Discotic liquid crystal compounds, flexible self-supporting quasicrystal thin films and applications, twelve-axis soft matter quasicrystal materials and preparation methods and applications

Abstract

The present application relates to soft matter quasicrystal material technical field, especially disc-shaped liquid crystal compound, flexible self-supporting quasicrystal film and application, twelve-axis soft matter quasicrystal material and preparation method and application, the disc-shaped liquid crystal compound described in the present application introduces specific side chain by periphery in benzophenanthrene, precisely controls the mutual effect between disc-shaped liquid crystal molecules, makes its columnar packing unit have specific " drive instruction ", introduces controllable transverse interaction outside pi-pi packing, thereby drives molecule spontaneously, intrinsic assembly into thermodynamic stable twelve times symmetry quasicrystal (i.e. twelve-axis soft matter quasicrystal material). The characteristics of single component avoid the phase separation problem of multi-component alloy, ensure the high purity and uniformity of structure. At the same time, through experimental verification, the type, position and distribution of the polar group at the end of the side chain in the molecule are the decisive factors for forming twelve times quasicrystal.

Description

Technical Field

[0001] This invention relates to the field of soft matter quasicrystalline materials technology, and particularly to disk-shaped liquid crystal compounds, flexible self-supporting quasicrystalline thin films and their applications, twelve-axis soft matter quasicrystalline materials and their preparation methods and applications. Background Technology

[0002] The main strategies for preparing soft matter quasicrystals include molecular alloying (multi-component blending), surface patterning-induced methods (template-dependent), and multi-level self-assembly methods. However, these methods suffer from poor controllability in preparing quasicrystal phases, require expensive equipment, and lack stability. Summary of the Invention

[0003] In view of this, the object of the present invention is to provide a disk-shaped liquid crystal compound, a flexible self-supporting quasicrystalline thin film and its application, a twelve-axis soft matter quasicrystalline material and its preparation method and application. The disk-shaped liquid crystal compound possesses specific "driving instructions" that can drive its spontaneous, intrinsic assembly into a thermodynamically stable twelve-fold symmetric quasicrystalline material (i.e., a twelve-axis soft matter quasicrystalline material).

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a disc-shaped liquid crystal compound having the structure shown in Formula 1: Formula 1; In Equation 1, R1, R2, R3, R4, R5, and R6 are independently -(CH2). m -X; The -(CH2) m In -X, X can be H, -CN, -NO2, -CF3, -OCF3, or -OCOC. n H 2n+1 The value of m ranges from 4 to 12; and the number of times X is H in R1, R2, R3, R4, R5 and R6 is ≤5. The -OCOC n H 2n+1 The range of values ​​for n is n≤12.

[0005] Preferably, in Formula 1, R1, R2, R3, R4, R5 and R6 are independently cyanohexyl, cyanobutyl, nitrohexyl or esteroctyl.

[0006] The present invention also provides the application of the disk-shaped liquid crystal compound described in the above technical solution in the preparation of twelve-axis soft matter quasi-crystalline materials.

[0007] This invention also provides a method for preparing a twelve-axis soft matter quasicrystalline material, comprising the following steps: The disk-shaped liquid crystal compound described in the above technical solution is subjected to initial melting, cooling, isothermal annealing and cooling in sequence to obtain the twelve-axis soft matter quasi-crystalline material.

[0008] Preferably, the initial melting target temperature is 20-30°C higher than the clearing point of the disc-shaped liquid crystal compound, the holding time is 5-10 min, and the heating rate to the initial melting target temperature is 5-20°C / min.

[0009] Preferably, the target temperature for cooling is located within the quasi-crystalline phase temperature range of the disk-shaped liquid crystal compound; The cooling rate is 0.5~2.0℃ / min.

[0010] Preferably, the isothermal annealing temperature is located within the quasi-crystalline phase temperature range of the disk-shaped liquid crystal compound; The isothermal annealing time is 2~10 hours; The cooling rate is 0.5~5.0℃ / min, and the target cooling temperature is room temperature.

[0011] The present invention also provides a twelve-axis soft matter quasi-crystalline material prepared by the preparation method described in the above technical solution.

[0012] The present invention also provides a flexible self-supporting quasicrystalline thin film, comprising the twelve-axis soft matter quasicrystalline material described in the above technical solution.

[0013] The present invention also provides the application of the twelve-axis soft quasi-crystalline material described in the above technical solution or the flexible self-supporting quasi-crystalline thin film described in the above technical solution in optoelectronic devices.

[0014] This invention provides a disc-shaped liquid crystal compound having the structure shown in Formula 1: Formula 1; In Equation 1, R1, R2, R3, R4, R5, and R6 are independently -(CH2). m -X; The -(CH2) m In -X, X can be H, -CN, -NO2, -CF3, -OCF3, or -OCOC. n H 2n+1 The value of m ranges from 4 to 12; and the number of times X is H in R1, R2, R3, R4, R5 and R6 is ≤5. The -OCOC n H 2n+1 The range of values ​​for n is n≤12.

[0015] The disk-shaped liquid crystal compound of this invention precisely controls the interactions between disk-shaped liquid crystal molecules by introducing specific side chains around benzo[a]phenanthrene, giving its columnar stacking units specific "driving instructions." This introduces controllable lateral interactions (such as dipole interactions, which originate from the directional dipole moments generated by the strongly polar groups at the ends of the side chains—like each side chain end carrying a tiny "magnet"—forcing adjacent molecular columns to align at specific relative angles and positions to reach the lowest energy state. It is this directional lateral force, breaking the spatial centrosymmetry, that forms a delicate game and balance with the inherent π-π stacking driving force of the benzo[a]phenanthrene core, which tends to form a regular periodic structure. This forces the system to abandon the simple hexagonal columnar phase and instead choose a more complex quasi-periodic arrangement with twelve rotational symmetries as its thermodynamic stable state, thereby driving the molecules to spontaneously and intrinsically assemble into thermodynamically stable twelve-fold symmetric quasi-crystals. The single-component nature avoids the phase separation problem of multi-component alloys, ensuring high purity and uniformity of the structure. Meanwhile, experiments have verified that the type, position, and distribution of the polar groups at the ends of the side chains in the molecule are the decisive factors for the formation of twelve-fold quasicrystals.

[0016] This invention also provides a method for preparing a twelve-axis soft matter quasi-crystalline material, comprising the following steps: sequentially subjecting a disk-shaped liquid crystal compound to initial melting, cooling, isothermal annealing, and cooling to obtain the twelve-axis soft matter quasi-crystalline material. The preparation method does not require expensive and complex micro / nano fabrication equipment such as electron beam lithography or nanoimprinting, nor does it require pre-preparation of patterned templates or application of complex external fields. The preparation method has a simple process flow, mild conditions, and is suitable for preparing large-area self-supporting thin films or bulk materials, possessing good potential for large-scale production. The main reason for this is that this invention fully integrates the "bottom-up" self-assembly driving force into the molecular design. Since the formation of twelve-fold symmetry is an inevitable result of molecular self-interaction, there is no need for "top-down" forced constraints; the preparation process only provides a suitable thermodynamic environment for molecular self-assembly and structural relaxation. This invention also provides a twelve-axis soft matter quasicrystalline material prepared by the preparation method described in the above technical solution. The twelve-axis soft matter quasicrystalline material exhibits a clear first-order reversible phase transition, a narrow phase transition temperature range, and a high enthalpy, indicating that the quasicrystalline phase is thermodynamically stable. Simultaneously, this material inherits the fast response characteristics of disk-shaped liquid crystals. Under stimulation by an external electric or light field, its columnar units can undergo collective and reversible reorientation, exhibiting excellent driving performance with threshold voltage, high contrast, and fast response speed. The main reasons for this are: Stability: Specific molecular design endows the quasicrystalline phase with thermodynamic advantages, and specific intermolecular force balance makes the twelve-fold symmetry structure its lowest free energy state within a specific temperature range; Functional driving performance: Dual sources: First, it retains the inherent dielectric anisotropy and other response characteristics of the columnar phase of benzo[a]phenanthrene disk-shaped liquid crystals; second, the long-range order of the quasicrystalline structure itself makes the collective movement of the columnar units highly coordinated, resulting in a more uniform and efficient response to external fields. The polar groups at the molecular ends also enhance the coupling ability of the molecules to external electric fields.

[0017] This invention also provides a flexible self-supporting quasicrystalline thin film, comprising the twelve-axis soft matter quasicrystalline material described in the above technical solution. The flexible self-supporting quasicrystalline thin film exhibits excellent photoelectric properties, and retains these excellent properties even when bent. Attached Figure Description

[0018] Figure 1 The images show the polarizing fiber texture of T8E36 described in Example 1 at different temperatures. Figure 2 The image shows the microstructure of T8E36 in the quasicrystalline phase as described in Example 1. Figure 3 The DSC curve of T8E36 described in Example 1; Figure 4 The image shows a two-dimensional wide-angle X-ray scattering pattern of the T8E36 described in Example 1. Figure 5 The carrier mobility curve of T8E36 in the columnar phase as described in Example 1; Figure 6 The image shows a polarized light microstructure of the self-supporting thin film (T8E36 / PVB) described in Example 3.

[0019] Figure 7 The differential scanning calorimetry (DSC) curve of T5E36PE described in Example 4. Figure 8 The images show the polarized light microtexture of T5E36PE as described in Example 4 at different temperatures. Figure 9 The image shows the microstructure of T5E36PE described in Example 4 in a quasicrystalline phase (i.e., a twelve-axis soft matter quasicrystalline material). Figure 10 The differential scanning calorimetry (DSC) curve of T5E36EE described in Example 5. Figure 11 The images show the polarized light microtexture of T5E36EE as described in Example 5 at different temperatures; Figure 12 This is a polarized light micrograph of the T5E36EE quasicrystalline state (i.e., the twelve-axis soft matter quasicrystalline material) described in Example 5. Detailed Implementation

[0020] This invention provides a disc-shaped liquid crystal compound having the structure shown in Formula 1: Formula 1; In Equation 1, R1, R2, R3, R4, R5, and R6 are independently -(CH2). m -X; The -(CH2) m In -X, X can be H, -CN, -NO2, -CF3, -OCF3, or -OCOC. n H 2n+1 The value of m ranges from 4 to 12; and the number of times X is H in R1, R2, R3, R4, R5 and R6 is ≤5. The -OCOC n H 2n+1 The range of values ​​for n is n≤12.

[0021] In this invention, the value of m is preferably 5, 6, 7, 8, 9, or 10, more preferably 8, 9, or 10. In this invention, the value of m ensures that the side chains have sufficient flexibility to promote molecular stacking in the columnar phase, while also providing the necessary steric effects and interactions.

[0022] In this invention, X is H, -CN, -NO2, -CF3, -OCF3, or -OCOC. n H 2n+1 The -OCOC n H 2n+1 The value of n is ≤12, preferably 4~12, and more preferably 4, 5, 6, 7, 8, 9, 10, 11 or 12.

[0023] In this invention, X is located in -(CH2). m The -X terminator is key to driving the formation of specific symmetries, namely -CN, -NO2, -CF3, -OCF3, and -OCOC. n H 2n+1 All of them are strong electron-withdrawing groups, which can generate significant and directional dipole moments, making them suitable for guiding transverse dipole-dipole interactions with twelve-fold symmetry.

[0024] In this invention, in Formula 1, R1, R2, R3, R4, R5 and R6 are preferably cyanohexyl, cyanobutyl, nitrohexyl or ester octyl; the ester octyl is preferably methyl ester octyl, ethyl ester octyl, propyl ester octyl, butyl ester octyl or pentyl ester octyl.

[0025] The present invention does not impose any particular limitation on the preparation method of the disc-shaped liquid crystal compound, which can be prepared by etherification or esterification reactions well known to those skilled in the art. In the present invention, when X in R1, R2, R3, R4, R5 and R6 includes H, -CN, -NO2, -CF3 or -OCF3, the substituent at the corresponding position is preferably prepared by etherification reaction; the present invention does not impose any particular limitation on the raw materials and conditions involved in the etherification reaction, which can be derived by conventional methods well known to those skilled in the art.

[0026] In this invention, when X in R1, R2, R3, R4, R5, and R6 includes -OCOC n H 2n+1 In this process, the substituents at the corresponding positions are preferably prepared by esterification. The present invention does not impose any special limitations on the raw materials and conditions involved in the esterification process, and the substituents can be obtained by conventional methods known to those skilled in the art.

[0027] The present invention also provides the application of the disk-shaped liquid crystal compound described in the above technical solution in the preparation of twelve-axis soft matter quasi-crystalline materials.

[0028] This invention also provides a method for preparing a twelve-axis soft matter quasicrystalline material, comprising the following steps: The disk-shaped liquid crystal compound described above was subjected to initial melting, cooling, isothermal annealing, and cooling sequentially to obtain the twelve-axis soft matter quasi-crystalline material.

[0029] In this invention, the target initial melting temperature is preferably 20-30°C higher than the clearing point of the disc-shaped liquid crystal compound, and more preferably 20°C, 22°C, 24°C, 26°C, 28°C, or 30°C higher. In an embodiment of this invention, the target initial melting temperature is specifically 140°C or 150°C. In this invention, the holding time for the initial melting is preferably 5-10 min, more preferably 5 min, 6 min, 7 min, 8 min, 9 min, or 10 min; the heating rate to the target initial melting temperature is preferably 5-20°C / min, more preferably 5°C / min, 10°C / min, 15°C / min, or 20°C / min. In an embodiment of this invention, the holding time for the initial melting can be 5 min, and the heating rate can be 10°C / min.

[0030] In this invention, the target temperature for cooling is preferably located within the quasi-crystalline phase temperature range of the disk-shaped liquid crystal compound; in embodiments of this invention, the target temperature for cooling can be 125°C, 110°C, or 128°C.

[0031] In this invention, the cooling rate is preferably 0.5~2.0℃ / min, more preferably 0.5℃ / min, 1.0℃ / min, 1.5℃ / min or 2.0℃ / min.

[0032] In this invention, the isothermal annealing temperature is preferably located within the quasi-crystalline phase temperature range of the disk-shaped liquid crystal compound; in embodiments of this invention, the isothermal annealing temperature can be 125°C, 110°C, or 128°C.

[0033] In this invention, the isothermal annealing time is preferably 2-10 hours, more preferably 2 hours, 4 hours, 6 hours, 8 hours, or 10 hours; the cooling rate is preferably 0.5-5.0 °C / min, more preferably 0.5 °C / min, 1 °C / min, 1.5 °C / min, 2.0 °C / min, 2.5 °C / min, 3.0 °C / min, 3.5 °C / min, 4.0 °C / min, 4.5 °C / min, or 5.0 °C / min; the target cooling temperature is room temperature. In an embodiment of this invention, the isothermal annealing time can be 5 hours, and the cooling rate can be 0.5 °C / min.

[0034] In this invention, by controlling the aforementioned initial melting, cooling, isothermal annealing, and cooling processes, sufficient time and energy can be provided for the built-in molecular driving commands to complete the long-range ordered assembly from disorder to a twelve-fold symmetric quasicrystalline structure. The assembly process is as follows: individual disk-shaped liquid crystal molecules self-assemble into one-dimensional columnar supramolecular polymers through face-to-face π-π stacking. These columnar supramolecular polymers, acting as "soft nanofibers," are spatially arranged in the transverse plane according to the quasi-periodic arrangement rules of the twelve-fold quasicrystalline structure.

[0035] The present invention also provides a twelve-axis soft matter quasi-crystalline material prepared by the preparation method described in the above technical solution.

[0036] In this invention, the twelve-axis soft matter quasi-crystalline material preferably comprises a material having a three-dimensional soft matter superstructure with long-range order but no translational periodicity, and the content is preferably ≥90wt%, more preferably ≥95wt%, and most preferably 100wt%.

[0037] In this invention, the twelve-axis soft matter quasi-crystalline material has twelve rotational symmetries, that is, in the direction perpendicular to the axis of the disk-shaped molecular column, its structural appearance is exactly the same as before the rotation for every 30° rotation.

[0038] In this invention, the melting temperature of the twelve-axis soft matter quasi-crystalline material is preferably 80~120℃; the clearing temperature is preferably 110~140℃.

[0039] In this invention, the twelve-axis soft matter quasi-crystalline material preferably has a focal cone texture of twelve or twenty-four lobes, which is a typical optical texture of a high-order rotationally symmetric liquid crystal phase.

[0040] The present invention also provides a flexible self-supporting quasicrystalline thin film, comprising the twelve-axis soft matter quasicrystalline material described in the above technical solution.

[0041] In this invention, the method for preparing the flexible self-supporting quasicrystalline thin film includes the following steps: The disc-shaped liquid crystal compound and an organic solvent are mixed to obtain a disc-shaped liquid crystal compound solution; After the disk-shaped liquid crystal compound solution is formed on the substrate, it is subjected to initial melting, cooling, isothermal annealing and cooling in sequence to obtain the flexible self-supporting quasicrystalline thin film.

[0042] The present invention involves mixing the disc-shaped liquid crystal compound with an organic solvent to obtain a disc-shaped liquid crystal compound solution.

[0043] In this invention, the organic solvent preferably includes tetrahydrofuran (THF) or chloroform.

[0044] The present invention does not impose any special limitations on the mixing process; any process known to those skilled in the art can be used.

[0045] After mixing, the present invention preferably includes filtration. The present invention does not have any special limitations on the filtration process, and any process known to those skilled in the art can be used.

[0046] In this invention, the concentration of the disk-shaped liquid crystal compound solution is preferably 3 to 30 wt%, more preferably 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, or 30 wt%.

[0047] After obtaining the disk-shaped liquid crystal compound solution, the present invention forms a film of the disk-shaped liquid crystal compound solution on a substrate, and then performs initial melting, cooling, isothermal annealing and cooling in sequence to obtain the flexible self-supporting quasicrystalline thin film.

[0048] In this invention, before forming the disc-shaped liquid crystal compound solution on the substrate, it is preferable to prepare a PVA film on the substrate surface.

[0049] In this invention, the preparation process of the PVA film preferably includes the following steps: Preparation of PVA solution; The PVA solution is coated onto the surface of the substrate to obtain a PVA film.

[0050] This invention relates to the preparation of PVA solutions.

[0051] In this invention, the concentration of the PVA solution is preferably 8 to 10 wt%, more preferably 8 wt%, 9 wt%, or 10 wt%.

[0052] In this invention, the PVA solution is preferably prepared by dissolving PVA in deionized water; the dissolution process is preferably carried out under stirring conditions, the stirring temperature is preferably 90°C, and the stirring time is preferably 4 hours. The stirring is to facilitate the formation of a homogeneous and transparent solution. After the dissolution is completed, this invention also preferably includes static degassing. This invention does not impose any special limitations on the static degassing process, and any process well known to those skilled in the art can be used.

[0053] After obtaining the PVA solution, the present invention coats the PVA solution onto the surface of the substrate to obtain a PVA film.

[0054] In this invention, the coating method is preferably a doctor blade coating method. This invention does not impose any special limitations on the process of the doctor blade coating method, and any process known to those skilled in the art can be used.

[0055] After the coating is completed, the present invention preferably includes pre-drying and drying in sequence; the pre-drying is preferably pre-drying at room temperature for 30 min; the drying is preferably vacuum drying at 60°C for 12 h.

[0056] In this invention, the substrate is preferably a polytetrafluoroethylene substrate (PTFE substrate).

[0057] In this invention, the film formation method is preferably spin coating or casting. This invention does not impose any special limitations on the casting process; any process well-known to those skilled in the art can be used. In this invention, the spin coating speed is preferably 800-1500 rpm, more preferably 800 rpm, 900 rpm, 1000 rpm, 1100 rpm, 1200 rpm, 1300 rpm, 1400 rpm, or 1500 rpm; the spin coating time is preferably 30-60 s, more preferably 30 s, 40 s, 50 s, or 60 s.

[0058] After the film is formed, the present invention preferably dries it. The drying is preferably carried out by evaporation at room temperature for 12 hours, or evaporation at room temperature for 30 minutes, followed by drying at 40°C for 2 hours, or vacuum drying at 40°C for 2 hours.

[0059] In this invention, the initial melting, cooling, isothermal annealing and cooling processes refer to the initial melting, cooling, isothermal annealing and cooling processes involved in the preparation of the above-mentioned twelve-axis soft matter quasi-crystalline material, and will not be repeated here.

[0060] After the cooling process is completed, the present invention preferably includes peeling. The present invention does not impose any special limitations on the peeling process, and any process known to those skilled in the art can be used.

[0061] This invention also provides the application of the twelve-axis soft quasi-crystalline material or the flexible self-supporting quasi-crystalline thin film described in the above-mentioned technical solutions in optoelectronic devices. This invention does not impose any special limitations on the methods for these applications; methods well-known to those skilled in the art can be used.

[0062] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0063] Example 1 Under nitrogen protection, 3,6-dihydroxy-2,7,10,11-trioctyloxybenzophenanthrene (1 g, 1.87 × 10⁻⁶) was added sequentially to a reaction apparatus equipped with a magnetic stirrer, a spherical condenser, and a 50 ml three-necked flask. -3 20 mL of anhydrous dichloromethane (DCM), dicyclohexylcarbodiimide (DCC), and 4-dimethylaminopyridine (DMAP) were added. After magnetic stirring for 15 minutes, acetic acid (0.51 g, 8.42 × 10⁻⁶ mol) was added using a syringe. -3 The solution (mol) was injected into a three-necked flask and immediately immersed in an oil bath at 45°C. The reaction was allowed to proceed for 12 hours, and the reaction progress was monitored by TLC. After the reaction was complete, the substrate was poured into a Buchner funnel and filtered to remove N,N-dicyclohexylurea (DCU). The solution was concentrated, purified by column chromatography, and recrystallized from ethanol to give the white product T8E36 (as shown in formula a, 1.04 g, yield 84.1%). 1H-NMR(300MHz, CDCl3)δ[ppm]:8.15(s,2H,Ar-H),7.92-7.81(d,4H,Ar-H),4.12-4.27(m,8H,-OCH2),2.68-2.77(dd,6 H,-OC(O)CH3),1.86-1.98(m,8H,-OCH2CH2),1.32-1.52(m,40H,-OCH2CH2CH2CH2CH2CH2CH2)0.94-1.00(t,12H,-CH3); FT-IR (cm) -1 ):2964,2934,1753,1620,1514,1434,1267,1183,1161. Formula a; The T8E36 was heated to 150℃ (20-30℃ higher than the clearing point) at a heating rate of 10℃ / min and held at that temperature for 30 min. Then, it was cooled from 150℃ to 125℃ (within the quasicrystalline phase temperature range) at a cooling rate of 1.0℃ / min and annealed at 125℃ for 5 h. Finally, it was cooled to room temperature (25℃) at a cooling rate of 2.0℃ / min to obtain a twelve-axis soft matter quasicrystalline material. Figure 1 The images show the polarization fiber texture of T8E36 described in Example 1 at different temperatures (where (a) is the polarization microtexture at 40°C, and (b) is the polarization microtexture at 100°C). Figure 1 As shown in (a), the T8E36 exhibits a distinct fan-shaped / petal-shaped polarization texture at 40℃, indicating that the sample possesses high orientational order and mesoscopic order at low temperatures; Figure 1 As shown in (b), after the temperature is raised to 100℃, the sample still maintains a clear polarization texture, but the texture morphology and birefringence color change significantly, indicating that T8E36 undergoes a phase structure transformation as the temperature increases, and forms an ordered liquid crystal phase at this temperature that is different from the low temperature state. Figure 2 The microstructure characterization diagram of T8E36 in the quasicrystalline phase described in Example 1 is shown (where (a) is a polarized light micrograph of the quasicrystalline state (in isotropic dark field), and (b) is an unpolarized light micrograph of the quasicrystalline state and a schematic diagram of its corresponding twelve-fold symmetry structure). Figure 2 As shown in (a), the quasicrystalline phase of the twelve-axis soft matter quasicrystalline material typically exhibits an approximately optically isotropic dark field under crossed polarization conditions, indicating that this phase differs from the obvious macroscopic birefringence texture characteristic of ordinary columnar liquid crystal phases. Figure 2As shown in (b) in the unpolarized micrograph, a local structural unit with twelve-fold symmetry can be observed. The corresponding structural schematic shows that the structure exhibits rotational symmetry that repeats approximately every 30° around the center, indicating that T8E36 has formed a mesoscopic ordered structure with twelve-fold rotational symmetry in the quasicrystalline phase. The twelve-axis soft matter quasicrystalline material was subjected to DSC testing. Figure 3 The DSC curve of T8E36 described in Example 1 is obtained from... Figure 3 It can be seen that the twelve-axis soft matter quasicrystalline material has a clear first-order reversible phase transition, and its phase transition sequence is crystal ↔ twelve-fold symmetric disk-shaped liquid crystal quasicrystalline phase ↔ isotropic liquid, with a Ti value of 123.6℃ and a ΔH value of 40.03kJ / mol; Figure 4 The two-dimensional wide-angle X-ray scattering pattern (2D WXRD pattern, 25°C) of T8E36 described in Example 1 is obtained from... Figure 4 It can be seen that the twelve-axis soft matter quasicrystal material satisfies the typical twelve-axis symmetry characteristic of a twelve-fold symmetric quasicrystal; The charge transport properties of the described twelve-axis soft matter quasicrystalline material were tested under the following conditions: the hole mobility of the sample at different temperatures was measured using the time-of-flight (TOF) method; during the test, the sample was clamped between two conductive electrodes, and an external electric field was applied when the sample was in the columnar liquid crystal phase temperature region, recording the carrier transport behavior in the sample. The test results are as follows: Figure 5 As shown. Figure 5 The carrier mobility curve of T8E36 in the columnar phase is given by... Figure 5 It can be seen that the hole mobility of T8E36 is approximately 8.85 × 10⁻⁶. -3 cm 2 ·V -1 ·s -1 Furthermore, the temperature of the Colhp phase remains largely unchanged within its range, indicating that T8E36 forms a stable one-dimensional π-π stacked charge transport channel within the columnar phase, exhibiting excellent columnar charge transport capability. After annealing to form a twelve-axis soft matter quasicrystalline phase, the sample exhibits insulating properties, suggesting that the formation of the quasicrystalline structure alters the arrangement of the columnar stacking units and the charge transport path, weakening or blocking continuous and effective carrier transport channels. These results demonstrate that the mesoscopic assembly structure of T8E36 has a significant regulatory effect on its electrical transport behavior, and the conductivity / insulation properties of the material can be adjusted through heat-induced phase structure transformation.

[0064] Example 2 The T8E36 and THF described in Example 1 were prepared into a T8E36 solution with a concentration of 50 mg / mL; After the T8E36 solution was cast onto a PTFE plate and dried, it was heated to 150°C (20-30°C above the cleaning point) at a heating rate of 10°C / min and held at that temperature for 30 min. Then, it was cooled from 150°C to 125°C (within the quasi-crystalline phase temperature range) at a cooling rate of 1.0°C / min, and annealed at 125°C for 5 h. Finally, it was cooled to room temperature (25°C) at a cooling rate of 2.0°C / min and peeled off to obtain a self-supporting film (carrier mobility 4 × 10⁻⁶). -4 cm 2 ·v -1 ).

[0065] Example 3 The T8E36 described in Example 1 was dissolved in chloroform and stirred at room temperature for 2 h until completely dissolved. The solution was then filtered through a 0.45 μm polytetrafluoroethylene filter membrane to remove particulate impurities, thus preparing a T8E36 solution with a concentration of 50 mg / mL. PVA was dissolved in deionized water to prepare a 10 wt% PVA solution. The solution was magnetically stirred at 90°C for 4 hours until a homogeneous and transparent solution was formed. The solution was then allowed to stand to remove bubbles, and the PVA solution was uniformly coated onto the surface of a clean glass substrate using a doctor blade coating method. After pre-drying at room temperature for 30 minutes, the solution was dried in a vacuum oven at 60°C for 12 hours to obtain a uniform and dense PVA film. The T8E36 chloroform solution was cast onto the surface of a PVA film, and the solvent was slowly evaporated at room temperature for 30 minutes. Then, it was dried at 40°C for 2 hours to fully remove the residual solvent, resulting in a T8E36 / PVA composite film with a uniform surface. Finally, the obtained film was heated to 150℃ at a heating rate of 10℃ / min (20~30℃ above the cleaning point) and held for 30 min. Then, it was cooled from 150℃ to 125℃ (within the quasi-crystalline phase temperature range) at a cooling rate of 1.0℃ / min, and annealed at 125℃ for 5 h. Finally, it was cooled to room temperature (25℃) at a cooling rate of 2.0℃ / min and peeled off to obtain a self-supported film (carrier mobility 3.0×10⁻⁶). -5 cm 2 ·v -1 ); Figure 6 The polarized light microstructure of the self-supporting thin film (T8E36 / PVA) described in Example 3 is shown below. Figure 9 It can be seen that the SAXS diagram of the self-supporting thin film is similar to the small-angle X-ray scattering (SAXS) diagram of the twelve-axis soft matter quasicrystalline material described in Example 1. Figure 1 To.

[0066] Example 4 Under nitrogen purging, the compound 3,6-dihydroxytetrapentoxybenzophenanthrene (4 g, 6.61 × 10⁻⁶) obtained in the previous step was subjected to nitrogen purging. -3 80 mL of anhydrous dichloromethane and appropriate amounts of dicyclohexylcarbodiimide and 4-dimethylaminopyridine were sequentially added to a 250 mL round-bottom three-necked flask equipped with a condenser and a magnetic stirrer. After the above reagents were added, the magnetic stirrer was turned on and the mixture was stirred for 30 minutes. After stirring for 30 minutes, 1.19 g of butyric acid (1.35 × 10⁻⁶ mol) was added using a syringe. 2 N,N-dicyclohexylurea (mol) was slowly injected into the reaction system, and the system was heated to 45°C in an oil bath. The reaction was carried out at this temperature for 12 hours, and the reaction progress was monitored by TLC. After the reaction was complete, the mixture in the flask was subjected to vacuum filtration using a Buchner funnel and a vacuum filtration flask to remove the N,N-dicyclohexylurea added to the reaction system. Excess solvent was then removed by rotary evaporation. Finally, the treated mixture was purified by column chromatography, and recrystallization from ethanol yielded 3.66 g of a white solid product T5E36PE (as shown in formula b), with a yield of 74.3%. Formula b; R f =0.50(EAC:PE=1:8);FT-IR (KBr): v max / cm -1 2960, 2934, 2873, 1739, 1617, 1521, 1437, 1394, 1267; 1H-NMR δH (300MHz, CDCl3) 8.00-7.82 (m, 6H, Ar-H), 4.26-4.19 (m, 8H, OCH2), 2.63-2.62 (t, 4H, OCH2), 1.97-1.86 (m, 8H, OCH2CH2), 1.59-1.42 (m, 20H, OCH2CH2CH2, OCH2CH2CH2CH2), 1.13-0.95(m, 18H, OCH2CH2CH2CH2CH3); The T5E36PE was heated to 220℃ at a heating rate of 10℃ / min and held at that temperature for 30 min to allow the sample to fully enter the isotropic liquid state. Then, it was cooled to the quasicrystalline phase temperature region at a cooling rate of 1.0℃ / min and annealed at this temperature region for 5 h. Finally, it was cooled to room temperature at a cooling rate of 2.0℃ / min to obtain the twelve-axis soft matter quasicrystalline material.

[0067] Figure 7 The differential scanning calorimetry (DSC) curve of T5E36PE described in Example 4 is obtained from... Figure 7It can be seen that during the first cooling process, a significant exothermic peak appears at approximately 208.50 °C, corresponding to the transformation of the material from the isotropic phase (Iso) to the hexagonal columnar liquid crystal phase (Colh), with a phase transition enthalpy of -31.87 J / g. Combined with polarized light microscopy observations, it is evident that this hexagonal columnar liquid crystal phase can be stably retained to room temperature, and no significant crystallization peaks were observed during subsequent cooling, indicating that the material did not undergo further crystallization. During the second heating process, a sharp endothermic peak appears at approximately 211.8 °C, corresponding to the transformation of the material from the hexagonal columnar liquid crystal phase (Colh) to the isotropic phase (Iso), with a phase transition enthalpy of approximately 31.98 J / g. This result indicates that the material exhibits good reversible liquid crystal phase transformation behavior.

[0068] Figure 8 The images show the polarized microtexture patterns of T5E36PE described in Example 4 at different temperatures, where (a) is the polarized microtexture pattern at 180°C and (b) is the polarized microtexture pattern at 58°C. Figure 8 It can be seen that T5E36PE exhibits a distinct fan-shaped / petal-shaped polarized texture at 180℃, indicating that the sample possesses high mesoscopic order at this temperature; Figure 8 As shown in (b), after cooling to 58℃, the sample still maintains obvious polarized texture, but the texture morphology and birefringence color change, indicating that T5E36PE undergoes a phase structure transformation with temperature change; Figure 9 This is a microstructure characterization image of T5E36PE in the quasicrystalline phase (i.e., a twelve-axis soft matter quasicrystalline material) as described in Example 4, from... Figure 9 It can be seen that in the quasicrystalline state, the sample exhibits an approximately optically isotropic dark field under crossed polarization conditions, indicating that this phase state is different from the obvious macroscopic birefringence texture in ordinary columnar liquid crystal phases, suggesting that T5E36PE can form a twelve-axis soft matter quasicrystalline phase.

[0069] Example 5 Under nitrogen protection, compound 6 (1g, 1.65×10⁻⁶) was added sequentially to a 50ml three-necked flask equipped with a magnetic stirrer and a spherical condenser. -3 20 mL of anhydrous dichloromethane, equimolar amounts of dicyclohexylcarbodiimide and 4-dimethylaminopyridine. After magnetic stirring for 20 minutes, acetic acid (0.25 g, 4.14 × 10⁻⁶ mol) was slowly added using a syringe. -3The solution (mol) was injected into a three-necked flask and immediately placed in an oil bath at 45°C for 12 h. The reaction was monitored by TLC. After the reaction was complete, the mixture was poured into a Buchner funnel and filtered to remove N,N-dicyclohexylurea. Excess solvent was removed by rotary evaporation under reduced pressure. Finally, the product was purified by column chromatography and recrystallized from ethanol to give 0.48 g of the white product T5E36EE (as shown in formula c), with a yield of 41.7%.

[0070] Formula c; TLC R f :0.67(ethyl acetate- petroleum ether 1:4); FT-IR (KBr): v max / cm - 1 3103, 2957,2853,1747,1521,1264; 1HNMR (300MHz, CDCl3), δ (ppm): 8.05-7.69 (m, 6H, Ar-H), 4.23-4.17 (m, 8H, OCH2), 2.41-2.40 (t, 6H, COOCH3), 1.96-1.86 (m, 8H, OCH2CH2),1.60-1.42(m,16H,OCH2CH2CH2,OCH2CH2CH2CH2)1-0.97(m,12H,OCH2CH2CH2CH2CH3); The T5E36EE was heated to 180°C at a heating rate of 10°C / min and held at that temperature for 30 min to allow the sample to fully enter the isotropic liquid state. Then, it was cooled to the quasicrystalline phase temperature region at a cooling rate of 1.0°C / min and annealed at this temperature region for 5 h. Finally, it was cooled to room temperature at a cooling rate of 2.0°C / min to obtain the twelve-axis soft matter quasicrystalline material. Figure 10 The differential scanning calorimetry (DSC) curve of the T5E36EE described in Example 5 is shown below. Figure 10 It was observed that during the second heating process, T5E36EE exhibited phase transition peaks at 134.9℃ and 173.1℃, corresponding to enthalpy changes of 6.11 J / g and 24.83 J / g, respectively. During the first cooling process, T5E36EE showed phase transition peaks at 121.1℃ and 167.4℃, corresponding to enthalpy changes of -4.28 J / g and -24.73 J / g, respectively. These results indicate that T5E36EE exhibits a clear multi-level reversible phase transition behavior during heating and cooling, suggesting that it can form different ordered liquid crystal phases or quasicrystalline phase structures with temperature changes. Figure 11The images show the polarized light microtexture of T5E36EE described in Example 5 at different temperatures, where (a) is a polarized light micrograph at 164°C and (b) is a polarized light micrograph at 40°C. Figure 11 As shown in (a), T5E36EE exhibits a distinct fan-shaped / petal-shaped polarized texture at 164℃, indicating that the sample possesses high orientational order at this temperature; Figure 11 As shown in (b), after cooling to 40℃, the sample still exhibits a clear polarization texture, indicating that it maintains a certain mesoscopic ordered structure at low temperatures. Figure 12 This is a polarized light micrograph (isotropic dark field) of the T5E36EE quasicrystalline state (i.e., a twelve-axis soft matter quasicrystalline material) described in Example 5. Figure 12 It can be seen that in the quasicrystalline state, the sample exhibits an approximately optically isotropic dark field under crossed polarization conditions, indicating that its quasicrystalline phase is different from the strong birefringence texture of ordinary columnar liquid crystal phase, indicating that T5E36EE can form a twelve-axis soft matter quasicrystalline material through heat treatment and annealing.

[0071] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A disc-shaped liquid crystal compound, characterized in that, It has the structure shown in Equation 1: Formula 1; In Equation 1, R1, R2, R3, R4, R5, and R6 are independently -(CH2). m -X; The -(CH2) m In -X, X can be H, -CN, -NO2, -CF3, -OCF3, or -OCOC. n H 2n+1 The value of m ranges from 4 to 12; and the number of times X is H in R1, R2, R3, R4, R5 and R6 is ≤5. The -OCOC n H 2n+1 The range of values ​​for n is n≤12.

2. The disk-shaped liquid crystal compound as described in claim 1, characterized in that, In Formula 1, R1, R2, R3, R4, R5 and R6 are independently cyanohexyl, cyanobutyl, nitrohexyl or esteroctyl.

3. The application of the disk-shaped liquid crystal compound according to claim 1 or 2 in the preparation of twelve-axis soft matter quasi-crystalline materials.

4. A method for preparing a twelve-axis soft matter quasicrystalline material, characterized in that, Includes the following steps: The disk-shaped liquid crystal compound of claim 1 is subjected to initial melting, cooling, isothermal annealing and cooling in sequence to obtain the twelve-axis soft matter quasi-crystalline material.

5. The preparation method according to claim 4, characterized in that, The initial melting target temperature is 20-30°C higher than the clearing point of the disk-shaped liquid crystal compound, the holding time is 5-10 min, and the heating rate to the initial melting target temperature is 5-20°C / min.

6. The preparation method according to claim 4, characterized in that, The target temperature for cooling is located within the quasi-crystalline phase temperature range of the disk-shaped liquid crystal compound; The cooling rate is 0.5~2.0℃ / min.

7. The preparation method according to claim 4, characterized in that, The isothermal annealing temperature is located within the quasi-crystalline phase temperature range of the disk-shaped liquid crystal compound; The isothermal annealing time is 2~10 hours; The cooling rate is 0.5~5.0℃ / min, and the target cooling temperature is room temperature.

8. The twelve-axis soft matter quasi-crystalline material prepared by the preparation method according to any one of claims 4 to 7.

9. A flexible self-supporting quasicrystalline thin film, characterized in that, Including the twelve-axis soft matter quasicrystalline material as described in claim 8.

10. The application of the twelve-axis soft matter quasi-crystalline material of claim 8 or the flexible self-supporting quasi-crystalline thin film of claim 9 in optoelectronic devices.

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