CN114573532A - Synthesis and luminescence of bis-benzophenanthrofuran discotic liquid crystal compound - Google Patents

Abstract

The invention relates to the research on the synthesis and optical properties of bistriphenanthrofuran discotic liquid crystal compounds. It is characterized by having general formulae (I) and (II). Wherein R is an alkyl chain of C ₈ ~C ₁₆ , the compounds of the general formula (I) and (II) can self-assemble into a hexagonal columnar liquid crystal mesophase in a wide temperature range, and the compound of the general formula (I) is more A gelling agent for polar/nonpolar organic solvents. The present invention also provides a method for preparing a bis-triphenanthrofuran discotic liquid crystal compound. The synthesis route is simple, quick and mild in conditions. ) compounds were obtained by intramolecular oxidation of FeCl ₃ to close the ring.

Description

Synthesis and Luminescence of Bistriphenanthrofuran Discotic Liquid Crystal Compounds

technical field

The present invention relates to the synthesis and luminescence of bistriphenanthrofuran discotic liquid crystal compounds.

Background technique

At present, discotic liquid crystals are a unique class of materials with significant electrical and photoconductive properties that can form nano-microstructures through self-assembly. Therefore, organic liquid crystal molecules can be used as a non-traditional organic semiconductor. Due to its unique properties, such as the characteristics of charge transport, organic liquid crystal semiconductor materials can undergo ordered self-assembly in the mesophase, and can be processed into films. Defect repairability and low cost, etc. Therefore, discotic liquid crystals have certain applications in the fields of molecular electronics, optoelectronics, photoconductivity, photovoltaics, and electroluminescence devices, and discotic liquid crystals are considered promising. For organic semiconductors, however, the intra-columnar stacking of the polymer-liquid mesophase due to topological defects, thermal fluctuations, and molecular diffusion also affects the parameters of the charge carrier flow efficiency. The improvement of these properties requires various methods such as very stable sensor materials, suitable temperature, and ideal operating environment to achieve the desired molecular ordering, making the reaction easy to handle, which can improve the performance of charge transfer. Discotic liquid crystal small molecules have simple and efficient design and synthesis, self-assemble into a stable columnar mesophase, and are easily soluble in many common organic solvents, providing the possibility of being processed into films. In order to explore the differences between the liquid crystallinity, optical properties and semiconductor properties of the same compound with different configurations in discotic liquid crystal compounds, we designed and synthesized the following compounds based on furan.

SUMMARY OF THE INVENTION

Based on this design, bistriphenanthrofuran discotic liquid crystal compounds were synthesized. Such compounds are mainly obtained by Suzuki coupling in synthesis. Mainly via 4,4,5,5-tetramethyl-2-(3',4,4',5-tetra(alkoxy)-[1,1'-biphenyl]-2-yl)-1 ,3,2-dioxaborane and 2,8-dibromofuran and 4,6-dibromofuran undergo Suzuki coupling, respectively, and the ring is closed. The target compound is obtained, and research shows that the compound forms a stable columnar phase in a wide temperature range and is a liquid crystal with excellent performance. At the same time, the compounds have good luminescence properties, and the absolute quantum yield can reach 60%.

In addition, it is also necessary to provide a method for preparing a bis-triphenylene furan discotic liquid crystal compound, a bis-triphenylene furan discotic liquid crystal compound, which is characterized in that it has the structures represented by the general formulas (I) and (II) :

wherein R is C _n H _2n+1 , and n represents an integer of 8-16 carbon atoms.

A bis(3',4,4',5-tetra(alkoxy)-[1,1'- Biphenyl]-2-yl)dibenzo[b,d]furan is characterized by comprising the following steps.

Step 1: The intermediate is the preparation of compound b:

Take the compound shown in formula a as a raw material, weigh it and bromine in a 250ml round-bottomed flask at a molar ratio of 1:1, add 150ml chloroform, put on a constant pressure dropping funnel, and add chloroform to it. Methane (20ml) and bromine, put the round-bottomed flask into the room temperature environment, the solution in the constant pressure dropping funnel is controlled at 2 seconds per drop, and the plate is tracked every 15 minutes. After the reaction is completed, add sodium bisulfite Terminate the reaction, filter, spin dry, pass through silica gel column chromatography (eluent: V dichloromethane: V petroleum ether=1:2), recrystallize with ethanol and ethyl acetate to obtain product b, wherein R ₁ is -C _n H _2n+1 , where n represents an integer having 6-16 carbon atoms.

Step 2: Intermediate 4,4,5,5-tetramethyl-2-(3',4,4',5-tetrakis(alkoxy)-[1,1'-biphenyl]-2-yl )-1,3,2-dioxaborane (c) synthesis:

2-Bromo-3',4,4',5-tetra(alkoxy)-1,1'-biphenyl(b):bisvaleryldiboron: _CH3COOK in a 100 ml reaction tube in a molar ratio : PdCl ₂ (dppf)= 1 : 1.5 : 0.05 : 3, weighed and added 25 ml of 1,4-dioxane, under the protection of argon, reacted at 90 ℃ for 24 h, cooled to room temperature, washed with dichloromethane Extraction was carried out, the organic phase was dried with anhydrous MgSO ₄ , filtered, spin-dried, passed through silica gel column chromatography (eluent: V dichloromethane: V petroleum ether=1:3), and recrystallized with ethyl acetate and methanol , to obtain a white solid (c), wherein, R is C _n H _{2n+1, and} n represents that the number of carbon atoms is 8-16.

Step 3:

(a), 2,8-bis(3',4,4',5-tetra(alkoxy)-[1,1'-biphenyl]-2-yl)dibenzo[b,d]furan (III) Synthesis:

In a 50 ml reaction tube, the molar ratio c : 2,8-dibromofuran: K ₂ CO ₃ : Pd(PPh ₃ ) ₄ = 2.5 : 1 : 30 : 0.2 was weighed and mixed solvent water (3 ml)/ THF (10 ml), reacted at 70 °C for 48 h under argon protection, cooled to room temperature, extracted with dichloromethane, the organic phase was dried over anhydrous MgSO ₄ , filtered, spin-dried, and passed through silica gel column chromatography (eluent: V dichloromethane: V petroleum ether=1:3), recrystallized with ethyl acetate and ethanol to obtain a white solid (III), wherein R is C _n H _2n+1, n represents carbon The number of atoms is 8-16.

(b), 4,6-bis(3',4,4',5-tetra(alkoxy)-[1,1'-biphenyl]-2-yl)dibenzo[b,d]furan (IV) Synthesis:

_In a 50 ml reaction tube, _weigh and add mixed solvent water ( _{3 ml} )/ THF (10 ml), reacted at 70 °C for 48 h under argon protection, cooled to room temperature, extracted with dichloromethane, the organic phase was dried over anhydrous MgSO ₄ , filtered, spin-dried, and passed through silica gel column chromatography (eluent: V dichloromethane: V petroleum ether=1:3), recrystallized with ethyl acetate and ethanol to obtain a white solid (IV), wherein R is C _n H _2n+1, n represents a carbon atom The numbers are 8-16.

Preparation of Bistriphenanthrofuran Discotic Liquid Crystal Compounds (I) and (II).

(a) a bistriphenylene furan discotic liquid crystal compound of the general formula (I) shown in claim 1, the preparation method of which is:

In a 100ml round-bottomed flask, the molar ratio of compound (III) : FeCl ₃ = 1 : 6 was weighed, and chloroform (60ml), nitromethane (5ml) were added, and the reaction was carried out at room temperature, every 15min. After the reaction was completed, methanol was added to terminate the reaction, extracted with chloroform, dried over MgSO ₄ , filtered, spin-dried, and passed through silica gel column chromatography (eluent: V dichloromethane: V petroleum ether=1:2 ), recrystallized from toluene and petroleum ether to obtain a tan solid (I), wherein R is C _n H _{2n+1, and} n represents 8-16 carbon atoms.

(b) a bistriphenylene furan discotic liquid crystal compound of the general formula (II) shown in claim 1, the preparation method of which is:

In a 100ml round-bottomed flask, the molar ratio of compound (IV) : FeCl ₃ = 1 : 6 was weighed, and chloroform (60ml), nitromethane (5ml) were added, and the reaction was carried out at room temperature, every 15min. After the reaction was completed, methanol was added to terminate the reaction, extracted with chloroform, dried over MgSO ₄ , filtered, spin-dried, and passed through silica gel column chromatography (eluent: V dichloromethane: V petroleum ether=1:2 ), recrystallized from toluene and petroleum ether to obtain a white solid (II), wherein R is C _n H _{2n+1, and} n represents the number of carbon atoms is 8-16.

The preparation method of the above-mentioned bis-triphenanthrofuran discotic liquid crystal compound, the synthesis route is simple, quick and mild, and the compound is 4,4,5,5-tetramethyl-2-(3',4,4 ',5-Tetrakis(alkoxy)-[1,1'-biphenyl]-2-yl)-1,3,2-dioxaborane and 4,6-dibromofuran after Suzuki coupling Perform ring closure and connect multiple aryl groups together by condensing. Under the regulation of multiple alkoxy flexible chains in the periphery, it can self-assemble into a stable form in a wide temperature range and at room temperature. The hexagonal columnar liquid crystal mesophase has good application value in liquid crystal materials.

Description of drawings

Figure 1 H NMR spectrum of intermediate b obtained in Example 1 where R is C ₁₀ H ₂₁ .

Fig. 2 H NMR spectrum of intermediate c obtained in Example 2 where R is C ₁₀ H ₂₁ .

Fig. 3 The hydrogen nuclear magnetic spectrum of the general formula (III) obtained in Example 3 when R is C ₁₀ H ₂₁ .

Figure 4 shows the hydrogen nuclear magnetic spectrum of the general formula (I) obtained in Example 4 when R is C ₁₀ H ₂₁ .

Figure 5. The hydrogen nuclear magnetic spectrum of the general formula (IV) obtained in Example 5 when R is C ₁₀ H ₂₁ .

Fig. 6 The hydrogen nuclear magnetic spectrum of the general formula (II) obtained in Example 6 when R is C ₁₀ H ₂₁ .

Figure ₇ is a DSC curve diagram of the general formula (I) obtained in Example 4 when R is _C10H21 .

Figure 8 shows the DSC curve of the general formula (II) obtained in Example 6 when R is C ₁₀ H ₂₁ .

Figure 9. The polarized light texture diagram of the general formula (I) obtained in Example 4 when R is C ₁₀ H ₂₁ .

Figure 10 The polarized light texture diagram of the general formula (II) obtained in Example 6 when R is C ₁₀ H ₂₁ .

Fig. 11 is the XRD diffraction pattern, and the curve is the XRD diffraction pattern of the general formula (I) in the mesophase obtained in Example 4 when R is C ₁₀ H ₂₁ .

12 is an XRD diffraction pattern, and the curve is the XRD diffraction pattern of the general formula (II) in the mesophase obtained in Example 6 when R is C ₁₀ H ₂₁ .

Figure 13 is a fluorescence emission spectrum diagram, curve F1 is the fluorescence emission spectrum diagram of general formula (I) obtained in Example 4 when R is C ₁₀ H ₂₁ ; Curve F2 is obtained in Example 6 when R is C ₁₀ H ₂₁ The fluorescence emission spectrum of the general formula (II).

Fig. 14 is an ultraviolet absorption spectrogram, curve F1 is the ultraviolet absorption spectrogram of general formula (I) when R obtained in Example 4 is C ₁₀ H ₂₁ ; Curve F2 is obtained in Example 6 when R is C ₁₀ H ₂₁ The UV absorption spectrum of the general formula (II).

Fig. 15 is an inverted gel picture, which is obtained in Example 4 when R is C ₁₀ H ₂₁ and the compound of general formula (I) in dichloromethane, ethyl acetate, tetrahydrofuran, toluene, hexane and cyclohexane in turn in dichloromethane, ethyl acetate, tetrahydrofuran Image of gel formed in organic solvent.

Detailed ways

The examples given below are specific descriptions of the present invention, and it must be emphasized that the examples given below are only further elaborations of the present invention, rather than a limitation to the protection scope of the present invention. Those skilled in the art will still fall within the protection scope of the present invention if the improvements or adjustments involved in the actual implementation process according to the above-mentioned contents of the invention are not changes in the essential sense.

The synthetic methods used in each of the following implementation cases are the prior art:

T. Yasuda, T. Shimizu, F. Liu, G. Ungar, T. Kato, J. Am. Chem. Soc. 2011, 133, 13437–13444.

Example 1.

The compound provided in this example is the preparation of compound intermediate b, wherein R is C ₁₀ H _{21, and} its preparation reaction is as follows:

Starting from 3,3',4,4'-tetrakis(decyloxy)-1,1'-biphenyl(a) (0.63 mg, 0.80 mmol), it was mixed with bromine (0.11 g, 0.80 mmol) Weigh the element in a 250 ml round-bottomed flask at a molar ratio of 1:1, add 150 ml of chloroform, cover with a constant-pressure dropping funnel, add chloroform (20 ml) and bromine to it, put the round-bottomed flask Put it in a room temperature environment, the solution in the constant pressure dropping funnel is controlled at 2 seconds per drop, and the plate is tracked every 15 minutes. After the reaction is completed, add sodium bisulfite to stop the reaction, filter, spin dry, and pass through a silica gel column. Chromatography (eluent: V dichloromethane: V petroleum ether=1:2), recrystallized with ethanol and ethyl acetate to obtain product b (0.65 g, yield 94%).

¹ H NMR(CDCl ₃ , TMS, 400 MHz), ¹ H NMR(CDCl ₃ , TMS, 400 MHz), δ: 7.10(s, 1H, ArH), 6.95(s, 1H, ArH), 6.89 (d, J = 4 Hz, 2H, ArH), 6.84(s, 1H, ArH), 4.02(t, J = 2.8 Hz, 8H, OCH ₂ ), 1.76-1.87(m, 8H, CH ₂ ), 1.27 -1.57(m, 56H, _CH2 ), 0.88(t, J = 2.8Hz, 12H, _CH3 ).

Example 2.

4,4,5,5-Tetramethyl-2-(3',4,4',5-tetra(alkoxy)-[1,1'-biphenyl]-2-yl)-1,3 , The preparation of 2-dioxaborane (c), wherein R is C ₁₀ H _21, the preparation reaction is as follows:

In a 100 ml reaction tube, in a molar ratio of 2-bromo-3',4,4',5-tetrakis(alkoxy)-1,1'-biphenyl:bisvaleryldiboron (b): _CH3COOK : PdCl ₂ (dppf)= 1 (1.2 g) : 1.5 (0.53 g) : 0.05 (0.06 g) : 3 (0.4 g) Weigh and add 25 ml of 1,4-dioxane, under argon protection , reacted at 90 °C for 24 h, cooled to room temperature, extracted with dichloromethane, the organic phase was dried with anhydrous MgSO ₄ , filtered, spin-dried, and passed through silica gel column chromatography (eluent: V dichloromethane: V petroleum ether=1:3), recrystallized from ethyl acetate and methanol to give white solid (c) (1.27 g, 40% yield).

¹ H NMR(CDCl ₃ , TMS, 400 MHz), ¹ H NMR(CDCl ₃ , TMS, 400 MHz), δ: 7.21(s, 1H, ArH), 6.92(s, 1H, ArH) , 6.85(s, 3H, ArH), 4.0-4.05(m, 8H, OCH ₂ ), 1.80-1.85(m, 8H, CH ₂ ), 1.27-1.50(m, 56H, CH ₂ ), 1.19(s, 12H, CH ₃ ), 0.88 (t, J = 4Hz, 12H, CH ₃ ).

Example 3.

The compound provided in this example is the preparation of the compound of general formula (III), wherein R is C ₁₀ H ₂₁ , and the preparation reaction is as follows:

In a 50 ml reaction tube, in a molar ratio c : 2,7-dibromofuran: K ₂ CO ₃ : Pd(PPh ₃ ) ₄ = 2.5 (0.35) : 1 (0.05) : 30 (0.64) : 0.2 (0.04) Weigh and add mixed solvent water (3 ml)/THF (10 ml), react at 70 °C for 48 h under argon protection, cool to room temperature, extract with dichloromethane, and use anhydrous MgSO ₄ for the organic phase Dry, filter, spin dry, pass through silica gel column chromatography (eluent: V dichloromethane: V petroleum ether=1:3), recrystallize with ethyl acetate and ethanol to obtain white solid (III), (0.20 g, 76% yield).

¹ H NMR(CDCl ₃ , TMS, 400 MHz), δ:7.73 (s, 2H, ArH), 7.31 (d, J =8.0 Hz,2H, ArH), 7.10(d, J = 8.0 Hz, 2H, ArH), 6.99 (d, J = 4.0 Hz, 4H, ArH), 6.70 (s, 4H, ArH), 6.59 (s, 2H, ArH), 4.10- 4.06 (m , 8H , OCH ₂ ), 3.91 (t, J =8.0 Hz, 4H, OCH ₂ ), 3.61 (t, J = 8.0 Hz , 4H, OCH ₂ ), 1.88-1.73 (m, 14H, CH ₂ ), 1.58-1.48 (m, 14H, CH 2 ₂ ), 1.38-1.19 (m, 100H, CH ₂ ), 0.88 (t, J = 8.0 Hz, 24H, CH ₃ ).

Example 4.

The compound provided in this example is the compound of general formula (I), wherein R ₁ is C ₁₀ H _{21, and} its preparation reaction is as follows:

In a 100ml round-bottomed flask, the molar ratio of compound (III) : FeCl ₃ = 1 (0.140) : 6 (0.08) was weighed, and chloroform (60ml), nitromethane (5ml) were added, and at room temperature The reaction was followed by spotting the plate every 15 min. After the reaction was completed, methanol was added to terminate the reaction, and the reaction was extracted with chloroform, dried over _MgSO4 , filtered, spin-dried, and passed through silica gel column chromatography (eluent: V dichloromethane: V Petroleum ether=1:2), toluene and petroleum ether were recrystallized to obtain a tan solid (I), (0.90 g, yield 65%).

¹ H NMR(CDCl ₃ , TMS, 400 MHz), ¹ H NMR(CDCl ₃ , TMS, 400 MHz), δ: 9.02 (s, 2H, ArH), 8.41 (s, 2H, ArH), 8.18 (s, 2H, ArH), 7.92 (s, 2H, ArH), 7.75 (s, 2H, ArH), 7.73 (s, 2H, ArH), 4.38-4.21 (m, 16H, OCH ₂ ), 2.01-1.94 (m, 16H, CH ₂ ), 1.66-1,57 (m, 16H, CH ₂ ), 1.45-1.26 (m, 96H, CH ₂ ), 0.91-0.86 (m, 24H, CH ₃ ).

Example 5.

The compound provided in this example is the preparation of the compound of general formula (IV), wherein R is C ₁₀ H ₂₁ , and the preparation reaction is as follows:

In a 50 ml reaction tube, in a molar ratio c : 2,7-dibromofuran: K ₂ CO ₃ : Pd(PPh ₃ ) ₄ = 2.5 (0.35) : 1 (0.05) : 30 (0.64) : 0.2 (0.04) Weigh and add mixed solvent water (3 ml)/THF (10 ml), react at 70 °C for 48 h under argon protection, cool to room temperature, extract with dichloromethane, and use anhydrous MgSO ₄ for the organic phase Dry, filter, spin dry, pass through silica gel column chromatography (eluent: V dichloromethane: V petroleum ether=1:3), recrystallize with ethyl acetate and ethanol to obtain white solid (IV), (0.20 g, 77% yield).

¹ H NMR (CDCl ₃ , TMS, 400 MHz) δ: 7.71-7.69 (m, 2H, ArH), 7.13(t, J = 4.0 Hz, 4H, ArH), 7.02 (s, 2H, ArH) , 6.96 (s, 2H, ArH), 6.50-6.44 (m,4H, ArH), 6.33 (d, J = 4.0 Hz, 2H, ArH), 4.09 (t, J = 8.0 Hz, 4H, OCH ₂ ), 3.90(t, J = 8.0 Hz, 4H, OCH ₂ ), 3.73 (t, J = 8.0 Hz, 4H, OCH ₂ ), 3.31 (t, J = 4.0 Hz, 4H, OCH ₂ ), 1.92-1.74 (m , 12H, CH ₂ ), 1.69-1.64 (m, 4H, CH ₂ ), 1.54-1.48 (m, 6H, CH ₂ ), 1.41-1.17 (m, 106H, CH ₂ ), 0.89-0.86 (m, 24H , _CH3 ).

Example 6.

The compound provided in this example is the compound of general formula (II), wherein R ₁ is C ₁₀ H _{21, and} its preparation reaction is as follows:

In a 100ml round-bottomed flask, the molar ratio of compound (IV) : FeCl ₃ = 1 (0.16) : 6 (0.09) was weighed, and dichloromethane (60ml), nitromethane (5ml) were added, and at room temperature The reaction was followed by spotting the plate every 15 min. After the reaction was completed, methanol was added to terminate the reaction, and the reaction was extracted with chloroform, dried over _MgSO4 , filtered, spin-dried, and passed through silica gel column chromatography (eluent: V dichloromethane: V Petroleum ether=1:2), toluene and petroleum ether were recrystallized to obtain white solid (II), (0.20 g, yield 85%).

¹ H NMR(CDCl ₃ , TMS, 600 MHz), δ: 9.37 (s, 2H, ArH), 8.58 (d, J =4.0 Hz, 2H, ArH), 8.24(d, J = 8.0 Hz, 2H, ArH), 8.13 (s, 2H, ArH), 7.98 (s, 2H, ArH), 7.93 (s, 2H, ArH), 4.32-4.15 (m, 16H, OCH ₂ ), 1.99-1.96 (m, 12H, CH ₂ ), 1.80-1,75 (m , 4H, CH ₂ ), 1.65-1.55 (m, 12H, CH ₂ ), 1.45-1.29 (m, 76H, CH ₂ ), 1.21-1.14 (m, 24H, _CH2 ), 0.90-0.82 (m, 24H, _CH3 ).

Claims (8)

1. A dibenzophenanthrofuran discotic liquid crystal compound is characterized by having a structure shown in general formulas (I) and (II):

。

2. bis (3 ',4,4', 5-tetrakis (alkoxy) - [1,1' -biphenyl ] -2-yl) dibenzo [ b, d ] furan characterized by the structure shown in positions (iii) 2,8 and (iv) 3,4 of the general formula:

。

3. the dibenzophenanthrofuran compounds (I), (II) according to claim 1 and bis (3 ',4,4', 5-tetra (alkoxy) - [1,1' -biphenyl) at the 2, 8-position (III) or 3, 4-position (IV) according to claim 2]-2-yl) dibenzo [ b, d]Furan, characterized in that said R is-C_nH_2n+1And n represents an integer of 8 to 16 carbon atoms.

4. A bis (3 ',4,4', 5-tetrakis (alkoxy) - [1,1' -biphenyl ] -2-yl) dibenzo [ b, d ] furan of formula 2, 8-position (iii), 3, 4-position (iv) according to claim 2, prepared by:

the method comprises the following steps: preparation of intermediate b (2-bromo-3 ',4,4', 5-tetra (alkoxy) -1,1' -biphenyl),

taking a compound shown as a formula 3,3',4,4' -tetra (alkoxy) -1,1' -biphenyl (a) as a raw material, weighing the compound and bromine in a molar ratio of 1:1 in a 250ml round-bottom flask, adding 150ml of trichloromethane, sleeving a constant pressure dropping funnel, adding trichloromethane (20 ml) and bromine into the constant pressure dropping funnel, putting the round-bottom flask into a room temperature environment, controlling the solution in the constant pressure dropping funnel to be 2 seconds per drop, performing plate tracking every 15 minutes, adding sodium bisulfite to terminate the reaction after the reaction is finished, filtering, spin-drying, performing silica gel column chromatography (eluent: V dichloromethane: V petroleum ether =1: 2), and recrystallizing with ethanol and ethyl acetate to obtain a product b, wherein R is₁is-C_nH_2n+1N represents an integer of 8 to 16 carbon atoms;

step two: synthesis of intermediate 4,4,5, 5-tetramethyl-2- (3 ',4,4', 5-tetra (alkoxy) - [1,1' -biphenyl ] -2-yl) -1,3, 2-dioxaborane (c):

2-bromo-3 ',4,4', 5-tetra (alkoxy) -1,1' -biphenyl to bis (valeryl) diboron CH in a molar ratio in a 100ml reaction tube₃COOK: PdCl₂(dppf) =1: 1.5: 0.05: 3 and adding 25 ml of 1, 4-dioxane, reacting at 90 ℃ for 24h under the protection of argon, cooling to room temperature, extracting with dichloromethane, and extracting the organic phase with anhydrous MgSO₄Drying, filtering, spin-drying, and recrystallizing with ethyl acetate and methanol by silica gel column chromatography (eluent: V dichloromethane: V petroleum ether =1: 3) to obtain a white solid (c);

step three:

(a) synthesis of bis (3 ',4,4', 5-tetrakis (alkoxy) - [1,1' -biphenyl ] -2-yl) dibenzo [ b, d ] furan (iii) in position 2, 8:

k in a molar ratio of c: 2, 8-dibromofuran in a 50ml reaction tube₂CO₃ : Pd(PPh₃)₄ Weighing and adding mixed solvent water (3 ml)/THF (10 ml) under the protection of argon, reacting at 70 deg.C for 48 h, cooling to room temperature, extracting with dichloromethane, and collecting organic phase with anhydrous MgSO₄Drying, filtering, spin-drying, and recrystallizing with ethyl acetate and ethanol by silica gel column chromatography (eluent: V chloroform: V petroleum ether =1: 3) to obtain white solid (III);

(b) synthesis of 4, 6-bis (3 ',4,4', 5-tetra (alkoxy) - [1,1' -biphenyl ] -2-yl) dibenzo [ b, d ] furan (iv):

in a 50ml reaction tube, in molar ratio c: 4, 6-dibromofuran: K₂CO₃ : Pd(PPh₃)₄ = 2.5: 1: 30: 0.2 weigh and add mixed solvent water (3 ml)/THF (10 ml), react at 70 ℃ for 48 h under argon protection, cool to room temperature, extract with dichloromethane, use anhydrous MgSO for organic phase and use anhydrous MgSO for organic phase₄Drying, filtering, spin-drying, and recrystallizing by silica gel column chromatography (eluent: V chloroform: V petroleum ether =1: 3) with ethyl acetate and ethanol to obtain white solid (IV).

(a) a discotic liquid crystal compound of bis-benzophenanthrofuran of the general formulae (I) and (II) as defined in claim 1, which is prepared by:

in a 100ml round-bottomed flask with compound (III) FeCl₃ Weighing at a molar ratio of 1: 6, adding trichloromethane (60 ml) and nitromethane (5ml), reacting at room temperature, tracking the reaction by a point plate every 15min, adding methanol to stop the reaction after the reaction is finished, extracting with trichloromethane, and MgSO₄Drying, filtering, spin-drying, and recrystallizing with toluene and petroleum ether by silica gel column chromatography (eluent: V dichloromethane: V petroleum ether =1: 2) to obtain a tan solid (I);

(b) a discotic liquid crystalline bis-benzophenanthrofuran compound of the general formula (II) as defined in claim 1, which is prepared by:

in a 100ml round-bottomed flask with compound (IV): FeCl₃ Weighing at a molar ratio of 1: 6, adding trichloromethane (60 ml) and nitromethane (5ml), reacting at room temperature, tracking the reaction by a point plate every 15min, adding methanol to stop the reaction after the reaction is finished, extracting with trichloromethane, and MgSO₄Drying, filtration, spin-drying, and recrystallization from toluene and petroleum ether by column chromatography on silica gel (eluent: V dichloromethane: V petroleum ether =1: 2) gave white solid (II).

6. Use of the discotic liquid crystal compounds of the general formulae (I) and (II) as defined in claim 1 as organic liquid crystal semiconductor materials.

7. Use of the bis-benzophenanthrofuran discotic liquid crystal compounds of the general formulae (I) and (II) as defined in claim 1 as organic photoluminescent materials.

8. Use of the bis-benzophenanthrofuran discotic liquid crystal compound in the general formula (i) as defined in claim 1 as an organogelator.

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