoporous fluorescent films exhibit not only the reversible response to acid and base stimuli but also mechanical and chemical robustness. Since the nanoporous fluorescent films have different sensitivities to trifluoroacetic acid (TFA) depending on the molecular orientation in the film, advanced acid vapor sensors that can display the risk level according to the concentration of TFA are demonstrated. Reactive AIEgens-based hierarchical nanostructure films with nanopores fabricated by a subsequent process of self-assembly, polymerization, and etching can open a new door for the development of advanced chemosensors.

Coatable Negative Dispersion Retarder: Kinetically Controlled Self-Assembly Pathway of Butterfly-Shaped Molecular Building Blocks for the Construction of Nanocolumns.

Disc-shaped building blocks with columnar phases have attracted attention for their potential in optical applications, including a retarder. However, to achieve coatable high-performance optical films, it is essential to understand a subtle interaction balance between building blocks and relevant self-assembled behaviors during material processing. Herein, we studied a self-assembled nanocolumn evaluation of linear butterfly-shaped dendrons (T-A3D) consisting of thiophene-based conjugated core and flexible alkyl dendron. X-ray diffraction provided insight into the unique hexagonal columnar liquid crystal phase of T-A3D, driven by intermolecular hydrogen bonding and coplanarity of the thiophene-based conjugated core. The formation of a self-assembled nanocolumn with high mobility enabled the uniaxial orientation of butterfly-shaped T-A3D on the aligned rod-shaped nematic reactive mesogens, resulting in a transparent and colorless two-layered negative retarder. The self-assembled nanocolumn consisting of butterfly-shaped molecule would break a new ground for developing advanced optical thin films.

When Chirophotonic Film Meets Wrinkles: Viewing Angle Independent Corrugated Photonic Crystal Paper.

Light manipulation strategies of nature have fascinated humans for centuries. In particular, structural colors are of considerable interest due to their ability to control the interaction between light and matter. Here, wrinkled photonic crystal papers (PCPs) are fabricated to demonstrate the consistent reflection of colors regardless of viewing angles. The nanoscale molecular self-assembly of a cholesteric liquid crystal (CLC) with a microscale corrugated surface is combined. Fully polymerizable CLC paints are uniaxially coated onto a wrinkled interpenetrating polymer network (IPN) substrate. Photopolymerization of the helicoidal nanostructures results in a flexible and free-standing PCP. The facile method of fabricating the wrinkled PCPs provides a scalable route for the development of novel chirophotonic materials with precisely controlled helical pitch and curvature dimensions. The reflection notch position of the flat PCP shifts to a lower wavelength when the viewing angle increased, while the selective reflection wavelength of wrinkled PCP is remained consistent regardless of viewing angles. The optical reflection of the 1D stripe-wrinkled PCP is dependent on the wrinkle direction. PCPs with different corrugated directions can be patterned to reduce the angular-dependent optical reflection of wrinkles. Furthermore, 2D wavy-wrinkled PCP is successfully developed that exhibit directionally independent reflection of color.

The transfer and amplification of cyanostilbene molecular function to advanced flexible optical paints through self-crosslinkable side-chain liquid crystal polysiloxanes.

A self-crosslinkable side-chain liquid crystal polysiloxane containing cyanostilbene (Si-CSM) was newly synthesized for the development of a new generation of flexible optical paints. The photoisomerization of the cyanostilbene moiety at the molecular level was transferred and amplified to the phase transition of Si-CSM, resulting in changes in the macroscopic optical properties of the Si-CSM thin film. The self-crosslinking reaction between Si-H groups in the Si-CSM polymer backbone caused the self-crosslinked Si-CSM thin film to be very elastic and both thermally and chemically stable. Therefore, the self-crosslinked Si-CSM thin film endured stretching and bending deformations under relatively harsh conditions. In addition, the uniaxially oriented and self-crosslinked Si-CSM thin film generated linearly polarized light emission. Polarization-dependent and photopatternable secret coatings were fabricated via a spontaneous self-crosslinking reaction after coating the Si-CSM paint and irradiating ultraviolet (UV) light through a photomask. This newly developed flexible optical Si-CSM paint can be applied in next-generation optical coatings.

Development of Diketopyrrolopyrrole-Based Smart Inks by Substituting Ionic Pendants and Engineering Molecular Packing Structures.

A series of diketopyrrolopyrrole (DPP) luminogen amphiphiles were newly designed and synthesized by a single-step anionic exchange reaction for controlling the photoluminescence properties in both solution and solid states. Multicolor emission in response to thermal, mechanical, and chemical stimuli was successfully demonstrated by engineering well-defined supramolecular assemblies. Phase transformation from the metastable amorphous solid to the stable orthorhombic crystal of [DP-Im][Br] provided the reversibly patternable light emission. Self-organization into the smectic crystalline phase of [DP-Im][TFSI] allowed us to show the linearly polarized light emission. By simultaneously applying [DP-Im][Br] and [DP-Im][TFSI], we demonstrated the fabrication of smart sensors for packaging of food or vaccines that can detect thermal attacks.

Transfer and Amplification of Iodine-Based Diacetylene Amphiphiles to Anisotropic Optical Properties by Uniaxial Orientation in Thin Films.

For flexible displays, there is a desperate need for a broadband coatable polarizer that can absorb light in a specific direction. Conventional polarizers fabricated by the polymer stretching process are too thick (50-200 µm) to be used as polarizers that can be applied to antireflective films in flexible displays. For the development of the broadband coatable thin film polarizer, diacetylene (DA) amphiphiles containing I- or I3- are newly designed and synthesized, and the content of DA amphiphiles in the 4,6-decadiyne solvent is optimized to form a lyotropic liquid crystal (LLC) phase. Topochemical polymerization of uniaxially oriented iodine-based DA not only stabilizes the film but also broadens the polarization light region from 350 to 700 nm. The transfer and amplification of iodine and DA functions in uniaxially oriented thin films enable the fabrication of broadband coatable thin film polarizers.

Imidazolium-Functionalized Diacetylene Amphiphiles: Strike a Lighter and Wear Polaroid Glasses to Decipher the Secret Code.

The development of smart inks that change color and transparency in response to external stimuli is very important for various fields, from modern art to safety and anticounterfeiting technology. A uniaxially oriented diacetylene thin film on a macroscopic area is obtained by coating, self-assembling and topochemical photopolymerizing of imidazolium-functionalized diacetylenes (M-DA and T-DA) and 4,6-decadiyne ink (70 wt%:20 wt%:10 wt%) exhibiting a lyotropic smectic A liquid-crystalline phase at room temperature. The color and transparency of letters and symbols written with the DA-based secret inks change reversibly from blue to red as well as from colorless transparent to black opaque depending on the temperature and polarization axis. A secret code written with thermoresponsive and polarization-dependent secret inks consisting of imidazolium-functionalized diacetylenes is successfully deciphered by wearing polaroid glasses and holding a burning torch.

Programmed Hierarchical Hybrid Nanostructures from Fullerene-Dendrons and Pyrene-Dendrons.

The construction of fullerene (C60 ) hierarchical nanostructures with the help of amphiphilic molecules remains a challenging task in nanoscience and nanotechnology. Utilizing the host-guest complex concept, sub-10 nm layered superstructures are constructed from a monofunctionalized C60 dendron (C60 D, guest) and tweezer-like pyrene dendron (PD, host). Since C60 D and PD are asymmetric shape amphiphiles having liquid crystal (LC) dendrons, both C60 D and PD construct head-to-head bilayer superstructures by themselves. From fluorescence titration experiments, it is realized that the host-guest complex shows 1:1 stoichiometric binding with a binding constant (Ksv = 2.45 × 105 m-1 ). Based on the morphological observations and scattering analyses, it is found that buckle-like asymmetric building blocks (C60 D·PD) are self-assembled by the host-guest complex and construct multilayer hybrid nanostructures. The hierarchical hybrid nanostructures consist of the self-assembled C60 D·PD bilayer with a 2D C60 ·P nanoarray sandwiched between LC dendrons. This advanced strategy is expected to be a practicable and rational guideline for the fabrication of programmed hierarchical hybrid nanostructures.

Anisotropic Thermal Interface Materials: Directional Heat Transfer in Uniaxially Oriented Liquid Crystal Networks.

For the development of anisotropic thermal interface materials (TIMs), a rod-shaped reactive monomer PNP-6MA is newly designed and successfully synthesized. PNP-6MA reveals a smectic A (SmA) mesophase between crystalline (K) and isotropic (I) phases. PNP-6MA can be oriented under a magnetic field ( B = 2 T), and its macroscopic orientation can be robustly stabilized by in situ polymerization. Even without macroscopic orientations, the fabricated thermal conducting liquid crystal (TCLC) films show the outstanding thermal conductivity of 1.21 W/m K, which is higher than conventional organic materials. The thermal conductivity of uniaxially and macroscopically oriented TCLC films can be 2.5 W/m K along the long axis of mesogenic core. The newly developed TCLC film can be used as a TIM between a high-power light-emitting diode and a heat sink.

Kinetically Controlled Polymorphic Superstructures of Pyrene-Based Asymmetric Liquid Crystal Dendron: Relationship Between Hierarchical Superstructures and Photophysical Properties.

To understand the relationship between kinetically controlled hierarchical superstructures and photophysical properties, pyrene-based asymmetric liquid crystal (LC) dendrons (abbreviated as PD) were newly synthesized by covalently attaching a pyrene moiety (P) at a biphenyl-based LC dendritic group (D). The phase transition behavior of PD has been systematically studied with a combined technique of thermal analysis, microscopy, spectroscopy, and scattering analysis. PD formed two different crystalline structures depending on the cooling rate: a stable crystalline phase (Ks , slow cooling) and a metastable crystalline phase (Kms , quenching). The kinetically controlled molecular packing structures of PD depend on the competition and cooperation of intermolecular physical interactions with nanophase separation. Upon slow cooling, the PD dimer formed by intermoelcular H-bonding constructed a layered hierarchical structure with the help of nanophase separation. Owing to the strong π-π stacking (J-aggregation) with weak H-bondings, the PD dimer in the layer was slightly tilted to give a monoclinic layered structure with a periodic layer d-spacing of 6.6 nm. In contrast, the metastable Kms phase formed by the quenching process showed a significant tilt of the PD dimer in the layer (d-spacing=4.4 nm) due to the weak π-π stacking (H-aggregation) and the strong H-bondings.

Topochemical polymerization of dumbbell-shaped diacetylene monomers: relationship between chemical structure, molecular packing structure, and gelation property.

Herein, we have synthesized novel photopolymerizable dumbbell-shaped diacetylene liquid crystal (LC) monomers by locating a diacetylene dicarboxylic acid group at the center and chemically connecting swallow-tails, such as hydrophobic alkyl chains (abbreviated as AT3DI) and amphiphilic biphenyl mesogens (abbreviated as BP3DI), with bisamide groups. Major phase transitions of dumbbell-shaped diacetylene monomers were identified using differential scanning calorimetry (DSC), polarized optical microscopy (POM), and Fourier transform infrared spectroscopy (FT IR). Molecular packing structures were studied based on structure-sensitive wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) analyses. Mainly, due to nanophase separations and strong intermolecular hydrogen bonding, AT3DI formed a low-ordered lamellar LC phase at room temperature. BP3DI self-assembled into highly-ordered crystal phases (K1 and K2) at lower temperatures below a low-ordered lamellar LC phase, in which BP3DI were intercalated with each other to compensate the mutual volume differences. From the photopolymerization of AT3DI and BP3DI, it was realized that the topochemical reactions of dumbbell-shaped diacetylene monomers were closely related to their chemical structures as well as molecular packing structures.