The well-defined hierarchical superstructures constructed by the self-assembly of programmed supramolecules can be organized for the fabrication of remote-controllable actuating and rewritable films. To realize this concept, we newly designed and synthesized a benzene-1,3,5-tricarboxamide (BTA) derivative (abbreviated as BTA-3AZO) containing photoresponsive azobenzene (AZO) mesogens on the periphery of the BTA core. BTA-3AZO was first self-assembled to nanocolumns mainly driven by the intermolecular hydrogen-bonds between BTA cores, and these self-assembled nanocolumns were further self-organized laterally to form the low-ordered hexagonal columnar liquid crystal (LC) phase below the isotropization temperature. Upon cooling, a lamello-columnar crystal phase emerged at room temperature via a highly ordered lamello-columnar LC phase. The three-dimensional (3D) organogel networks consisted of fibrous and lamellar superstructures were fabricated in the BTA-3AZO cyclohexane-methanol solutions. By tuning the wavelength of light, the shape and color of the 3D networked thin films were remote-controlled by the conformational changes of azobenzene moieties in the BTA-3AZO. The demonstrations of remote-controllable 3D actuating and rewritable films with the self-assembled hierarchical BTA-3AZO thin films can be stepping stones for the advanced flexible optoelectronic devices.
For the demonstration of remote-controllable actuators, a dendronized polymer (denpol) is newly designed and successfully synthesized by ringopening metathesis polymerization of azobenzene-based macromonomers. The incorporation of azobenzene mesogens into the denpols helps to construct finely tuned hierarchical superstructures with anisotropic physical properties and reversible photoisomerization. The polynorbornene backbones and azobenzene side chains in the uniaxially oriented films are aligned perpendicularly and parallel to the layer normal, respectively. Based on photoreversible actuation experiments combined with diffraction results, direct relationships between the chemical structures, hierarchical superstructures, and their corresponding photomechanical behaviors are proposed. Smart denpols possess great potential for practical applications in photoresponsive switches.
For liquid crystal (LC) alignment, polyhedral oligomeric silsesquioxanes (POSS) can be considered as one of the promising candidates for the formation of vertical alignment (VA) of LC. However, because of their poor compatibility and weak interaction with LC hosts, the pristine POSS are highly aggregate themselves in the LC media and create the macroscopic particles, resulting in severe light scatterings. To overcome this barrier, we proposed and successfully synthesized the cyanobiphenyl monosubstituted POSS giant molecule (abbreviated as POSS-CBP 1 ), which showed an excellent dispersion in nematic (N) LC media and formed the perfect VA of LC without using conventional polymer-based VA layers. On the basis of the systematic experiments and careful analysis, we realized that the cyanobiphenyl moiety chemically attached to the pristine POSS with an alkyl chain can significantly improve the initial solubility and interaction with LC media but finely tune POSS-CBP 1 to gradually diffuse onto the substrate of LC cell for the formation of VA layer without forming the macroscopic aggregations. Therefore, the newly developed POSS-CBP 1 VA layer can allow us to significantly cut the manufacturing cost as well as to open the new doors for electro-optical applications.
Bandwidth-tunable anisotropic spatial light modulators are fabricated with redox-responsive dichroic mesogens. By introducing an ionic group and a polymerizable group into the chromophore, the programmed reactive mesogen (PDI-MA) exhibits a lyotropic chromonic liquid crystal (LCLC) phase. The PDI-MA molecule forms a stable aromatic dianion state so that the absorption wavelengths of the dichroic mesogen can be reversibly tuned by redox reactions. Through a continuous process of coating, molecular self-assembly, and polymerization, redoxresponsive and uniaxially oriented LCLC polymer films are fabricated. Because of the high dichroic ratio of PDI-MA, the uniaxially oriented LCLC network is capable of anisotropic light modulation in the visible-light spectrum. Uniaxially oriented LCLC films are applied to flexible multichromic smart windows and optical security filters for anticounterfeiting.
A photopolymerizable itaconic acid-based amphiphile (abbreviated as Ita3C 12 ) consisting of a hydrophilic carboxylic acid, three alkyl tails, and a reactive vinyl function was newly designed and synthesized for the formation of automatic and robust vertical alignment (VA) layer of nematic liquid crystals (NLC). Since a hydrophilic carboxylic acid was chemically attached to the end of Ita3C 12 , the Ita3C 12 amphiphiles initially dissolved in the host NLC medium were migrated toward the substrates for the construction of VA layer of NLC. The alkyl tails of Ita3C 12 in the VA layer directly interacted with host NLC molecules and made them to automatically align vertically. Because of the reactive vinyl functions of Ita3C 12 amphiphiles, it was possible to stabilize the automatic VA layer by the photopolymerization with methacryl polyhedral oligomeric silsesquioxane (MAPOSS) cross-linkers. The polymer-stabilized robust Ita3C 12 VA layer exhibited a strong surface anchoring energy without generating any light scatterings. The automatic fabrication of robust LC alignment layers can allow us to reduce the manufacturing cost and to open new doors for electro-optical applications.
A programed light‐responsive chiral liquid crystal (LC) containing four photochromic azobenzene moieties covalently connected to a central bicyclic chiral core (abbreviated as AZ4ICD) is newly designed, precisely synthesized, and efficiently applied as a remote‐controllable molecular knob for the optically tunable thin film. First of all, phase evolutions and ordered structures of AZ4ICD are systematically investigated by a combination of thermal, microscopic, scattering, and simulation techniques. Wide‐angle X‐ray diffractions of oriented AZ4ICD samples indicate that the AZ4ICD molecule itself basically forms layer structures: one is a low‐ordered chiral smectic A LC phase (SmA*) with 5.61 nm layer periodicity at high temperatures, and two highly ordered smectic crystal (SmCr1 and SmCr2) phases are subsequently formed at lower temperatures with the anticlinically tilted molecular packing structures. The helical superstructures of chiral nematic LC phase (N*) can be spontaneously constructed by doping AZ4ICD chiral agents into the achiral nematic molecules. Due to the bent conformational geometry of AZ4ICD, the thermal window of blue LC phase (BP) is expanded by stabilizing the double twisted cylindrical building blocks. Remote‐controllable phase transformations in the mesomorphic helical superstructures are demonstrated by tuning the wavelength of light.
To understand the kinetically controlled polymorphic superstructures of asymmetric supramolecules, a pyrene-based asymmetric supramolecule (abbreviated as Py3M) was newly synthesized by connecting two pyrene headgroups (Py) to a biphenyl-based dendritic tail (3M) with an isophthalamide connector. On the basis of thermal, microscopic, spectroscopic, and scattering results, it was realized that Py3M exhibited the monotropic phase transition between a stable crystalline phase (K1) and a metastable crystalline phase (K2). This monotropic phase transition behavior was mainly originated from the competitions of intra- and intermolecular interactions (π–π interactions and hydrogen bonds) as well as from the nanophase separations. From the two-dimensional (2D) wide-angle X-ray diffraction patterns and transmission electron microscopy images of the self-assembled Py3M superstructures, it was found that Py3M formed two synclinically tilted crystalline superstructures: the 6.75 and 4.4 nm periodicities of layered structures for K1 and K2 phases, respectively. The stable K1 phase was predominantly induced by the π–π interactions between pyrenes, while the intermolecular hydrogen bonds between isophthalamides were the main driving forces for the formation of the metastable K2 phase. Ultraviolet–visible and photoluminescence experiments indicated that the photophysical properties of Py3M were directly related to their molecular packing superstructures.
Smart windows are very attractive because they not only provide comfortable indoor conditions for cars and buildings, but also protect privacy. However, current smart windows have problems such as high energy consumption, slow response time, and poor stability. To solve these problems, a single‐step dual stabilization (SSDS) is newly proposed for the fabrication of robust liquid crystal (LC) smart windows switching fast at low voltage. Upon irradiating ultraviolet light on the selected area of the nematic (N) LC optical cell with photoisomerizable macrogelators (B3AZ) and photopolymerizable monomers, NLC physical gels (LCPGs) and partition walls are simultaneously constructed. LCPGs play a role of light shutter under a low electric field (9.6 Vpp) which is ten times lower than that of the conventional polymer‐stabilized LC‐based smart windows. Partition walls constructed by the selected area photopolymerization significantly enhance the mechanical stabilities. Based on the experimental results, it is realized that the NLC layer generated near the partition walls makes the LCPGs respond to a low voltage. Robust SSDS smart windows could open new doors for the development of high‐performance smart windows.
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