Preparation method of star-like graphene conjugated bridged benzophenanthrene discotic liquid crystal

Abstract

The invention belongs to the field of organic material chemistry, and discloses a preparation method and properties of star-like graphene conjugated bridged benzophenanthrene discotic liquid crystals, and the star-like graphene conjugated bridged benzophenanthrene discotic liquid crystals have structures shown in general formulas I, II and III. The compounds as shown in the general formulas I, II and III are mainly synthesized from a polybrominated hexaphenylbenzene compound and a benzophenanthrene borate derivative through Suzuki-Miyaura cross-coupling, the steps are simple and efficient, the atom utilization rate is high, and the yield is stable. The compounds have reversible thermotropic liquid crystal properties, most of the mesophases are hexagonal (Colh) and rectangular (Colr) columnar phases, the melting point and clearing point of the concatemer compounds are effectively improved through expansion of the conjugation degree and introduction of ortho-position methyl, the temperature range of the liquid crystal mesophases is widened, the types of the liquid crystal mesophases are enriched, and the compounds have rich self-assembly morphologies in organic solvents. Meanwhile, good fluorescence emission and absolute quantum yield are achieved in a solution and a thin film aggregation state, and the maximum emission wavelength and the maximum quantum yield in the solution are 401-409 nm and 63.89% respectively (the maximum emission wavelength and the maximum quantum yield in the aggregation state are 415-434 nm and 61.38% in the aggregation state).

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic material chemistry, and particularly relates to a preparation method and properties of star-shaped graphenoid conjugated bridged phenanthrene discotic liquid crystal. BACKGROUND

[0002] Organic small molecule discotic liquid crystals (DLCs) usually form columnar nanostructures through self-assembly in thermal cycles, and are a unique intelligent soft material with one-dimensional (1D) conductive properties. In the mesophase, the carriers can hop along the 1D supramolecular column, and the saturated flexible chains around the rigid discotic core fill in the column to act as an insulator, effectively preventing the energy or momentum dissipation (non-radiative transition) caused by the collision of carriers between columns due to Auger recombination. Therefore, the enhanced carrier transport performance of DLCs depends on the "rigid-flexible" properties in the molecular structure, which is usually composed of a large rigid central π-conjugated core and several peripheral flexible chains. The commonly reported planar central aromatic core includes phenanthrene, perylene imide, fluorene, pyrene, carbazole, fused thiophene, etc. The central aromatic core with flexible conformation is relatively lacking. Compared with organic macrocyclic conjugated aromatic single crystals, π-conjugated polymers and inorganic polycrystalline silicon materials, DLCs show the advantages of high carrier mobility and easy processing into high-performance thin films, and have wide application prospects in the field of organic thin film optoelectronic devices such as organic light-emitting diodes (OLEDs), organic field effect transistors (OFETs), organic photovoltaics (OPVs), etc. Based on this, we designed and synthesized a class of star-shaped graphenoid discotic liquid crystal molecules with flexible conformation of hexaphenylbenzene-phenanthrene multimer, and focused on comparing and studying the characteristics of the discotic compounds (HPB-TP2, HPB-TP4 and HPB-TP6) coupled with 2, 4 and 6 5-chain-containing phenanthrene multimers (-OC 10 H 21 chains and the corresponding discotic compounds (HPB-MTP2, HPB-MTP4 and HPB-MTP6) with the adjacent shortening of the phenanthrene connection point to -OCH3 in terms of liquid crystal properties, self-assembly order, and photophysical properties. SUMMARY

[0003] The present application belongs to the field of organic material chemistry, and particularly relates to a preparation method and properties of star-shaped graphenoid conjugated bridged phenanthrene discotic liquid crystal.

[0004] In the material synthesis work, mainly with commercial cheap diphenylacetylene derivatives as starting material, through Diels-Alder reaction, polymerization reaction and the like, important intermediates - polybrominated hexaphenylbenzene derivatives (HPB-2Br, HPB-4Br and HPB-6Br) are synthesized;Further, through Pd-catalyzed Suzuki-Miyaura cross-coupling reaction, a series of peripheral containing 2 (HPB-TP2 and HPB-MTP2), 4 (HPB-TP4 and HPB-MTP4), 6 (HPB-TP6 and HPB-MTP6) triphenylene units "star-shaped" multimeric compounds are precisely constructed, and the yield is stable;The target compounds obtained in the application, the liquid crystal, thermal performance, self-assembly and photo-physical properties are preliminarily studied;Research shows that it has a wide mesophase temperature range, can form stable hexagonal (Col h ), rectangular (Col r ) columnar mesophase, and the compound (HPB-TP6 and HPB-MTP6) coupled with 6 triphenylene units can also form an uncommon cubic phase (Cub);At the same time, the compound is not sensitive to oxygen, water and other environments, has good thermal stability, and has good photoelectric performance in solution or aggregate state, and has potential application in organic optoelectronic devices.

[0005] To achieve the above-mentioned purposes, the technical solution adopted is: a star-shaped graphene-like conjugated bridged triphenylene discotic liquid crystal compound, characterized in that the compound has the structures of I, II and III;Wherein R = -C n H 2n+1 , R' = -CH3 or -C n H 2n+1 , {n|6≤n≤10, n∈Z *};The content of the application relates to R = -C 10 H 21 , R' = -CH3 and -C 10 H 21 .

[0006] Compared with the prior art, the star-shaped graphene-like conjugated bridged triphenylene discotic liquid crystal compound of the general formula I, II and III has the following beneficial effects: First, in the method of the application, the drugs and reagents used are low in price, easy to obtain, the reaction conditions are mild, the atomic utilization rate is high, the steps are simple and efficient, the post-treatment operation is simple, the yield is stable, and it meets the basic requirements of laboratory or industrial production; II. Chemical structure is various, the property of discotic liquid crystal can be adjusted by adjusting the kind or chain length of R and R' group and the number and position of triphenylene group, so that the target compound has rich phase state, wide mesophase temperature range, excellent photoelectric functional properties, etc., so that it has wide application prospect in the field of organic thin film optoelectronic materials and devices.

[0007] The preparation method of the star-shaped graphene-like conjugated bridged triphenylene discotic liquid crystal compound of general formula I, II and III is simple and efficient, and the liquid crystal performance is excellent, and the application will be further described in detail below with specific examples. BRIEF DESCRIPTION OF DRAWINGS

[0008] Figure 1 It is the nuclear magnetic resonance hydrogen spectrum of the intermediate compound TP10-Br obtained in example 1.

[0009] Figure 2 It is the nuclear magnetic resonance carbon spectrum of the intermediate compound TP10-Br obtained in example 1.

[0010] Figure 3 It is the nuclear magnetic resonance hydrogen spectrum of the intermediate compound MTP10-Br obtained in example 2.

[0011] Figure 4 It is the nuclear magnetic resonance carbon spectrum of the intermediate compound MTP10-Br obtained in example 2.

[0012] Figure 5 It is the nuclear magnetic resonance hydrogen spectrum of the intermediate compound TP10-Bpin obtained in example 3.

[0013] Figure 6 It is the nuclear magnetic resonance carbon spectrum of the intermediate compound TP10-Bpin obtained in example 3.

[0014] Figure 7 It is the nuclear magnetic resonance hydrogen spectrum of the intermediate compound MTP10-Bpin obtained in example 4.

[0015] Figure 8 It is the nuclear magnetic resonance carbon spectrum of the intermediate compound MTP10-Bpin obtained in example 4.

[0016] Figure 9 It is the nuclear magnetic resonance hydrogen spectrum of the intermediate compound HPB-2Br obtained in example 5.

[0017] Figure 10 It is the nuclear magnetic resonance carbon spectrum of the intermediate compound HPB-2Br obtained in example 5.

[0018] Figure 11 It is the nuclear magnetic resonance hydrogen spectrum of the intermediate compound HPB-4Br obtained in example 6.

[0019] Figure 12 NMR carbon spectrum of the intermediate compound HPB-4Br obtained in Example 6.

[0020] Figure 13 NMR hydrogen spectrum of the intermediate compound HPB-6Br obtained in Example 7.

[0021] Figure 14 NMR carbon spectrum of the intermediate compound HPB-6Br obtained in Example 7.

[0022] Figure 15 NMR hydrogen spectrum of the target compound HPB-TP2 obtained in Example 8.

[0023] Figure 16 NMR carbon spectrum of the target compound HPB-TP2 obtained in Example 8.

[0024] Figure 17 High resolution mass spectrum of the target compound HPB-TP2 obtained in Example 8.

[0025] Figure 18 Polarized optical texture of the target compound HPB-TP2 obtained in Example 8.

[0026] Figure 19 DSC chart of the target compound HPB-TP2 obtained in Example 8.

[0027] Figure 20 XRD chart of the target compound HPB-TP2 obtained in Example 8.

[0028] Figure 21 NMR hydrogen spectrum of the target compound HPB-MTP2 obtained in Example 8.

[0029] Figure 22 NMR carbon spectrum of the target compound HPB-MTP2 obtained in Example 8.

[0030] Figure 23 High resolution mass spectrum of the target compound HPB-MTP2 obtained in Example 8.

[0031] Figure 24 Polarized optical texture of the target compound HPB-MTP2 obtained in Example 8.

[0032] Figure 25 DSC chart of the target compound HPB-MTP2 obtained in Example 8.

[0033] Figure 26 XRD chart of the target compound HPB-MTP2 obtained in Example 8.

[0034] Figure 27 NMR spectrum of the target compound HPB-TP4 obtained in Example 9.

[0035] Figure 28 NMR spectrum of the target compound HPB-TP4 obtained in Example 9.

[0036] Figure 29 High resolution mass spectrum of the target compound HPB-TP4 obtained in Example 9.

[0037] Figure 30 Polarizing optical texture of the target compound HPB-TP4 obtained in Example 9.

[0038] Figure 31 DSC chart of the target compound HPB-TP4 obtained in Example 9.

[0039] Figure 32 XRD chart of the target compound HPB-TP4 obtained in Example 9.

[0040] Figure 33 NMR spectrum of the target compound HPB-MTP4 obtained in Example 9.

[0041] Figure 34 NMR spectrum of the target compound HPB-MTP4 obtained in Example 9.

[0042] Figure 35 High resolution mass spectrum of the target compound HPB-MTP4 obtained in Example 9.

[0043] Figure 36 Polarizing optical texture of the target compound HPB-MTP4 obtained in Example 9.

[0044] Figure 37 DSC chart of the target compound HPB-MTP4 obtained in Example 9.

[0045] Figure 38 XRD chart of the target compound HPB-MTP4 obtained in Example 9.

[0046] Figure 39 NMR spectrum of the target compound HPB-TP6 obtained in Example 10.

[0047] Figure 40 NMR spectrum of the target compound HPB-TP6 obtained in Example 10.

[0048] Figure 41High resolution mass spectrum of the target compound HPB-TP6 obtained in Example 10.

[0049] Figure 42 Polarized optical texture of the target compound HPB-TP6 obtained in Example 10.

[0050] Figure 43 DSC plot of the target compound HPB-TP6 obtained in Example 10.

[0051] Figure 44 XRD plot of the target compound HPB-TP6 obtained in Example 10.

[0052] Figure 45 Proton nuclear magnetic resonance spectrum of the target compound HPB-MTP6 obtained in Example 10.

[0053] Figure 46 Carbon nuclear magnetic resonance spectrum of the target compound HPB-MTP6 obtained in Example 10.

[0054] Figure 47 High resolution mass spectrum of the target compound HPB-MTP6 obtained in Example 10.

[0055] Figure 48 Polarized optical texture of the target compound HPB-MTP6 obtained in Example 10.

[0056] Figure 49 DSC plot of the target compound HPB-MTP6 obtained in Example 10.

[0057] Figure 50 XRD plot of the target compound HPB-MTP6 obtained in Example 10.

[0058] Figure 51 Thermogravimetric analysis TGA plot of the target compounds HPB-TP2, HPB-MTP2, HPB-TP4, HPB-MTP4, HPB-TP6 and HPB-MTP6 obtained in Examples 8-10.

[0059] Figure 52 UV-visible absorption spectrum of the target compounds HPB-TP2, HPB-TP4 and HPB-TP6 obtained in Examples 8-10 in organic solvents.

[0060] Figure 53 Fluorescence emission spectrum and quantum yield of the target compounds HPB-TP2, HPB-TP4 and HPB-TP6 obtained in Examples 8-10 in organic solvents.

[0061] Figure 54Fluorescence emission spectra of the target compounds HPB-TP2, HPB-TP4 and HPB-TP6 obtained in Examples 8-10 in thin film state and quantum yield.

[0062] Figure 55 UV-Vis absorption spectra of the target compounds HPB-TP2, HPB-TP4 and HPB-TP6 obtained in Examples 8-10 in tetrahydrofuran solvent with gradient water content.

[0063] Figure 56 Fluorescence emission spectra of the target compounds HPB-TP2, HPB-TP4 and HPB-TP6 obtained in Examples 8-10 in tetrahydrofuran solvent with gradient water content.

[0064] Figure 57 Self-assembly morphology scanning electron microscopy (SEM) of the target compounds HPB-TP2, HPB-TP4 and HPB-TP6 obtained in Examples 8-10 in cyclohexane solvent.

[0065] Figure 58 A designated specification abstract drawing, wherein I, II, III are general formulae of a star-shaped graphenic conjugated bridged phenanthrene discotic liquid crystal compound. DETAILED DESCRIPTION

[0066] The present application will be further described in the following specific examples, but not used to limit the protection scope of the present application. Those skilled in the art can make improvements to the preparation method and use instruments within the scope of the claims without departing from the concept of the present application, and these improvements should also be considered as the protection scope of the present application.

[0067] Example 1: Synthesis of intermediate TP10-Br (2-bromo-3,6,7,10,11-pentakis (decyloxy) phenanthrene) A preparation method of 2-bromo-3,6,7,10,11-pentakis (decyloxy) phenanthrene TP10-Br, its synthesis and steps are as follows: Step one (synthesis of TP1-Br): BP1 (5.00 g, 18.23 mmol) and 2-bromoanisole (5.11 g, 27.34 mmol) were stirred in dry CH2Cl2(80.0 mL) at room temperature, then a solution of FeCl3(17.74 g, 109.36 mmol) dissolved in CH3NO2(20.0 mL) was added to the above solution; after 2 hours, the solution was poured into ice water (30.0 mL)-methanol (30.0 mL) and stirred at room temperature for another 10 minutes to obtain the precipitated product; then, the mixture was filtered through a Buchner funnel, the residue was purified by silica gel column chromatography (pure CH2Cl2), and recrystallized in ethanol to obtain TP1-Br (6.24 g, 75%) as a gray-white powder; the structure of TP1-Br was identified by nuclear magnetic resonance hydrogen spectrum, carbon spectrum: 1 H NMR (CDCl3, TMS, 600MHz) δ (ppm): 8.06 (s, 1H), 7.49 (s, 1H), 7.40 (s, 1H), 7.35 (s, 1H), 7.31 (s, 1H),7.17 (s, 1H), 4.09 (s, 6H), 4.04 (s, 6H), 4.00 (s, 3H). 13 C NMR (CDCl3, 151MHz) δ (ppm): 153.38, 149.20, 148.46, 148.42, 148.28, 128.72, 127.22, 124.04, 123.55, 122.44, 122.10, 121.87, 111.04, 104.00, 103.73, 103.51, 103.39, 56.06, 55.96, 55.87, 55.85. Step two (synthesis of TP10-Br): TP1-Br (5.00 g, 10.93 mmol) was added to a schlenk reaction tube under argon, stirred with dry CH2Cl2(20.0 mL); the mixture was placed in -78 °C, then BBr3(7.37 mL, 76.53 mmol) was injected into the reaction system, and stirred overnight; then, the solution was poured into ice water (200.0 mL) and stirred until the mixture returned to room temperature; subsequently, the mixture was filtered with a Buchner funnel (double-layer filter paper) and the residue was dried under argon to obtain a purple-black solid, 11-bromotriphenylen-2,3,6,7,10-pentanol; immediately, 11-bromotriphenylen-2,3,6,7,10-pentanol, 1-bromodecane (14.51 g, 65.60 mmol), K2CO3(18.13 g, 131.20 mmol), zinc powder (356.10 mg, 5.47 mmol) and KI (907.47 mg, 5.47 mmol) were added to a 250 mL round-bottom flask, and solvent DMF (70.0 mL) was added; the system was heated to 90 °C and stirred for 24 hours; then, immediately pour the hot mixture into ice water in a 500 mL beaker, and add dilute hydrochloric acid to the solution until the system is acidic, filter in a Buchner funnel (double-layer filter paper), evaporate the solvent; purify the product by silica gel column chromatography (CH2Cl2 / petroleum ether, 1:2, v / v), and recrystallize from ethyl acetate and ethanol to obtain white solid TP10-Br (8.37 g, 70%); in this example, the structure of the intermediate TP10-Br was identified by nuclear magnetic resonance hydrogen spectrum, carbon spectrum: 1 H NMR (CDCl3, TMS, 600MHz) δ (ppm): 8.55 (s, 1H), 7.82 (s, 1H), 7.77-7.76 (m, 3H), 7.74 (s, 1H), 4.25-4.23 (m, 10H), 1.99-1.92 (m, 10H), 1.63-1.57 (m, 10H), 1.45-1.40 (m, 10H),1.36-1.29 (m, 50H), 0.89 (t, J = 6.6 Hz, 15H). 13C NMR (CDC13, 151 MHz) δ (ppm): 153.58, 149.97, 149.37, 149.03, 148.81, 129.31, 127.72, 124.82, 124.07, 123.12, 122.70, 112.23, 107.71, 107.27, 106.84, 106.20, 105.69, 69.86, 69.80, 69.48, 69.46, 69.28, 31.93, 29.70, 29.62, 29.59, 29.55, 29.51, 29.49, 29.48, 29.45, 29.42, 29.38, 29.35, 29.25, 26.21, 26.15, 22.69, 14.11.

[0068] Example 2: Synthesis of intermediate MTP10-Br (2-bromo-6,7,10,11-tetra(decyloxy)-3-methoxytriphenylenyl) A method for preparing 2-bromo-6,7,10,11-tetra(decyloxy)-3-methoxytriphenylenyl MTP10-Br, its synthesis and steps are as follows: Step one (synthesis of BP10): The synthesis and purification of BP10 refer to TP10-Br in Example one; wherein the feeding amount is BP1 (5.00 g, 18.23 mmol), BBr3 (10.54 mL, 109.36 mmol), 1-bromodecane (24.19 g, 109.36 mmol), K2CO3 (25.19 g, 182.27 mmol), zinc powder (593.66 mg, 9.11 mmol), KI (1.51 g, 9.11 mmol), and finally white solid BP10 (9.07 g, 64%) is obtained; the structure of BP10 is identified by nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1 H NMR (CDC13, TMS, 600MHz) δ (ppm): 7.07-7.05 (m, 4H), 6.92 (d, J = 8.0 Hz, 2H), 4.06 (t, J = 6.6 Hz, 4H), 4.03 (t, J = 6.6 Hz, 4H), 1.87-1.81 (m, 8H), 1.51-1.46 (m, 8H), 1.39-1.26 (m, 48H), 0.90-0.88 (m, 12H). 13C NMR (CDCI3, 151 MHz) δ (ppm): 149.27, 148.47, 134.35, 119.30, 114.20, 113.19, 69.53, 69.44, 31.91, 29.64, 29.59, 29.45, 29.40, 29.35, 26.07, 26.06, 22.68, 14.10. Step two (synthesis of MTP10-Br): The synthesis and purification of MTP10-Br refer to TP1-Br in Example one; wherein the feeding amount is BP10 (5.00 g, 6.42 mmol), 2-bromoanisole (2.40 g, 12.83 mmol), FeCl3(5.20 g, 32.08 mmol), respectively. Finally, white solid MTP10-Br (3.54 g, 57%) was obtained; in this example, the structure of intermediate MTP10-Br was identified by nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1 H NMR (CDCI3, TMS, 600MHz) δ (ppm): 8.50 (s, 1H), 7.80 (s, 1H), 7.74 (d, J = 3.0 Hz, 2H), 7.70 (d, J = 6.6 Hz, 2H), 4.25-4.20 (m, 8H), 4.10 (s, 3H), 1.98-1.92 (m, 8H), 1.61-1.55 (m, 8H), 1.46-1.40 (m, 8H), 1.36-1.27 (m, 40H), 0.89 (t, J = 6.6 Hz, 12H). 13 C NMR (CDCI3, 151 MHz) δ (ppm): 153.84, 149.99, 149.32, 149.05, 148.79, 129.29, 127.77, 124.83, 124.15, 123.13, 122.67, 122.58, 111.44, 107.58, 107.18, 106.75, 106.16, 104.31, 69.84, 69.76, 69.42, 69.27, 56.33, 31.93, 29.70, 29.62, 29.55, 29.50, 29.49, 29.43, 29.41, 29.38, 26.20, 26.17, 22.69, 14.10.

[0069] Example 3: Synthesis of intermediate TP10-Bpin (4,4,5,5-tetramethyl-2-(3,6,7,10,11-pentakis(decyloxy)triphenylen-2-yl)-1,3,2-dioxaborolane) A method for preparing 4,4,5,5-tetramethyl-2-(3,6,7,10,11-pentakis(decyloxy)triphenylen-2-yl)-1,3,2-dioxaborolane TP10-Bpin, its synthesis and steps are as follows: Synthesis of TP10-Bpin: In a dry flask under argon atmosphere protection, TP10-Br (2.0 g, 1.84 mmol), bis(pinacolato)diboron (1.03 g, 4.04 mmol), Pd(dppf)Cl2·CH2Cl2(90.03 mg, 0.11 mmol) and CH3COOK (540.96 mg, 5.51 mmol) were added; after adding 1,4-dioxane (70.0 mL), the reaction was stirred at 90°C for 24 hours; then, the reaction mixture was cooled to room temperature and extracted with CH2Cl2; the combined organic layers were dried over anhydrous MgSO4, evaporated, and the residue was purified by column chromatography (eluent petroleum ether / CH2Cl2, 1:3, v / v); recrystallized from ethyl acetate and ethanol to obtain white solid TP10-Bpin (1.44 g, 69%); in this example, the structure of intermediate TP10-Bpin was identified by nuclear magnetic resonance hydrogen spectrum, carbon spectrum: 1 H NMR (CDCl3, TMS, 600MHz) δ (ppm): 8.96 (s,1H), 8.05 (s, 1H), 7.90 (s, 1H), 7.82-7.76 (m, 3H), 4.33-4.22 (m, 10H), 1.99-1.91 (m, 10H), 1.58-1.40 (m, 26H), 1.35-1.23 (m, 56H), 0.88 (t, J = 6.8 Hz,15H). 13C NMR (CDCl3, 151 MHz) δ (ppm): 162.03, 150.38, 150.24, 149.49, 149.29, 148.90, 148.67, 132.68, 132.22, 125.59, 124.19, 122.88, 108.31, 107.46, 107.35, 106.85, 103.01, 102.86, 70.03, 69.89, 69.51, 69.41, 69.38, 68.53, 58.48, 58.39, 31.93, 31.89, 29.70, 29.62, 29.55, 29.51, 29.44, 29.38, 29.32, 26.25, 26.20, 22.69, 22.68, 14.11.

[0070] Example 4: Synthesis of intermediate MTP10-Bpin (4,4,5,5-tetramethyl-2-(6,7,10,11-tetra(decaoxy)-3-methoxytriphenylen-2-yl)-1,3,2-dioxaborolane) A method for preparing 4,4,5,5-tetramethyl-2-(6,7,10,11-tetra(decaoxy)-3- methoxytriphenylen-2-yl)-1,3,2-dioxaborolane MTP10-Bpin, the synthesis and steps of which are as follows: Synthesis of MTP10-Bpin: The synthesis and purification of MTP10-Bpin refer to TP10-Bpin of Example 3; wherein the feeding amount is MTP10-Br (2.0 g, 2.08 mmol), pinacol diboronic acid (1.58 g, 6.24 mmol), Pd(dppf)Cl2·CH2Cl2(101.84 mg, 0.12 mmol), CH3COOK (408.0 mg, 4.16 mmol), and finally white solid MTP10-Bpin (1.27 g, 60%) is obtained; in this example, the structure of the intermediate MTP10-Bpin is identified by nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1H NMR (CDC13, TMS, 600MHz) δ (ppm): 8.97 (s, 1H), 8.05 (s, 1H), 7.91(s, 1H), 7.82 (s, 2H), 7.79 (s, 1H), 4.27-4.21 (m, 8H), 4.15 (s, 3H), 1.97-1.91 (m, 8H), 1.59-1.55 (m, 8H), 1.44 (s, 12H), 1.43-1.39 (m, 8H), 1.35-1.25(m, 40H), 0.88 (t, J = 6.6 Hz, 12H). 13 C NMR (CDC13, 151 MHz) δ (ppm): 162.45,150.38, 149.49, 148.94, 148.72, 132.70, 132.52, 125.72, 124.13, 123.06,122.96, 122.85, 108.17, 107.45, 106.99, 106.78, 102.17, 83.67, 69.89, 69.77,69.43, 69.38, 55.61, 31.92, 29.69, 29.62, 29.53, 29.40, 29.38, 26.19, 24.91,22.69, 14.11.。

[0071] Example 5: Synthesis of intermediate HPB-2Br (4,4''-dibromo-3',4',5',6'- tetraphenyl-1,1':2',1''-terphenyl) A method for preparing 4,4''-dibromo-3',4',5',6'-tetraphenyl-1,1':2',1''- terphenyl HPB-2Br, its synthesis and steps are as follows: M1 (1.31 g, 3.90 mmol), M2 (1.0 g, 2.60 mmol) and benzophenone (5.5 g) were added into a glass reaction tube under argon protection; the mixture was stirred and heated to 305°C, refluxing for 3 hours; after stopping heating, when the temperature of the reaction system dropped to about 100°C, diphenyl ether (2 mL) was added to prevent M2 from solidifying at low temperature in the system; after cooling to room temperature, toluene was added to dilute the reaction solution; then, the mixture was filtered with a Buchner funnel, washed with toluene several times, and dried to obtain off-white solid powder HPB-2Br (1.72 g, 64%); in this example, the structure of the intermediate HPB-2Br was identified by nuclear magnetic resonance hydrogen spectrum and carbon spectrum:1 H NMR (CDCl3, TMS, 600MHz) δ (ppm): 7.68-7.66 (m, 2H), 7.60-7.59(m, 2H), 7.44 (d, J = 8.4 Hz, 4H), 7.30-7.27 (m, 8H), 7.23-7.20 (m, 8H), 7.11(d, J = 8.4 Hz, 4H). 13 C NMR (CDCl3, 151 MHz) δ (ppm): 140.86, 140.38, 140.20,140.03, 139.32, 138.80, 137.85, 132.89, 131.22, 130.02, 129.02, 128.21,126.84, 126.62, 125.51, 125.33, 125.28, 119.70.。

[0072] Example 6: Synthesis of intermediate HPB-4Br (2',3',5',6'-Tetra(4-bromophenyl)-1,1':4',1''-terphenyl) A method for preparing 2',3',5',6'-tetra(4-bromophenyl)-1,1':4',1''-terphenyl HPB-4Br, its synthesis and steps are as follows: The synthesis and purification of HPB-4Br refer to HPB-2Br in Example 5; wherein the feeding amount is M1 (929.50 mg, 2.77 mmol), M3 (1.0 g, 1.84 mmol), benzophenone (5.0 g), respectively, and finally the off-white solid powder HPB-4Br (961.10 mg, 61%) is obtained; in this example, the structure of the intermediate HPB-4Br is identified by nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1 HNMR (C2D2Cl4, TMS, 600MHz) δ (ppm): 7.02 (d, J = 8.4 Hz, 8H), 6.91-6.89 (m,5H), 6.77-6.74 (m, 5H), 6.66 (d, J = 8.4 Hz, 8H). 13 C NMR (C2D2Cl4, 151 MHz) δ(ppm): 139.05, 132.68, 130.91, 129.95, 129.86, 128.30, 126.96, 119.49.。

[0073] Example 7: Synthesis of intermediate HPB-6Br (4,4''-dibromo-3',4',5',6'-tetra(4- bromophenyl)-1,1':2',1''-terphenyl) A method for preparing 4,4''-dibromo-3',4',5',6'-tetra(4-bromophenyl)-1,1':2',1''- terphenyl HPB-6Br, its synthesis and steps are as follows: M1 (6.72 g, 20.00 mmol) was dissolved in 150 mL of 1, 4-dioxane under argon protection, then Co2(CO)8(1.37 g, 4.00 mmol) was added, and the mixed system was refluxed at 120°C in an argon atmosphere for 12 hours, then cooled to room temperature and concentrated under reduced pressure; the obtained residue was refluxed and eluted with heated petroleum ether for 3 hours; then recrystallized with methanol to obtain off-white powder HPB-6Br (5.90 g, 88%); in this example, the structure of the intermediate HPB-6Br was identified by nuclear magnetic resonance hydrogen spectrum and carbon spectrum: 1 H NMR (C2D2Cl4, TMS, 600MHz) δ (ppm): 7.06 (d, J = 8.4 Hz, 12H), 6.63 (d, J = 8.4 Hz, 12H). 13 C NMR (C2D2Cl4, 151 MHz) δ (ppm): 139.21, 138.39, 132.45, 130.21, 119.96..

[0074] Example 8: Synthesis of target compounds HPB-TP2 and HPB-MTP2 A method for preparing a hexaphenylbenzene-benzo[ghi]phenanthrene dimer compound HPB-TP2 and HPB-MTP2, its synthesis and steps are as follows: Synthesis of HPB-TP2: HPB-2Br (100.0 mg, 0.14 mmol), TP10-Bpin (983.92 mg, 0.87 mmol), K2CO3(399.15 mg, 2.89 mmol) and Pd(PPh3)4(100.12 mg, 0.09 mmol) were mixed in a solvent mixture of THF / H2O (9.0 mL / 3.0 mL) under argon protection and stirred; the mixture was heated to 70 °C for 24 h under stirring; after cooling, the mixture was extracted with CH2Cl2, dried over MgSO4, and the solvent was removed under vacuum; the residue was eluted by silica gel column chromatography (petroleum ether / CH2Cl2, 1.5 / 1, v / v); recrystallized from ethyl acetate-ethanol to obtain HPB-TP2 (222.50 mg, 60%) as a white solid; the structure of the target compound HPB-TP2 was identified by1H NMR,13C NMR, HRMS, elemental analysis in this example: 1 H NMR (CDCl3, TMS, 600MHz) δ (ppm): 8.15 (s,2H), 7.84 (s, 2H), 7.79 (s, 2H), 7.77 (d, J = 6.0 Hz, 4H), 7.74 (s, 2H), 7.30(d, J = 8.4 Hz, 4H), 7.03 (d, J = 8.4 Hz, 4H), 6.97-6.87 (m, 20H), 4.23-4.12(m, 8H), 4.13 (t, J = 6.0 Hz, 4H), 3.94 (t, J = 6.0 Hz, 4H), 3.89 (t, J = 6.3Hz, 4H), 1.95-1.87 (m, 10H), 1.63-1.49 (m, 20H), 1.43-1.11 (m, 130H), 0.89-0.84 (m, 30H). 13 C NMR (CDCl3, 151 MHz) δ(ppm): 155.03, 149.59, 149.10,148.76, 140.76, 140.73, 140.47, 140.41, 140.38, 139.38, 135.47, 131.57,131.50, 131.19, 130.82, 129.17, 128.07, 126.65, 126.59, 125.16, 124.63,124.03, 123.24, 123.13, 107.68, 107.03, 105.91, 69.82, 69.72, 69.53, 69.44,68.93, 31.96, 31.93, 29.70, 29.64, 29.62, 29.56, 29.52, 29.49, 29.47, 29.38,29.31, 29.24, 26.21, 26.19, 26.04, 26.00, 22.69, 14.13, 14.11. HRMS (MALDI):[M] + calcd for C 178 H 250 O 10 , m / z: 2548.9088 (100.0%), 2549.9121 (95.7%), 2547.9054 (51.9%), 2550.9155 (33.6%), 2550.9155 (27.1%); found, 2548.9085,2549.9125, 2547.9046, 2550.9164, 2551.9202. Elemental analysis: calculated for C 178 H 250 O 10 (2549.95), C 83.84%, H 9.88%; found, C 83.73%, H 9.64%.; In terms of performance, its good thermal stability, typical liquid crystal texture, wide liquid crystal phase transition range, and hexagonal columnar (Col) structure were tested using a polarizing microscope (POM) with a hot stage, differential scanning calorimetry (DSC), and small-angle / wide-angle X-ray scattering (S / WAXS) techniques. h The intermediate phase stacking method was studied, and its ultraviolet-visible absorption spectroscopy, fluorescence emission spectroscopy, and absolute quantum yield were tested. Synthesis of HPB-MTP2: The synthesis and purification of HPB-MTP2 were according to the above HPB-TP2; where the feeding amount and condition were HPB-2Br (102.91 mg, 0.15 mmol), MTP10-Bpin (600.00 mg, 0.59 mmol), K2CO3 (205.38 mg, 1.49 mmol), Pd(PPh3)4 (51.52 mg, 0.04 mmol) and THF / H2O (9.0 mL / 3.0 mL); the mixture was heated to 70 °C with stirring for 24 h; the residue was eluted by silica gel column chromatography (petroleum ether / CH2Cl2, 1 / 1, v / v); recrystallized from ethyl acetate-ethanol to give white solid HPB-MTP2 (225.70 mg, 66%); the structure of target compound HPB-MTP2 was identified by 1H NMR, 13C NMR, HRMS and elemental analysis in this example: 1 H NMR (C6D6, TMS, 600MHz) δ (ppm): 8.63 (s, 2H), 8.12 (s, 2H), 8.08 (d, J = 9.6 Hz, 4H), 7.99 (s, 2H), 7.94 (s, 2H), 7.63 (d, J = 8.0 Hz, 4H), 7.39(d, J = 8.0 Hz, 4H), 7.23 (d, J = 7.8 Hz, 4H), 7.13 (d, J = 7.8 Hz, 4H),6.89-6.81 (m, 10H), 6.75 (t, J = 7.4 Hz, 2H), 4.12-4.07 (m, 12H), 3.74 (t, J = 6.1 Hz, 4H), 3.41 (s, 6H), 1.90-1.84 (m, 12H), 1.66-1.53 (m, 18H), 1.44-1.28 (m, 98H), 0.97-0.90 (m, 24H). 13 C NMR (C6D6, 151 MHz) δ(ppm): 156.24,150.74, 150.31, 149.82, 149.75, 141.50, 141.43, 141.39, 141.37, 141.32,140.28, 136.47, 132.16, 132.03, 130.93, 130.21, 128.93, 127.47, 127.32,125.95, 125.80, 125.66, 124.77, 124.25, 123.90, 123.86, 108.30, 108.16,107.50, 107.04, 105.59, 69.83, 69.64, 69.42, 68.98, 55.80, 32.47, 32.41,32.40, 32.38, 30.26, 30.21, 30.15, 30.11, 30.07, 30.04, 29.95, 29.90, 29.89,29.87, 26.77, 26.70, 23.22, 23.17, 14.46, 14.41. HRMS (MALDI): [M] + calcd forC 160 H 214 O 10 , m / z: 2296.6271 (100.0%), 2297.6304 (61.3%), 2295.6237 (57.8%), 2298.6338 (42.2%), 2297.6304 (24.7%); found, 2296.6268, 2297.6307, 2295.6236,2298.6350, 2299.6392. Elemental analysis: calculated for C 160 H 214 O 10 (2297.46), C 83.65%, H 9.39%; found, C 83.47%, H 9.35%.; In terms of performance, its good thermal stability, typical liquid crystal texture, wide liquid crystal phase transition range, and hexagonal columnar structure were tested using a polarizing microscope (POM) with a hot stage, differential scanning calorimetry (DSC), and small-angle / wide-angle X-ray scattering (S / WAXS) techniques. h Intermediate phase stacking method.

[0075] Example 9: Synthesis of target compounds HPB-TP4 and HPB-MTP4 A preparation method of hexaphenylbenzene-benzo[ghi]phenanthrene tetramer compounds HPB-TP4 and HPB-MTP4, the synthesis and steps of which are as follows: Synthesis of HPB-TP4: The synthesis and purification of HPB-TP4 refer to HPB-TP2 of Example 8; wherein, the feeding amount and conditions are HPB-4Br (100.00 mg, 0.12 mmol), TP10-Bpin (801.33 mg, 0.71 mmol), K2CO3 (325.08 mg, 2.35 mmol), Pd(PPh3)4 (81.54 mg, 0.07 mmol) and THF / H2O (9.0 mL / 3.0 mL); the mixture is heated to 70°C for 48 hours under stirring; the residue is eluted by silica gel column chromatography (petroleum ether / CH2Cl2, 1.25 / 1, v / v); recrystallized from ethyl acetate-ethanol to obtain white solid HPB-TP4 (278.20 mg, 52%); in this example, the structure of the target compound HPB-TP4 is identified by nuclear magnetic resonance hydrogen spectrum, carbon spectrum, high resolution mass spectrum and elemental analysis: 1 HNMR (CDCl3, TMS, 600MHz) δ (ppm): 8.19 (s, 4H), 7.86 (s, 4H), 7.80 (s, 8H),7.77 (d, J = 10.2 Hz, 8H), 7.34 (d, J = 8.4 Hz, 8H), 7.09 (d, J = 8.4 Hz,12H), 7.02-6.98 (m, 4H), 6.94-6.92 (m, 2H), 4.24-4.20 (m, 16H), 4.13 (t, J =6.6 Hz, 8H), 3.96 (t, J = 6.6 Hz, 8H), 3.91 (t, J = 6.6 Hz, 8H), 1.97-1.86(m, 20H), 1.65-1.50 (m, 40H), 1.43-1.14 (m, 260H), 0.90-0.85 (m, 60H). 13 C NMR(CDCl3, 151 MHz) δ(ppm): 155.06, 149.60, 149.11, 148.78, 140.93, 140.65,140.53, 139.53, 135.46, 131.73, 131.28, 130.85, 129.18, 128.11, 126.77,125.05, 124.65, 124.05, 123.25, 123.16, 107.68, 107.59, 107.09, 107.00,105.98, 69.83, 69.72, 69.54, 69.47, 68.96, 31.96, 31.93, 29.70, 29.68, 29.65,29.57, 29.55, 29.54, 29.50, 29.47, 29.39, 29.34, 29.27, 26.22, 26.20, 26.08,26.02, 22.70, 14.14, 14.11. HRMS (MALDI): [M] + calcd for C 314 H 470 O 20 , m / z:4564.5861 (100.0%), 4563.5828 (88.9%), 4565.5895 (83.9%), 4566.5928 (55.7%), 4562.5794 (52.5%); found, 4564.5870, 4563.5913, 4565.5762, 4566.5625,4562.6023. Elemental analysis: calculated for C 314 H 470 O 20 (4565.1940), C 82.61%, H 10.38%; found, C 82.82%, H 10.55%.; In terms of performance, its good thermal stability, typical liquid crystal texture, wide liquid crystal phase transition range, and rectangular columnar structure were tested using a polarizing microscope (POM) with a hot stage, differential scanning calorimetry (DSC), and small-angle / wide-angle X-ray scattering (S / WAXS) techniques. r The intermediate phase stacking method was studied, and its ultraviolet-visible absorption spectroscopy, fluorescence emission spectroscopy, and absolute quantum yield were tested. Synthesis of HPB-MTP4: The synthesis and purification of HPB-MTP4 refer to HPB-TP2 of Example 8; wherein, the feeding amount and condition are HPB-4Br (140.40 mg, 0.17 mmol), MTP10-Bpin (1.00 g, 0.99 mmol), K2CO3 (456.41 mg, 3.3 mmol), Pd(PPh3)4 (114.49 mg, 0.1 mmol) and THF / H2O (9.0 mL / 3.0 mL), respectively; the mixture was heated to 70 °C for 48 h under stirring; the residue was eluted by silica gel column chromatography (petroleum ether / CH2Cl2, 1 / 1.5, v / v); recrystallized from ethyl acetate-ethanol to give white solid HPB-MTP4 (318.60 mg, 48%); the structure of target compound HPB-MTP4 was identified by1H NMR,13C NMR, HRMS and elemental analysis in this example: 1 H NMR (CDCl3, TMS, 600MHz) δ (ppm): 8.20 (s, 4H), 7.86 (s, 4H), 7.83(s, 4H), 7.81 (s, 4H), 7.78 (d, J = 5.4 Hz, 8H), 7.34 (d, J = 8.0 Hz, 8H),7.14-7.11 (m, 12H), 7.06-7.04 (m, 4H), 6.99-6.97 (m, 2H), 4.24 (t, J = 6.6Hz, 8H), 4.21 (t, J = 6.6 Hz, 8H), 4.16 (t, J = 6.6 Hz, 8H), 4.04 (t, J = 6.6Hz, 8H), 3.72 (s, 12H), 1.98-1.88 (m, 24H), 1.75-1.70 (m, 8H), 1.60-1.52 (m,28H), 1.44-1.29 (m, 196H), 0.90-0.86 (m, 48H). 13 C NMR (CDCl3, 151 MHz) δ(ppm): 155.69, 149.63, 149.14, 148.93, 148.88, 140.94, 140.58, 139.67,135.41, 131.75, 131.41, 130.75, 129.20, 128.00, 126.89, 125.20, 124.59,123.93, 123.32, 123.26, 123.22, 107.49, 107.27, 107.10, 105.46, 69.80, 69.63,69.61, 69.59, 56.48, 31.93, HRMS (MALDI):[M] + calcd for C 278 H 398 O 20 , m / z: 4059.0194 (100.0%), 4060.0227 (87.9%), 4058.0160 (66.8%), 4061.0261 (57.3%), 4062.0294 (29.2%); found, 4060.0228,4059.0205, 4059.0202, 4061.0270, 4058.0155. Elemental analysis: calculated for C 278 H 398 O 20 (4060.2220), C 82.24%, H 9.88%; found, C 82.20%, H 9.94%.; In terms of performance, its good thermal stability, typical liquid crystal texture, wide liquid crystal phase transition range, and hexagonal columnar structure were tested using a polarizing microscope (POM) with a hot stage, differential scanning calorimetry (DSC), and small-angle / wide-angle X-ray scattering (S / WAXS) techniques. h Intermediate phase stacking method.

[0076] Example 10: Synthesis of target compounds HPB-TP6 and HPB-MTP6 A method for preparing hexaphenylbenzene-benzophenanthrene hexameric compounds HPB-TP6 and HPB-MTP6, the synthesis steps of which are as follows: Synthesis of HPB-TP6: The synthesis and purification of HPB-TP6 refer to HPB-TP2 of Example 8; wherein, the feeding amount and condition are HPB-6Br (100.00 mg, 0.10 mmol), TP10-Bpin (1.13 g, 0.99 mmol), K2CO3 (479.84 mg, 3.47 mmol), Pd(PPh3)4 (91.71 mg, 0.08 mmol) and THF / H2O (10.5 mL / 4.5 mL), respectively; the mixture was heated to 70 °C with stirring for 72 h; the residue was eluted by silica gel column chromatography (petroleum ether / CH2Cl2, 1.75 / 1, v / v); recrystallized from ethyl acetate-ethanol to obtain white solid HPB-TP6 (313.70 mg, 48%); in this example, the structure of target compound HPB-TP6 was identified by 1H NMR, 13C NMR, HRMS and elemental analysis: 1 HNMR (CDCl3, TMS, 600MHz) δ (ppm): 8.25 (s, 6H), 7.83 (s, 6H), 7.79 (s, 6H),7.75 (s, 6H), 7.72 (d, J = 4.8 Hz, 12H), 7.48 (d, J = 8.0 Hz, 12H), 7.25 (d, J = 8.0 Hz, 12H), 4.23-4.18 (m, 24H), 4.05 (t, J = 6.6 Hz, 12H), 3.83 (t, J =6.6 Hz, 12H), 3.68 (t, J = 6.6 Hz, 12H), 1.97-1.90 (m, 24H), 1.86-1.81 (m,12H), 1.61-1.54 (m, 30H), 1.50-0.93 (m, 366H), 0.90-0.80 (m, 138H). 13 C NMR(CDCl3, 151 MHz) δ(ppm): 155.05, 149.55, 149.25, 148.74, 148.63, 140.68,139.68, 135.45, 131.26, 130.55, 129.22, 128.17, 125.03, 124.68, 124.17,123.23, 123.18, 123.01, 107.88, 107.54, 106.90, 106.59, 105.67, 69.97, 69.67,69.50, 69.25, 68.87, 31.98, 31.93, 31.92, 29.71, 29.67, 29.65, 29.63, 29.61,29.59, 29.52, 29.40, 29.34, 29.28, 29.21, 29.12, 26.26, 26.19, 26.04, 25.81,22.70, 14.14, 14.13, 14.11. HRMS (MALDI): [M] + calcd for C 450 H 690 O 30 , m / z:6580.2635 (100.0%), 6579.2601 (84.3%), 6581.2668 (60.5%), 6578.2568 (56.2%), 6577.2534 (38.8%); found, 6580.2635, 6579.2949, 6581.2430, 6578.3052,6577.3101. Elemental analysis: calculated for C 450 H 690 O 30 (6580.4400), C 82.14%, H 10.57%; found, C 81.92%, H 10.48%.; In terms of performance, its good thermal stability, typical liquid crystal texture, wide liquid crystal phase transition range and cubic (Cub) mesophase packing mode were tested by polarizing microscope (POM) with hot stage, differential scanning calorimeter (DSC) and small angle / wide angle X-ray scattering (S / WAXS) technology. It was also tested by ultraviolet-visible absorption spectroscopy, fluorescence emission spectroscopy and absolute quantum yield. Synthesis of HPB-MTP6: The synthesis and purification of HPB-MTP6 refer to HPB-TP2 of Example 8; wherein, the feeding amount and condition are HPB-6Br (99.87 mg, 0.10 mmol), MTP10-Bpin (1.00 g, 1.00 mmol), K2CO3 (479.23 mg, 3.47 mmol), Pd(PPh3)4 (91.59 mg, 0.08 mmol) and THF / H2O (10.5 mL / 4.5 mL), respectively; the mixture was heated to 70 °C with stirring for 72 h; the residue was eluted by silica gel column chromatography (petroleum ether / CH2Cl2, 1 / 1.75, v / v); recrystallized from ethyl acetate-ethanol to obtain white solid HPB-MTP6 (70.40 mg, 12%); in this example, the structure of target compound HPB-MTP6 was identified by nuclear magnetic resonance hydrogen spectrum, carbon spectrum, high resolution mass spectrum, elemental analysis: 1 H NMR (CDCl3, TMS, 600MHz) δ (ppm): 8.23 (s, 6H), 7.81 (s, 6H), 7.78 (s, 6H), 7.73 (s, 6H), 7.71 (s, 12H), 7.46 (d, J = 7.6 Hz, 12H), 7.28 (d, J = 7.6 Hz, 12H), 4.23 (t, J = 6.0 Hz, 12H), 4.19 (t, J = 6.0 Hz, 12H), 4.05 (t, J = 6.0 Hz, 12H), 3.76 (t, J = 6.0 Hz, 12H), 3.65 (s, 18H), 1.96-1.91 (m, 24H), 1.85-1.82 (m, 12H), 1.59-1.54 (m, 30H), 1.49-1.37 (m, 80H), 1.30-1.21 (m, 158H), 1.16-0.96 (m, 80H), 0.90-0.83 (m, 72H). 13 C NMR(CDCl3, 151 MHz) δ(ppm): 155.65, 149.60, 149.21, 148.86, 140.72, 139.83,135.53, 131.52, 130.57, 129.23, 128.14, 125.17, 124.61, 123.95, 123.40,123.18, 123.12, 107.70, 107.36, 107.05, 106.88, 105.36, 69.92, 69.62, 69.57,69.36, 56.37, 31.96, 29.74, 29.72, 29.69, 29.67, 29.64, 29.61, 29.55, 29.51,29.42, 29.40, 29.32, 26.27, 26.21, 25.92, 22.71, 14.14, 14.12. HRMS (MALDI):[M] + calcd for C 396 H 582 O 30 , m / z: 5822.4150 (100.0%), 5823.4184 (74.6%), 5821.4117 (70.8%), 5820.4083 (48.9%), 5819.4050 (23.7%); found, 5822.4135,5823.3951, 5821.4316, 5824.3755, 5820.4382. Elemental analysis: calculated for C 396 H 582 O 30 (5822.9820), C 81.68%, H 10.07%; found, C 81.31%, H 10.08%.; In terms of performance, its good thermal stability, typical liquid crystal texture, wide liquid crystal phase transition range, and cubic (Cub) mesophase stacking mode were tested by polarizing microscope (POM) with hot stage, differential scanning calorimeter (DSC), and small angle / wide angle X-ray scattering (S / WAXS) techniques.

Claims

1. A star-shaped graphene-like conjugated bridged benzophenanthrene disk-shaped liquid crystal compound, characterized in that, The star-shaped graphene-conjugated bridged benzophenanthrene disk-shaped liquid crystal compound has the following structures: Formula I, II, and III, where R represents an alkyl chain -C. 10 H 21 R' indicates an alkyl chain -C 10 H 21 and methyl-CH3 。 2. A method for preparing star-shaped hexaphenylbenzene-benzophenanthrene dual-disc liquid crystal compounds HPB-TP2 and HPB-MTP2, characterized in that... Includes the following steps: Step 1: Preparation of intermediate HPB-2Br: Under argon protection, M1 (1.31 g, 3.90 mmol), M2 (1.0 g, 2.60 mmol), and benzophenone (5.5 g) were added to a glass reaction tube; the mixture was stirred and heated to 305 °C and refluxed for 3 hours; after heating was stopped, when the temperature of the reaction system dropped to about 100 °C, diphenyl ether (2 mL) was added to prevent M2 from solidifying at low temperature in the system; after cooling to room temperature, toluene was added to dilute the reaction solution; subsequently, the mixture was filtered through a Buchner funnel, washed several times with toluene, and dried to obtain a grayish-white solid powder HPB-2Br (1.72 g, 64%). Step 2: Preparation of star-shaped hexaphenylbenzene-benzophenanthrene dual-disc liquid crystal compounds HPB-TP2 and HPB-MTP2: Synthesis of HPB-TP2: Under argon protection, HPB-2Br (100.0 mg, 0.14 mmol), TP10-Bpin (983.92 mg, 0.87 mmol), K2CO3 (399.15 mg, 2.89 mmol), and Pd(PPh3)4 (100.12 mg, 0.09 mmol) were mixed and stirred in a THF / H2O (9.0 mL / 3.0 mL) solvent mixture. The mixture was heated to 70 °C and reacted for 24 hours with stirring. After cooling, the mixture was extracted with CH2Cl2, dried over MgSO4, and the solvent was removed under vacuum. The residue was eluted by silica gel column chromatography (petroleum ether / CH2Cl2, 1.5 / 1, v / v). Recrystallization from ethyl acetate-ethanol gave a white solid HPB-TP2 (222.50 mg, 60%). Synthesis of HPB-MTP2: The synthesis and purification of HPB-MTP2 were performed according to the method described above for HPB-TP2. The feed amounts and conditions were as follows: HPB-2Br (102.91 mg, 0.15 mmol), MTP10-Bpin (600.00 mg, 0.59 mmol), K2CO3 (205.38 mg, 1.49 mmol), Pd(PPh3)4 (51.52 mg, 0.04 mmol), and THF / H2O (9.0 mL / 3.0 mL). The mixture was heated to 70 °C with stirring and reacted for 24 hours. The residue was eluted by silica gel column chromatography (petroleum ether / CH2Cl2, 1 / 1, v / v). Recrystallization from ethyl acetate-ethanol yielded a white solid, HPB-MTP2 (225.70 mg, 66%).

3. A method for preparing star-shaped hexaphenylbenzene-benzophenanthrene tetrameric disk-shaped liquid crystal compounds HPB-TP4 and HPB-MTP4, characterized in that... Includes the following steps: Step 1: Preparation of intermediate HPB-4Br: Under argon protection, M1 (929.50 mg, 2.77 mmol), M3 (1.0 g, 1.84 mmol), and benzophenone (5.5 g) were added to a glass reaction tube; the mixture was stirred and heated to 305 °C and refluxed for 3 hours; after heating was stopped, when the temperature of the reaction system dropped to about 100 °C, diphenyl ether (2 mL) was added to prevent M3 from solidifying at low temperature in the system; after cooling to room temperature, toluene was added to dilute the reaction solution; subsequently, the mixture was filtered through a Buchner funnel, washed several times with toluene, and dried to obtain a grayish-white solid powder HPB-4Br (961.10 mg, 61%). Step 2: Preparation of star-shaped hexaphenylbenzene-benzophenanthrene tetrameric disc-shaped liquid crystal compounds HPB-TP4 and HPB-MTP4: Synthesis of HPB-TP4: Under argon protection, HPB-4Br (100.00 mg, 0.12 mmol), TP10-Bpin (801.33 mg, 0.71 mmol), K2CO3 (325.08 mg, 2.35 mmol), and Pd(PPh3)4 (81.54 mg, 0.07 mmol) were mixed and stirred in a THF / H2O (9.0 mL / 3.0 mL) solvent mixture. The mixture was heated to 70 °C and reacted for 48 hours with stirring. After cooling, the mixture was extracted with CH2Cl2, dried over MgSO4, and the solvent was removed under vacuum. The residue was eluted by silica gel column chromatography (petroleum ether / CH2Cl2, 1.25 / 1, v / v). Recrystallization from ethyl acetate-ethanol gave a white solid HPB-TP4 (278.20 mg, 52%). Synthesis of HPB-MTP4: The synthesis and purification of HPB-MTP4 were performed according to the method described above for HPB-TP4. The feed amounts and conditions were as follows: HPB-4Br (140.40 mg, 0.17 mmol), MTP10-Bpin (1.00 g, 0.99 mmol), K2CO3 (456.41 mg, 3.3 mmol), Pd(PPh3)4 (114.49 mg, 0.1 mmol), and THF / H2O (9.0 mL / 3.0 mL). The mixture was heated to 70 °C with stirring and reacted for 48 hours. The residue was eluted by silica gel column chromatography (petroleum ether / CH2Cl2, 1 / 1.5, v / v). Recrystallization from ethyl acetate-ethanol yielded a white solid HPB-MTP4 (318.60 mg, 48%).

4. A method for preparing star-shaped hexaphenylbenzene-benzophenanthrene hexameric disk-shaped liquid crystal compounds HPB-TP6 and HPB-MTP6, characterized in that... Includes the following steps: Step 1: Preparation of intermediate HPB-6Br: Under argon protection, M1 (6.72 g, 20.00 mmol) was dissolved in 150 mL of 1,4-dioxane, and then Co2(CO)8 (1.37 g, 4.00 mmol) was added. The mixture was refluxed at 120 °C under an argon atmosphere for 12 hours, then cooled to room temperature and concentrated under reduced pressure. The resulting residue was refluxed and eluted with heated petroleum ether for 3 hours. Recrystallization from methanol yielded a grayish-white powder, HPB-6Br (5.90 g, 88%). Step 2: Preparation of star-shaped hexaphenylbenzene-benzophenanthrene hexaplex disk-shaped liquid crystal compounds HPB-TP6 and HPB-MTP6: Synthesis of HPB-TP6: Under argon protection, HPB-6Br (100.00 mg, 0.10 mmol), TP10-Bpin (1.13 g, 0.99 mmol), K2CO3 (479.84 mg, 3.47 mmol), and Pd(PPh3)4 (91.71 mg, 0.08 mmol) were mixed and stirred in a THF / H2O (10.5 mL / 4.5 mL) solvent mixture. The mixture was heated to 70 °C and reacted for 72 hours with stirring. After cooling, the mixture was extracted with CH2Cl2, dried over MgSO4, and the solvent was removed under vacuum. The residue was eluted by silica gel column chromatography (petroleum ether / CH2Cl2, 1.75 / 1, v / v). Recrystallization from ethyl acetate-ethanol gave a white solid HPB-TP6 (313.70 mg, 48%). Synthesis of HPB-MTP6: The synthesis and purification of HPB-MTP6 were performed according to the method described above for HPB-TP6. The feed amounts and conditions were as follows: HPB-6Br (99.87 mg, 0.10 mmol), MTP10-Bpin (1.00 g, 1.00 mmol), K2CO3 (479.23 mg, 3.47 mmol), Pd(PPh3)4 (91.59 mg, 0.08 mmol), and THF / H2O (10.5 mL / 4.5 mL). The mixture was heated to 70 °C with stirring and reacted for 72 hours. The residue was eluted by silica gel column chromatography (petroleum ether / CH2Cl2, 1 / 1.75, v / v). Recrystallization from ethyl acetate-ethanol yielded a white solid, HPB-MTP6 (70.40 mg, 12%).

5. The use of the star-shaped hexaphenylbenzene-benzophenanthrene multi-linked disk-shaped liquid crystal target compounds HPB-TP2 and HPB-MTP2, HPB-TP4 and HPB-MTP4, HPB-TP6 and HPB-MTP6 as organic liquid crystal materials, liquid crystal optoelectronic materials and in organic thin film electronic devices.

6. Without departing from the concept of the present invention, those skilled in the art can make improvements to the preparation method and the instruments used within the scope of the claims, and such improvements should also be considered within the scope of protection of the present invention.

Images