Polarization-Dependent Thin Films with Biaxial Anisotropic Absorption Constructed by a Single Coating and Subsequent Topochemical Polymerization of Chromophores.

For the construction of hierarchical superstructures with biaxial anisotropic absorption, a newly synthesized diacetylene-functionalized bipyridinium is self-assembled to use an electron-accepting host for capturing and arranging guests. The formation of the donor-acceptor complex triggers an intermolecular charge transfer, leading to chromophore activation. Polarization-dependent multichroic thin films are prepared through a sequential process of single-coating, self-assembly, and topochemical polymerization of host-guest chromophores. Molecular packing structures constructed in the single-layer optical thin film possess orthogonal absorption axes for two different wavelengths. By tuning the linear polarization angle, the color of the optical thin film can be intentionally controlled. This single-layered multichroic film provides a new pathway for the development of anticounterfeiting and multiplexing encryptions.

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.

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.

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.

Thermal Energy Harvest and Reutilization by the Combination of Thermal Conducting Reactive Mesogens and Heat-Storage Mesogens.

Utilizing a newly programmed and synthesized heat storage mesogen (HSM) and reactive mesogen (RM), advanced heat managing polymer alloys that exhibit high thermal conductivity, high latent heat, and phase transition at high temperatures were developed for use as smart thermal energy harvesting and reutilization materials. The RM in the heat-managing RM-HSM polymer alloy was polymerized to form a robust polymeric network with high thermal conductivity. The phase-separated HSM domains between RM polymeric networks absorbed and released a lot of thermal energy in response to changes in the surrounding temperature. For the fabrication of smart heat-managing RM-HSM polymer alloys, the composition and polymerization temperature were optimized based on the constructed phase diagram and thermal energy managing properties of the RM-HSM mixture. From morphological investigation and thermal analysis, it was realized that the heat storage capacity of polymer alloys depends on the size of the phase-separated HSM domain. The structure-morphology-property relationship of the heat managing polymer alloys was built based on the combined techniques of thermal, scattering, and morphological analysis. The newly developed mesogen-based polymer alloys can be used as smart thermal energy-harvesting and reutilization materials.

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.