CN103524399B - A kind of organic compound and use the electroluminescent device of this organic compound - Google Patents

Abstract

The present invention relates to an organic compound, which has the structure shown in formula I: wherein: R1, R2 and R3 are each independently selected from hydrogen atoms, substituted or unsubstituted C1-C30 alkyl, substituted or substituted C1 -C30 cycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 arylamino , a substituted or unsubstituted C2-C30 heterocycle, a substituted or unsubstituted C6-C30 condensed polycyclic group, a hydroxyl group, a cyano group, and a substituted or unsubstituted amino group. The invention also relates to an electroluminescent device comprising using at least one of said compounds as a hole injection layer and/or a hole transport layer.

Description

An organic compound and an electroluminescent device using the organic compound

technical field

The invention relates to an organic compound, in particular to a naphthoazepine derivative used in an organic electroluminescence device and its application in the technical field of electroluminescence display.

Background technique

Organic electroluminescence technology, or organic light-emitting diode technology, is seen as the next generation display technology. Compared with traditional liquid crystal (Liquid Crystal Display, LCD) technology, there is no need for backlight illumination and color filters, and the pixels can emit light by themselves and appear on the color display panel. Moreover, it has the characteristics of ultra-high contrast, ultra-wide viewing angle, curved surface, and thin profile.

Organic electroluminescent devices can be traced back to 1963 when Pope et al. studied blue electroluminescence with anthracene as a single crystal (10-20 μm). Because of the thick anthracene single crystal light-emitting layer and the constraints of the electrode materials used, the device The starting voltage of the luminescence is as high as 400V, and the efficiency and brightness are low. However, this does not affect its position in the history of the development of organic electroluminescence diodes (OLEDs). In the past two decades, the research progress of organic electroluminescence has been very slow. Until 1987, CW Tang of Kodak Corporation of the United States developed a double-layer structure with 8-hydroxyquinoline aluminum (Alq ₃ ) as the light-emitting layer, aromatic diamine as the hole transport layer, ITO as the anode, Mg: Ag (10:1 ) alloy as the cathode of the "sandwich" device, only to open a new chapter in OLED devices. In 1990, the Cavendish Laboratory of Cambridge University discovered EL light-emitting devices based on polymers, which opened up another new way for EL devices. In the next ten years, due to the limitation of high-resolution RGB color pixels, the limitation of TFT backplane and the difficulty of large area, the research progress of OLED has been very slow. In recent years, people's research on OLED has become a hot spot of flat panel display. With the device technology becoming more and more mature, the material design and synthesis are continuously improved, and the dream of mass production of full-color "OLED dream display" has been basically realized.

Materials play a decisive role in the research of organic electroluminescent devices, because the thin film is prepared by vacuum evaporation in the preparation process and is in an amorphous state. The crystallization of materials will reduce the luminescent performance and is considered to be the main reason for device aging. In view of this, it is usually necessary to take appropriate measures to reduce or prevent the crystallization of organic layer materials in the thin film preparation process. First, increase the asymmetry of the molecular structure; second, increase the steric hindrance of the molecular structure and reduce molecular aggregation.

Although the performance of the known OLED materials has been greatly improved compared with the previous ones, they have not yet achieved satisfactory luminous efficiency, lifetime and light purity.

Therefore, it is of great practical significance to develop stable and efficient OLED materials, improve device efficiency, prolong device life, and improve light purity.

Contents of the invention

The present invention synthesizes a series of new electroluminescent materials through molecular design, which can be used in hole transport layer, hole injection layer and optical coupling layer, greatly reduces the starting voltage of the device, improves the current efficiency of the device, and makes the device have Higher luminous efficiency, longer life, while improving the purity of light.

In order to realize above-mentioned device performance, the technical scheme that the present invention adopts is as follows:

The present invention provides a kind of organic compound, it has the structure shown in formula I:

in:

R ₁ , R ₂ and R ₃ are each independently selected from a hydrogen atom, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkoxy , substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C2-C30 heterocycle, substituted or unsubstituted C6 -C30 condensed and polycyclic groups, hydroxyl, cyano and substituted unsubstituted amino groups.

In a preferred embodiment of the compound of the present invention, the C6-C30 aryl group is selected from phenyl, biphenyl, naphthyl or anthracenyl.

In a preferred embodiment of the compound of the present invention, the compound is selected from compounds having structures shown in G1-G20:

The present invention also provides an electroluminescent device comprising using at least one of the above-mentioned compounds as a hole injection layer and/or a hole transport layer.

In a preferred embodiment of the electroluminescent device of the present invention, the device comprises a substrate and an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode sequentially stacked on the substrate.

In a preferred embodiment of the electroluminescent device according to the invention, the device further comprises an optical coupling layer arranged above the cathode.

In a preferred embodiment of the electroluminescent device of the present invention, the material of the optical coupling layer is selected from at least one of the compounds described in the present invention.

In a preferred embodiment of the electroluminescent device of the present invention, the anode material is at least one selected from indium tin oxide, indium zinc oxide and tin dioxide.

In a preferred embodiment of the electroluminescent device of the present invention, the light-emitting layer material is selected from dicarbazole biphenyl, 9,10-bis(2-naphthyl)anthracene, Ir(ppy ₃ ) or TPBi doped Dicarbazole biphenyl and at least one of Ir(ppy ₃ ) or TPBi doped 9,10-bis(2-naphthyl)anthracene.

In a preferred embodiment of the electroluminescent device of the present invention, the electron transport layer material is selected from 4,7-diphenyl-1,10-phenanthroline and tris(8-hydroxyquinoline)aluminum at least one.

In a preferred embodiment of the electroluminescent device of the present invention, the cathode is at least one selected from magnesium, aluminum and silver.

Beneficial effects of the present invention:

The compound provided by the present invention is an asymmetric structure, and other group modifications are added to make the material have higher carrier injection and transport capabilities. The compound of the present invention also has excellent thermal stability, higher glass Temperature, larger triplet state energy level, and then obtain an organic light-emitting device with high luminous efficiency, low driving voltage, long life, high brightness, and high color purity, which can be used as a new light-emitting center.

Description of drawings

Figure 1 is a schematic diagram of an electroluminescent device according to the present invention;

Fig. 2 is the absorption spectrum of compound G11 in the present invention;

Fig. 3 is the emission spectrum of compound G11 in the present invention;

Fig. 4 is a thermogravimetric diagram of compound G11 in the present invention.

detailed description

Preferred embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings and examples, but the scope of the present invention is not limited to the following examples.

Compound Synthesis Example

Embodiment 1: the preparation of compound G1

The first step: prepare intermediate A according to the following steps:

(1) Synthesis of intermediate A-1:

Add 21.5g (0.1mole) of methyl o-bromobenzoate, 17.2g (0.1mole) of 1-naphthylboronic acid, 41.5g (0.3mole) of potassium carbonate, 200ml of toluene, 100ml of ethanol, and 100ml of water into the first reactor. Under nitrogen atmosphere, add tetrakis(triphenylphosphine)palladium 2.3g (0.002mole), raise the temperature to reflux overnight, point the plate to monitor until the reaction is complete, end the reaction, spin the reaction solution to dry, add 100ml of dichloromethane to dissolve completely And pass through a silica gel column, add 100ml of water to the filtrate, wash with water to separate the organic phase, spin it to dryness and boil it twice with ethanol to obtain 21g of solid intermediate A-1, with a yield of 80%.

(2) Synthesis of intermediates A-2 and A-3:

Add 2.62g (0.01mole) of intermediate A-1 and 50ml of tetrahydrofuran (THF) into the second reactor, pass through nitrogen protection, cool the ice-salt bath to below zero, slowly add 35ml of methyl lithium (CH ₃ Li) dropwise , exothermic violently, the solution turned red, the dropwise addition was completed in 15 minutes, kept stirring for 30 minutes, removed the ice-water bath, raised the temperature naturally, stirred at room temperature for 1 hour, quenched with water, adjusted to acidity with hydrochloric acid, separated to obtain an organic phase, and used for the water phase Extract with ethyl acetate, combine the organic phases and spin-dry them to obtain the oily intermediate A-2. Add 100ml of acetic acid and a few drops of hydrochloric acid to the oil, heat to reflux, add 150ml of water after cooling, precipitate a solid, filter and wash with water, and pass through a silica gel column to obtain 1.6g of solid intermediate A-3. The total yield is 65%.

(3) Synthesis of intermediate A-4:

Add 2.44g (0.01mole) of intermediate A-3 and 60ml of dimethylformamide (DMF) into the third reactor to dissolve them completely, and add 1.78g (0.01mole) of N-bromosuccinic acid dropwise under stirring at room temperature The DMF solution (30% by mass) of imide (NBS) was used for 30 minutes, and after the dripping was completed, the stirring reaction was continued for 1 hour, and then the reaction was stopped. The solid was precipitated by adding water, filtered, rinsed with ethanol, and the crude product was recrystallized with toluene-ethanol system to obtain 2.6 g of solid intermediate A-4 with a yield of 80%.

(4) Synthesis of intermediate A-5:

Add 3.23g (0.01mole) of intermediate A-4, 2.5g (0.015mole) of o-nitrophenylboronic acid, 4.15g (0.03mole) of potassium carbonate, 30ml of toluene, 15ml of ethanol, and 15ml of water into the fourth reactor. Under nitrogen atmosphere, add tetrakis(triphenylphosphine)palladium 0.23g (0.0002mole), raise the temperature to reflux, point the plate to monitor until the reaction is complete, stop the reaction, spin the reaction solution to dryness, add 100ml of dichloromethane, dissolve it completely and Pass through a silica gel column, add 100ml of water to the filtrate, wash with water, separate the organic phase, spin it dry, boil it twice with ethanol, and filter to obtain 3g of solid intermediate A-5, with a yield of 80%.

(5) Synthesis of intermediate A-6:

Add 3.65g (0.01mole) of intermediate A-5 to the fifth reactor, then add 60ml of DMF to dissolve it completely, add 1.78g (0.01mole) of NBS in three batches under stirring at room temperature for 30 minutes, continue after dropping After reacting for 1 hour, stop the reaction, add water to precipitate the solid, filter, rinse with ethanol, and recrystallize the crude product with toluene-ethanol system to obtain 3.5 g of solid intermediate A-6 with a yield of 80%.

(6) Synthesis of intermediate A-7:

Add 4.44g (0.01mole) intermediate A-6, 37ml triethoxyphosphorus [P(OEt) ₃ ], 37ml 1,2-dichlorobenzene to the sixth reactor, stir at 150°C for 9 hours, then After cooling, it was washed with distilled water, and the solvent was evaporated to obtain an oil, which was dissolved in dichloromethane and separated by column to obtain 3 g of off-white solid intermediate A-7, with a yield of 75%.

(7) Synthesis of Intermediate A:

Add 4.12g (0.01mle) of intermediate A, 2.04g (0.01mole) of iodobenzene, 4.14g (0.03mole) of potassium carbonate, 0.064g (0.001mloe) of copper powder, and 0.198 g (0.001mole), 50ml of xylene, heated to reflux, reacted overnight, spotted the plate to monitor until the reaction was complete, cooled down, added 100ml of toluene to filter, the filtrate was spin-dried, and recrystallized with ethanol-toluene to obtain 3.9g of solid intermediate A , the yield is 80%.

Preparation of core compound B, its structural formula and synthetic route are as follows:

The second step: preparation of target compound G1

The compound G1 to be prepared in this example has a structural formula and a synthetic route as follows:

The specific reaction process includes:

(1) Preparation of intermediate G1-2:

Mix 2.86g (0.01mole) of 1,4-dibromonaphthalene, 1.21g (0.01mole) of phenylboronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, and add four ( Triphenylphosphine) palladium 0.23g (0.0002mole), heat up to reflux for reaction, point the plate to monitor until the reaction is complete, end the reaction, spin the reaction solution to dryness, add 100ml of dichloromethane to dissolve it completely and pass it through a silica gel column, the filtrate Add 100 g of water, wash with water, separate the organic phase, spin it dry, boil it twice with ethanol, and filter to obtain 2.3 g of solid intermediate G1-2, with a yield of 80%.

(2) Preparation of intermediate G1-2:

Mix 2.83g (0.01mole) of intermediate G1-1, 2.09g (0.01mole) of 2-amino-9,9-dimethylfluorene and 50ml of toluene, and add 0.18g (0.0002mole) of tri( Dibenzylideneacetone) combined with dipalladium Pd ₂ (dba) ₃ , 1.44g (0.015mole) potassium tert-butoxide and 0.809g (0.0004mole, 10 mass% toluene solution) tri-tert-butylphosphine, heating to 80°C Reaction, spot plate monitoring, after the reaction is complete, cool to room temperature, add 100ml of toluene, pass through a silica gel funnel to obtain a filtrate, wash the filtrate with water 3 times to obtain an organic phase, spin it dry and pass it through a silica gel column to obtain 3.3g of solid intermediate G1-2 , the yield is 80%.

(3) Preparation of intermediate G1-3:

Mix 4.88g (0.01mole) of intermediate A, 4.11g (0.01mole) of intermediate G1-2 and 50ml of toluene, and add 0.18g (0.0002mole) of Pd2(dba) ₃ , 1.44g (0.015mole ) Potassium tert-butoxide and 0.809g (0.0004mole, 10% by mass toluene solution) tri-tert-butylphosphine, heated to 85°C for reaction, spot plate monitoring, after the reaction was complete, cooled to room temperature, added 100ml toluene, passed through a silica gel funnel, The filtrate was collected, and the filtrate was washed with water three times to obtain an organic phase, which was spin-dried and passed through a silica gel column to obtain 6.4 g of solid intermediate G1-3 with a yield of 78%.

(4) Preparation of intermediate G1-4:

Put 8.19g (0.01mole) of intermediate G1-3 in 60ml of DMF to dissolve it completely, add 1.78g (0.0095mole) of NBS solution in DMF (30% by mass) dropwise under stirring at room temperature for 30 minutes, and continue the reaction for 1 After one hour, stop the reaction, add water to precipitate the solid, filter, rinse with ethanol, and recrystallize with toluene-ethanol system to obtain 7.18 g of solid intermediate G1-4 with a yield of 80%.

(5) Preparation of compound G1:

Add 8.98g (0.01mole) of compound G-4, 2.72g (0.01mole) of triphenylene-2-boronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol, and 30ml of water, and add four ( Triphenylphosphine) palladium 0.23g (0.0002mole), heat up to reflux for reaction, point the plate to monitor until the reaction is complete, end the reaction, spin the reaction solution to dryness, add 100ml of dichloromethane to dissolve it completely and pass it through a silica gel column, the filtrate Wash with 100ml of water, separate the organic phase, spin it dry, boil it twice with ethanol, and filter to obtain 8.3g of light yellow solid compound G1, with a yield of 80%. MS (m/e): 1044.44, elemental analysis: C ₈₀ H ₅₆ N ₂ , theoretical value C: 91.92, H: 5.40, N: 2.68; found value C: 91.87, H: 5.42, N: 2.71.

Embodiment 2: the preparation of compound G2

The preparation of the target compound G2 of this embodiment, its structural formula and synthetic route are as follows:

Concretely, the preparation method of the compound of the present invention comprises:

(1) Intermediate G1-4 was prepared according to the same method as in Example 1;

(2) Mix 8.98g (0.01mole) of intermediate G1-4, 2.46g (0.01mole) of fluoranthene-3-boronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, and in nitrogen atmosphere Under the atmosphere, add 0.23g (0.0002 mole) of tetrakis(triphenylphosphine) palladium to react, raise the temperature to reflux, spot the plate to monitor until the reaction is complete, then end the reaction, spin the reaction solution to dry, add 100ml of dichloromethane to dissolve it completely Pass through a silica gel column, add 100ml of water to the filtrate, wash with water, separate the organic phase, spin it to dryness, boil it twice with ethanol, and filter to obtain 7.6g of light yellow solid compound G2, with a yield of 75%. MS (m/e): 1018.43, elemental analysis: C ₇₈ H ₅₄ N ₂ , theoretical value C: 91.91, H: 5.34, N: 2.75; found value C: 91.90, H: 5.35, N: 2.75.

Embodiment 3: the preparation of compound G3

The preparation of the target compound G3 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation method of the compound G3 includes:

(1) Intermediate G1-4 was prepared according to the same method as in Example 1;

(2) Mix 8.48g (0.01mole) of intermediate G1-4, 2.74g (0.01mole) of 3,5-diphenylphenylboronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water , under a nitrogen atmosphere, add tetrakis(triphenylphosphine) palladium 0.23g (0.0002mole) to react, raise the temperature to reflux, point the plate to monitor until the reaction is complete, end the reaction, spin the reaction solution to dry, add 100ml of dichloromethane, make The solution was completely dissolved and passed through a silica gel column. The filtrate was added with 100ml of water, washed with water to separate the organic phase, spin-dried and boiled twice with ethanol, and filtered to obtain 7.7g of solid compound G3 with a yield of 77%. MS (m/e): 996.44,. Elemental analysis: C ₇₆ H ₅₆ N ₂ , theoretical value C: 91.53, H: 5.66, N: 2.81; measured value C: 91.55, H: 5.63, N: 2.82.

Embodiment 4: the preparation of compound G4

The preparation of the target compound G4 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation method of the compound G4 includes:

(1) Intermediate G1-4 was prepared according to the same method as in Example 1;

(2) Mix 8.48g (0.01mole) of intermediate G1-4, 3.6g (0.01mole) of 9,9-spirobifluorene-2-boronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and water Mix 30ml, under nitrogen atmosphere, add 0.23g (0.0002mole) tetrakis (triphenylphosphine) palladium to react, raise the temperature to reflux, point the plate to monitor until the reaction is complete, end the reaction, spin the reaction solution dry, add 100ml of dichloromethane , make it dissolve completely and pass through a silica gel column, add 100ml of water to the filtrate, wash with water to separate the organic phase, spin it to dryness and boil twice with ethanol, filter to obtain 7.58g of light yellow solid compound G4, yield 70%. MS (m/e): 1082.46, elemental analysis: C ₈₃ H ₅₈ N ₂ , theoretical value C: 92.02, H: 5.40, N: 2.59; found value C: 92.00, H: 5.41, N: 2.59.

Embodiment 5: the preparation of compound G5

The preparation of the target compound G5 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation method of the compound G5 includes:

(1) Preparation of intermediate G5-1:

Add 3.33g (0.03mole) o-fluoroaniline to the first container, then add 60ml DMF to dissolve it completely, add 28.92g (0.06mole) DMF solution of tetrabutylammonium tribromide dropwise under stirring at room temperature for 30 minutes , After the dropwise reaction was continued for 1 hour, the reaction was basically complete. The solid was precipitated by adding water, filtered, rinsed with ethanol, and recrystallized with toluene-ethanol system to obtain solid intermediate G5-1 with a yield of 80%.

(2) Preparation of intermediate G5-2:

Add 2.69g (0.01mole) of intermediate G5-1, 2.44g (0.02mole) of phenylboronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water into the second container. , add tetrakis (triphenylphosphine) palladium 0.23g (0.0002mole), raise the temperature to reflux to react, point the plate to monitor until the reaction is complete, turn off the heating, spin dry, add 100ml of dichloromethane to dissolve completely and pass through the silica gel column , the filtrate was added with 100ml of water, washed with water, and the organic phase was separated, spin-dried and boiled twice with ethanol, filtered to obtain off-white solid intermediate G5-2, with a yield of 70%.

(3) Preparation of intermediate G5-3:

Add 2.63g (0.01mole) of intermediate G5-2, 1.22g (0.01mole) of bromobenzene and 50ml of toluene to the third container respectively, and add 0.18g (0.0002mole) of Pd ₂ (dba) ₃ , 1.44g (0.015mole) potassium tert-butoxide and 0.809g (0.0004mole, 10% by mass toluene solution) tri-tert-butylphosphine, heated to 70°C for reaction, spot plate monitoring, cooled to room temperature after the reaction was complete, and added 100ml toluene , passed through a silica gel funnel to obtain a filtrate, and washed the filtrate with water three times to obtain an organic phase, which was spin-dried and passed through a silica gel column to obtain a solid intermediate G5-3 with a yield of 75%.

(4) Preparation of intermediate G5-4:

Intermediate A is provided, and Intermediate A is prepared according to the same method as in Example 1;

Mix 3.39g (0.01mole) of intermediate G5-3, 4.88g (0.01mole) of intermediate A and 50ml of toluene, and add 0.18g (0.0002mole) of Pd ₂ (dba) ₃ , 1.44g (0.015 mole) Potassium tert-butoxide and 0.809g (0.0004mole, 10% by mass toluene solution) tri-tert-butylphosphine, heated to 70°C for reaction, spot plate monitoring, cooled to room temperature after the reaction was complete, added 100ml toluene, passed through a silica gel funnel The filtrate was obtained, and the filtrate was washed with water three times to obtain an organic phase, which was spin-dried and passed through a silica gel column to obtain a solid intermediate G5-4 with a yield of 75%.

(5) Preparation of intermediate G5-5:

Add 14.94g (0.02mole) of intermediate G5-4 to the fourth container, then add 100ml of DMF to dissolve it completely, add 1.78g (0.0095mole) of NBS solution in DMF (30% by mass) dropwise under stirring at room temperature for 30 minutes , after continuing to react for 1 hour, stop the reaction, add water to precipitate the solid, filter, rinse with ethanol, and recrystallize with toluene-ethanol system to obtain solid intermediate G5-5 with a yield of 70%.

(6) Preparation of Compound G5:

Put 8.25g (0.01mole) of intermediate G5-5, 2.46g (0.01mole) of fluoranthene-3-boronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, and blow nitrogen gas for 10 minutes, Then add tetrakis(triphenylphosphine) palladium 0.23g (0.0002mole), raise the temperature to reflux to react, point the plate to monitor until the reaction is complete, turn off the heating, spin dry, add 100ml of dichloromethane to dissolve completely and pass through the silica gel column , the filtrate was added with 100ml of water, washed with water to separate the organic phase, spin-dried and boiled twice with ethanol to obtain light yellow solid compound G5 with a yield of 70%. MS (m/e): 946.37, elemental analysis: C ₇₁ H ₄₇ FN ₂ , theoretical value C: 90.03, H: 5.00, F: 2.01, N: 2.96; measured value C: 90.04, H: 4.96, F: 2.02 , N: 2.98.

Embodiment 6: the preparation of compound G6

The preparation of the target compound G6 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation method of the compound G6 includes:

(1) Preparation of intermediate G6-1:

Intermediate A is provided, and Intermediate A is prepared according to the same method as in Example 1;

Add 3.21g (0.01mole) of bis-(4-biphenyl)amine, 4.88g (0.01mole) of intermediate A and 50ml of toluene under nitrogen atmosphere, add 0.18g (0.0002mole) of Pd ₂ (dba) ₃ , 1.44g (0.015mole) potassium tert-butoxide and 0.809g (0.0004mole, 10% by mass toluene solution) tri-tert-butylphosphine, heated to 70°C for reaction, spot plate monitoring, cooled to room temperature after the reaction was complete, and added 100ml toluene , passed through a silica gel funnel to obtain a filtrate, and washed the filtrate with water three times to obtain an organic phase, which was spin-dried and passed through a silica gel column to obtain a solid intermediate G6-1 with a yield of 75%.

(2) Preparation of intermediate G6-2:

Add 7.29g (0.01mole) of intermediate G6-1 into 100ml of DMF to dissolve it completely, add 1.78g (0.0095mole) of NBS solution in DMF (30% by mass) dropwise under stirring at room temperature for 30 minutes, and continue the reaction for 1 hour Afterwards, stop the reaction, add water to precipitate the solid, filter, rinse with ethanol, and recrystallize with toluene-ethanol system to obtain solid intermediate G6-2 with a yield of 70%.

(3) Preparation of compound G6:

Mix 8.08g (0.01mole) of intermediate G6-2, 2.46g (0.01mole) of fluoranthene-3-boronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, and blow nitrogen gas for 10 minutes , then add tetrakis (triphenylphosphine) palladium 0.23g (0.0002mole), raise the temperature to reflux to react, point the plate to monitor until the reaction is complete, turn off the heating, spin dry, add 100ml of dichloromethane, 100ml of water to dissolve completely And passed through a silica gel column, the filtrate was added with 100ml of water, washed with water to separate the organic phase, spin-dried and boiled twice with ethanol to obtain light yellow solid compound G6 with a yield of 70%. MS (m/e): 928.38, Elemental Analysis: C ₇₁ H ₄₈ N ₂ , C: 91.78, H: 5.21, N: 3.01; Found C: 91.80, H: 5.22, N: 2.98.

Embodiment 7: the preparation of compound G7

The preparation of the target compound G7 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation method of the compound G7 includes:

(1) Preparation of intermediate G7-1:

Intermediate A is provided, and Intermediate A is prepared according to the same method as in Example 1;

Mix 2.19g (0.01mole) of N-phenyl-N-(1-naphthyl)amine, 4.88g (0.01mole) of intermediate A and 50ml of toluene, and then add 0.18g (0.0002mole ) Pd ₂ (dba) ₃ , 1.44g (0.015mole) potassium tert-butoxide and 0.809g (0.0004mole, 10 mass% toluene solution) tri-tert-butylphosphine, heated to 70°C for reaction, spot plate monitoring, the reaction was complete After cooling to room temperature, 100ml of toluene was added, and the filtrate was obtained through a silica gel funnel. The filtrate was washed with water three times to obtain an organic phase, which was spin-dried and passed through a silica gel column to obtain a solid intermediate G7-1 with a yield of 80%.

(2) Preparation of intermediate G7-2:

Add 6.27g (0.01mole) of intermediate G7-1 into 100ml of DMF to dissolve it completely, add 1.78g (0.0095mole) of NBS solution in DMF (30% by mass) dropwise under stirring at room temperature for 30 minutes, and continue the reaction for 1 hour Afterwards, stop the reaction, add water to precipitate the solid, filter, rinse with ethanol, and recrystallize with toluene-ethanol system to obtain the solid intermediate G7-2 with a yield of 70%.

(3) Preparation of compound G7:

Mix 7.05g (0.01mole) of intermediate G7-2, 2.74g (0.01mole) of 3,5-diphenylphenylboronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, and pass into Nitrogen for 10 minutes, then add tetrakis (triphenylphosphine) palladium 0.23g (0.0002mole), raise the temperature to reflux, point the plate to monitor until the reaction is complete, turn off the heating, spin dry, add 100ml of dichloromethane to dissolve completely and pass through Silica gel column, the filtrate was added with 100ml of water, washed with water to separate the organic phase, spin-dried, and boiled twice with ethanol to obtain light yellow solid compound G7 with a yield of 77%. MS (m/e): 854.37, elemental analysis: C ₆₅ H ₄₆ N ₂ , theoretical value C: 91.30, H: 5.42, N: 3.28; found value C: 91.28, H: 5.44, N: 3.28

Embodiment 8: the preparation of compound G8

The preparation of the target compound G8 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation method of the compound G8 includes:

(1) Preparation of intermediate G8-1:

Intermediate A is provided, and Intermediate A is prepared according to the same method as in Example 1;

Add 10g of Intermediate A (0.02mole) into 150ml of THF, cool down to -78°C, add 12ml (2.5M/L, 0.03mole) n-BuLi dropwise at -78°C, keep warm for 30 minutes, add dropwise 4.26g (0.041 mole) trimethyl borate, reacted for 2 hours to end the reaction, added 50ml of water to the reaction solution, stirred for 20 minutes, added hydrochloric acid to adjust the pH value to acidity, stirred for 30 minutes, extracted the reaction solution three times with ethyl acetate, combined the organic layers and washed with water Once, the organic phase was separated, the organic liquid was spin-dried, boiled in petroleum ether twice, and filtered to obtain an off-white solid intermediate G8-1 with a yield of 60%.

(2) Preparation of intermediate G8-2:

4.53g (0.01mole) of intermediate G8-1, 2.68g (0.01mole) of 2-chloro-4,6-diphenyltriazine, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water Mixed, under nitrogen atmosphere, then add tetrakis (triphenylphosphine) palladium 0.23g (0.0002mole), raise the temperature to reflux for reaction, point the plate to monitor until the reaction is complete, stop the reaction, spin the reaction solution to dry, add 100ml of dichloromethane, Make it completely dissolve and pass through a silica gel column, add 100ml of water to the filtrate, wash with water to separate the organic phase, spin dry, boil the solid with ethanol twice to obtain an off-white solid intermediate G8-2, with a yield of 75.4%.

(3) Preparation of intermediate G8-3:

Add 6.41g (0.01mole) of intermediate G8-3 to 100ml of DMF, stir well to dissolve it completely, add 1.78g (0.01mole) of NBS solution in DMF (30% by mass) dropwise at room temperature for 30 minutes, continue after dropping Stir the reaction for 1 hour, add water to precipitate a solid, filter, rinse with ethanol, and recrystallize with toluene-ethanol system to obtain a solid intermediate G8-3 with a yield of 70%.

(4) Preparation of compound G8:

Mix 7.20g (0.01mole) of intermediate G8-3, 2.74g (0.01mole) of 3,5-diphenylphenylboronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, and Under the atmosphere, add 0.23g (0.0002 mole) of tetrakis(triphenylphosphine) palladium, raise the temperature to reflux for reaction, point the plate to monitor until the reaction is complete, turn off the heating, spin dry, add 100ml of dichloromethane to dissolve completely and pass Silica gel column, the filtrate was added with 100ml of water, washed with water, the organic phase was separated, spin-dried, and boiled twice with ethanol to obtain white solid compound G8 with a yield of 77%. MS (m/e): 868.36, elemental analysis: C ₆₄ H ₄₄ N ₄ , theoretical value C: 88.45, H: 5.10, N: 6.45; found value C: 88.40, H: 5.12, N: 6.48.

Embodiment 9: Preparation of compound G9

The preparation of the target compound G9 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation method of the compound G9 includes:

(1) Preparation of intermediate G9-1:

Add 7g of 2-(4-bromophenyl)-1-phenylbenzimidazole (0.02mole) into 150ml of THF, cool down to -78°C, add 12ml (2.5M/L, 0.03mole) dropwise at -78°C -BuLi, keep warm for 30 minutes, add 4.26g (0.041mole) trimethyl borate dropwise, finish the reaction after 2 hours of reaction, add 50ml of water to the reaction solution, stir for 20 minutes, add hydrochloric acid to adjust the pH value to acidity, stir for 30 minutes, The reaction solution was extracted three times with ethyl acetate, the combined organic layers were washed once with water, the organic phase was separated, spin-dried, the solid was boiled twice with petroleum ether, and filtered to obtain an off-white solid intermediate G9-1 with a yield of 65%.

(2) Preparation of intermediate G9-2:

Intermediate A is provided, and Intermediate A is prepared according to the same method as in Example 1;

Mix 3.14g (0.01mole) of intermediate G9-1, 4.88g (0.01mole) of intermediate A, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, and add four ( Triphenylphosphine) palladium 0.23g (0.0002mole), heat up and reflux for 5 hours to react, point the plate to monitor until the reaction is complete, turn off the heating, spin the reaction solution to dryness, add 100ml of dichloromethane to completely dissolve it and pass it through a silica gel column, Add 100ml of water to the filtrate, wash with water, separate the organic phase, spin the organic phase to dryness, boil it twice with ethanol, and filter to obtain a white solid intermediate G9-2 with a yield of 75%.

(3) Preparation of intermediate G9-3:

Add 6.78g (0.01mole) of intermediate G9-2 to 100ml of DMF to dissolve it completely, add 1.78g (0.01mole) of NBS solution in DMF (30% by mass) dropwise under stirring at room temperature for 30 minutes, then continue the reaction at room temperature 1 hour. The solid was precipitated by adding water, filtered, rinsed with ethanol, and recrystallized with toluene-ethanol system to obtain solid intermediate G9-3 with a yield of 70%.

(4) Preparation of compound G9:

Mix 7.56g (0.01mole) of intermediate G9-3, 2.46g (0.01mole) of fluoranthene-3-boronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water. Under nitrogen atmosphere, Add 0.23g (0.0002 mole) of tetrakis(triphenylphosphine)palladium, raise the temperature to reflux for reaction, point the plate to monitor until the reaction is complete, stop the reaction, spin the reaction solution to dryness, add 100ml of dichloromethane to dissolve completely and pass through silica gel column, the filtrate was added with 100ml of water, washed with water, the organic phase was separated, spin-dried and boiled twice with ethanol, and filtered to obtain white solid compound G9 with a yield of 77%. MS (m/e): 877.35, elemental analysis: C ₆₆ H ₄₃ N ₃ , theoretical value C: 90.28, H: 4.94, N: 4.79; found value C: 90.35, H: 4.91, N: 4.84.

Embodiment 10: Preparation of compound G10

The preparation of the target compound G10 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation method of the compound G8 includes:

(1) Preparation of intermediate G10-1:

Intermediate A is provided, and Intermediate A is prepared according to the same method as in Example 1;

Mix 2.12g (0.01mole) of dibenzofuran-4-boronic acid, 4.88g (0.01mole) of intermediate A, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, under nitrogen atmosphere, Add tetrakis(triphenylphosphine)palladium 0.23g (0.0002mole), raise the temperature to reflux to react, react for 5 hours, the reaction is completed, spin the reaction solution to dryness, add 100ml of dichloromethane, dissolve it completely and pass it through a silica gel column, The filtrate was added with 100ml of water, washed with water, and the organic phase was separated, spin-dried, boiled twice with ethanol, and filtered to obtain a white solid intermediate G10-1 with a yield of 73%.

(2) Preparation of intermediate G10-2:

Add 5.76g (0.01mole) of intermediate G10-1 into 100ml of DMF to dissolve it completely, add 1.78g (0.01mole) of NBS solution in DMF (30% by mass) dropwise under stirring at room temperature for 30 minutes, and continue the reaction for 1 hour , stop responding. The solid was precipitated by adding water, filtered, rinsed with ethanol, and the crude product was recrystallized with a toluene-ethanol system to obtain a solid intermediate G10-2 with a yield of 70%.

(3) Preparation of Compound G10:

Mix 6.56g (0.01mole) of intermediate G10-2, 2.48g (0.01mole) of 1-pyrene boronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, and add four (Triphenylphosphine) palladium 0.23g (0.0002mole), heat up to reflux for reaction, point the plate to monitor until the reaction is complete, end the reaction, spin the reaction solution to dryness, add 100ml of dichloromethane, dissolve it completely and pass it through a silica gel column, Add 100ml of water to the filtrate, wash with water, separate the organic phase, spin it dry and heat it with ethanol twice, and filter to obtain white solid compound G10 with a yield of 73%. MS (m/e): 777.30, elemental analysis: C ₅₉ H ₃₉ NO, theoretical value C: 91.09, H: 5.05, N: 1.80, O: 2.06; found value C: 91.09, H: 5.10, N: 1.78, O: 2.03.

Embodiment 11: Preparation of compound G11

The preparation of the target compound G11 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation method of the compound G8 includes:

(1) Preparation of intermediate G11-1:

Intermediate A is provided, and Intermediate A is prepared according to the same method as in Example 1;

Mix 2.12g (0.01mole) of dibenzofuran-2-boronic acid, 4.88g (0.01mole) of intermediate A, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, and under nitrogen atmosphere, Add tetrakis(triphenylphosphine)palladium 0.23g (0.0002mole), raise the temperature to reflux for reaction, point the plate to monitor until the reaction is complete, end the reaction, spin the reaction solution to dryness, add 100ml of dichloromethane to dissolve completely and pass through silica gel column, the filtrate was added to 100ml of water, washed with water, the organic phase was separated, spin-dried and boiled twice with ethanol, and filtered to obtain a white solid intermediate G11-1 with a yield of 73%.

(2) Preparation of intermediate G11-2:

Add 5.76g (0.01mole) of intermediate G11-1 into 100ml of DMF to dissolve it completely, add 1.78g (0.01mole) of NBS solution in DMF (30% by mass) dropwise under stirring at room temperature for 30 minutes, and continue the reaction for 1 hour End the reaction. The solid was precipitated by adding water, filtered, rinsed with ethanol, and the crude product was recrystallized with a toluene-ethanol system to obtain a solid intermediate G11-2 with a yield of 70%.

(3) Preparation of compound G11:

Mix 6.56g (0.01mole) of intermediate G11-2, 2.46g (0.01mole) of fluoranthene-3-boronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water. Under nitrogen atmosphere, Add tetrakis(triphenylphosphine)palladium 0.23g (0.0002mole), raise the temperature to reflux for reaction, point the plate to monitor until the reaction is complete, end the reaction, spin the reaction solution to dryness, add 100ml of dichloromethane to dissolve completely and pass through silica gel column, add 100ml of water to the filtrate, wash with water, separate the organic phase, spin it dry and boil it twice with ethanol, and filter to obtain white solid compound G11 with a yield of 73%. MS (m/e): 775.29, elemental analysis: C ₅₉ H ₃₇ NO, theoretical value C: 91.33, H: 4.81, N: 1.81, O: 2.06; found value C: 91.35, H: 4.82, N: 1.77, O: 2.06.

The absorption and emission spectra of the compound G11 in this example are shown in Figures 2 and 3, as can be seen from the absorption spectrum in Figure 2, G11 mainly absorbs the ultraviolet light in the 200-350nm section, and it can be known from the emission spectrum that the emission of G11 The light is mainly blue light in the 450-550nm segment. It can be seen from the thermogravimetric diagram that G11 shows good stability at 450°C.

Embodiment 12: Preparation of Compound G12

The compound G12 to be prepared in this example has a structural formula and a synthetic route as follows:

Specifically, the preparation method of the compound G8 includes:

(1) Preparation of intermediate G12-1:

Intermediate A is provided, and Intermediate A is prepared according to the same method as in Example 1;

Mix 2.28g (0.01mole) of dibenzothiophene-4-boronic acid, 4.88g (0.01mole) of intermediate A, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, under nitrogen atmosphere, Add 0.23g (0.0002 mole) of tetrakis(triphenylphosphine) palladium, raise the temperature and reflux for 5 hours to react, spot the plate to monitor until the reaction is complete, stop the reaction, spin the reaction solution to dryness, add 100ml of dichloromethane to dissolve completely and pass through Silica gel column, add 100ml water to the filtrate, wash with water, separate the organic phase, spin it dry and boil it twice with ethanol, filter to obtain white solid intermediate G12-1, the yield is 70%.

(2) Preparation of intermediate G12-2:

Add 5.92g (0.01mole) of intermediate G12-1 into 100ml of DMF to dissolve it completely, add 1.78g (0.01mole) of NBS solution in DMF (30% by mass) dropwise with stirring at room temperature for 30 minutes, then continue the reaction 1 Hours, the reaction is complete, add water to precipitate the solid and filter, rinse with ethanol, and recrystallize the crude product with a toluene-ethanol system to obtain a solid intermediate G12-2 with a yield of 72%.

(3) Preparation of compound G12:

Mix 6.7g (0.01mole) of intermediate G12-2, 2.46g (0.01mole) of fluoranthene-3-boronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water. Under nitrogen atmosphere, Add tetrakis(triphenylphosphine)palladium 0.23g (0.0002mole), raise the temperature to reflux for reaction, point the plate to monitor until the reaction is complete, end the reaction, spin the reaction solution to dryness, add 100ml of dichloromethane to dissolve completely and pass through silica gel Column, add 100ml water to the filtrate, wash with water, separate the organic phase, spin it dry and boil it twice with ethanol, filter to obtain off-white solid compound G12, the yield is 70%. MS (m/e): 791.26, elemental analysis: C ₅₉ H ₃₇ NS, theoretical value C: 89.47, H: 4.71, N: 1.77, S: 4.05; found value C: 89.50, H: 4.72, N: 1.75, S: 4.03.

Embodiment 13: Preparation of Compound G13

The preparation of the target compound G13 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation method of the compound G8 includes:

(1) Preparation of intermediate G13-1:

Intermediate A is provided, and Intermediate A is prepared according to the same method as in Example 1;

Mix 2.28g (0.01mole) of dibenzothiophene-2-boronic acid, 4.88g (0.01mole) of intermediate A, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, under nitrogen atmosphere, Add 0.23 g (0.0002 mole) of tetrakis(triphenylphosphine)palladium, raise the temperature and reflux for 5 hours to react, spot the plate to monitor until the reaction is complete, then end the reaction, spin the reaction solution to dryness, add 100ml of dichloromethane to dissolve completely and pass through Silica gel column, add 100ml of water to the filtrate, separate the organic phase, spin it to dryness, boil it twice with ethanol, and filter to obtain the white solid intermediate G13-1 with a yield of 70%.

(2) Preparation of intermediate G13-2:

Add 5.92g (0.01mole) of intermediate G13-1 into 100ml of DMF to dissolve it completely, add 1.78g (0.01mole) of NBS solution in DMF (30% by mass) dropwise with stirring at room temperature for 30 minutes, and continue to stir the reaction after dropping After 1 hour, the reaction was stopped, and the solid was precipitated by adding water, filtered, rinsed with ethanol, and the crude product was recrystallized with toluene-ethanol system to obtain a solid intermediate G13-2 with a yield of 72%.

(3) Preparation of compound G13:

Mix 6.7g (0.01mole) of compound G13-2, 3.6g (0.01mole) of 9,9-diphenylfluorene-2-boronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, Under a nitrogen atmosphere, add 0.23 g (0.0002 mole) of tetrakis(triphenylphosphine) palladium, raise the temperature to reflux for reaction, monitor the plate until the reaction is complete, and end the reaction. The reaction solution is spin-dried, and 100 ml of methylene chloride is added to make Dissolve completely and pass through a silica gel column, add 100ml of water to the filtrate, wash with water, separate the organic phase, spin it dry and boil it twice with ethanol, and filter to obtain a white solid compound G13 with a yield of 70%. MS (m/e): 907.33, elemental analysis: C ₆₈ H ₄₅ NS, theoretical value C: 89.93, H: 4.99, N: 1.54, S: 3.53; found value C: 89.90, H: 4.98, N: 1.55, S: 3.57.

Embodiment 14: Preparation of Compound G14

Intermediate B was prepared as follows;

Intermediate A-7 is provided, and Intermediate A-7 is prepared according to the same method as in Example 1;

4.12g (0.01mle) of intermediate A-7, 2.8g (0.01mole) of 4-iodobiphenyl, 4.14g (0.03mole) of potassium carbonate, 0.064g (0.001mloe) of copper powder, 0.198g ( 0.001mole) mixed with 50ml of xylene, heated to reflux for reaction, spot plate monitoring until the reaction was complete, cooled down, added 100ml of toluene to filter, the filtrate was spin-dried, and recrystallized with ethanol-toluene to obtain solid intermediate B with a yield of 80 %.

The preparation of the target compound G14 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation method of the compound G8 includes:

(1) Preparation of intermediate G14-1:

Intermediate B is provided, and the intermediate B is prepared according to the method of this example;

Intermediate G1-2 is provided, and the intermediate G1-2 is prepared according to the method of Example 1;

Mix 5.64g (0.01mole) of intermediate B, 4.12g (0.01mole) of intermediate G1-2 and 50ml of toluene, and add 0.18g (0.0002mole) of Pd ₂ (dba) ₃ , 1.44g (0.015 mole) Potassium tert-butoxide and 0.809g (0.0004mole, 10% by mass toluene solution) tri-tert-butylphosphine, heated to 70°C for reaction, spot plate monitoring, cooled to room temperature after the reaction was complete, added 100ml toluene, passed through a silica gel funnel The filtrate was obtained, and the filtrate was extracted with water three times to obtain an organic phase, which was spin-dried and passed through a silica gel column to obtain a solid intermediate G14-1 with a yield of 75%.

(2) Preparation of intermediate G14-2:

Add 8.9g (0.01mole) of intermediate G14-1 into 100ml of DMF to dissolve it completely, add 1.78g (0.01mole) of NBS solution in DMF (30% by mass) dropwise under stirring at room temperature for 30 minutes, and continue the reaction after dropping After 1 hour, the reaction was stopped. The solid was precipitated by adding water, filtered, rinsed with ethanol, and the crude product was recrystallized with a toluene-ethanol system to obtain a solid intermediate G14-2 with a yield of 70%.

(3) Preparation of Compound G14:

Mix 9.74g (0.01mole) of intermediate G14-2, 2.74g (0.01mole) of 3,5-diphenylphenylboronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, and Under the atmosphere, add 0.23g (0.0002 mole) of tetrakis(triphenylphosphine)palladium, raise the temperature to reflux for reaction, point the plate to monitor until the reaction is complete, then end the reaction, spin the reaction solution to dry, add 100ml of dichloromethane to dissolve it completely And pass through a silica gel column, add 100ml of water to the filtrate, wash with water, separate the organic phase, spin it dry and boil it twice with ethanol, and filter to obtain a white solid compound G14 with a yield of 77%. MS (m/e): 1122.49, elemental analysis: C ₈₈ H ₆₂ N ₂ , theoretical value C: 91.94, H: 5.56, N: 2.49; found value C: 91.90, H: 5.60, N: 2.50.

Embodiment 15: Preparation of Compound G15

The preparation of the target compound G15 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation of compound G15 includes the following steps:

(1) Preparation of intermediate G15-1

Intermediate B is provided, which is prepared according to the method in Example 14;

Intermediate G1-2 is provided, and the intermediate G1-2 is prepared according to the method in Example 1;

Mix 5.64g (0.01mol) of intermediate B, 3.61g (0.01mol) of intermediate G1-2 and 50ml of toluene, and add 0.18g (0.0002mol) of Pd ₂ (dba) ₃ , 1.44g (0.015 mol) Potassium tert-butoxide, 0.809g (0.0004mole, 10% by mass toluene solution) tri-tert-butylphosphine, heated to 70°C for reaction, spot plate monitoring, cooled to room temperature after the reaction was complete, added 100ml toluene, passed through a silica gel funnel The filtrate was obtained, and the filtrate was extracted with water three times to obtain an organic phase, which was spin-dried and passed through a silica gel column to obtain a solid intermediate G15-1 with a yield of 75%.

(2) Preparation of intermediate G15-2:

Add 8.45g (0.01mol) of intermediate G15-1 into 100ml of DMF to dissolve it completely, add 1.78g (0.01mol) of NBS solution in DMF (30% by mass) dropwise under stirring at room temperature for 30 minutes, and continue the reaction after dropping After 1 hour, the reaction was stopped. The solid was precipitated by adding water, filtered, rinsed with ethanol, and the crude product was recrystallized with a toluene-ethanol system to obtain a solid intermediate G15-2 with a yield of 70%.

(3) Preparation of compound G15:

Mix 9.24g (0.01mole) of intermediate G15-2, 2.74g (0.01mole) of 3,5-diphenylphenylboronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, and Under the atmosphere, add tetrakis(triphenylphosphine) palladium 0.23g (0.0002mole), raise the temperature to reflux to react, point the plate to monitor until the reaction is complete, stop the reaction, spin the reaction solution to dry, add 100ml of dichloromethane to dissolve completely And pass through a silica gel column, add 100ml of water to the filtrate, wash with water, separate the organic phase, spin it dry and boil it twice with ethanol, and filter to obtain a white solid compound G15 with a yield of 77%. MS (m/e): 1072.48, elemental analysis: C ₈₂ H ₆₀ N ₂ , theoretical value C: 91.76, H: 5.63, N: 2.61; found value C: 91.80, H: 5.65, N: 2.55.

Embodiment 16: Preparation of Compound G16

The preparation of the target compound G16 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation of compound G16 includes the following steps:

Intermediate G5-5 is provided, and the intermediate G5-5 is prepared according to the method in Example 5; 8.25 g (0.01 mole) of intermediate G5-5, 2.72 g (0.01 mole) of triphenylene-2-boronic acid, carbonic acid Potassium 4.15g (0.03mole), toluene 50ml, ethanol 30ml and water 30ml, nitrogen gas was introduced for 10 minutes, then tetrakis (triphenylphosphine) palladium 0.23g (0.0002mole) was added, the temperature was raised to reflux for reaction, and the plate was monitored to After the reaction is complete, turn off the heating, spin dry, add 100ml of dichloromethane to dissolve completely and pass through a silica gel column, add 100ml of water to the filtrate, wash with water to separate the organic phase, spin dry and boil twice with ethanol to obtain a light yellow solid Compound G16, yield 70%. MS (m/e): 972.39, elemental analysis: C ₇₃ H ₄₉ FN ₂ , theoretical value C: 90.09, H: 5.08, F: 1.95, N: 2.88; measured value C: 90.05, H: 4.95, F: 2.02 , N: 2.98.

Embodiment 17: Preparation of Compound G17

The preparation of the target compound G17 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation of compound G17 includes the following steps:

Intermediate B is provided, which is prepared according to the method in Example 15;

Intermediate G5-3 is provided, and the intermediate G5-3 is prepared according to the method in Example 5;

Mix 3.39g (0.01mole) of intermediate G5-3, 5.64g (0.01mole) of intermediate B and 50ml of toluene, and add 0.18g (0.0002mole) of Pd ₂ (dba) ₃ , 1.44g (0.015 mole) Potassium tert-butoxide and 0.809g (0.0004mole, 10% by mass toluene solution) tri-tert-butylphosphine, heated to reflux for reaction, spot plate monitoring, after the reaction was complete, cooled to room temperature, added 100ml toluene, passed through a silica gel funnel to obtain The filtrate was extracted three times with water to obtain an organic phase, which was spin-dried and passed through a silica gel column to obtain a solid compound G17 with a yield of 75%. MS (m/e): 822.34, elemental analysis: C ₆₁ H ₄₃ FN ₂ , theoretical value C: 89.02, H: 5.27, F: 2.31N: 3.40; found value C: 89.02, H: 5.30, F: 2.34N : 3.34.

Embodiment 18: Preparation of Compound G18

The preparation of the target compound G18 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation of compound G18 includes the following steps:

(1) Preparation of intermediate G18-1:

Intermediate B is provided, which is prepared according to the method in Example 15;

Mix 2.12g (0.01mole) of dibenzofuran-4-boronic acid, 5.65g (0.01mole) of intermediate B, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water. Under nitrogen atmosphere, Add tetrakis(triphenylphosphine)palladium 0.23g (0.0002mole), raise the temperature to reflux for reaction, point the plate to monitor until the reaction is complete, end the reaction, spin the reaction solution to dryness, add 100ml of dichloromethane to dissolve completely and pass through silica gel column, the filtrate was added to 100ml of water, washed with water, the organic phase was separated, spin-dried and boiled twice with ethanol, and filtered to obtain an off-white solid intermediate G18-1 with a yield of 73%.

(2) Preparation of intermediate G18-2:

Add 6.52g (0.01mole) of intermediate G18-1 into 100ml of DMF to dissolve it completely, add 1.78g (0.01mole) of NBS solution in DMF (30% by mass) dropwise under stirring at room temperature for 30 minutes, and continue the reaction after dropping After 1 hour, the reaction was stopped. The solid was precipitated by adding water, filtered, rinsed with ethanol, and the crude product was recrystallized with a toluene-ethanol system to obtain a solid intermediate G18-2 with a yield of 70%.

(3) Preparation of Compound G18:

Mix 7.31g (0.01mole) of intermediate G18-2, 2.46g (0.01mole) of fluoranthene-3-boronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water. Under nitrogen atmosphere, Add tetrakis(triphenylphosphine)palladium 0.23g (0.0002mole), raise the temperature to reflux for reaction, point the plate to monitor until the reaction is complete, end the reaction, spin the reaction solution to dryness, add 100ml of dichloromethane to dissolve completely and pass through silica gel column, add 100ml of water to the filtrate, wash with water, separate the organic phase, spin it dry and boil it twice with ethanol, and filter to obtain a white solid compound G18 with a yield of 73%. MS (m/e): 851.32, elemental analysis: C ₆₅ H ₄₁ NO, theoretical value C: 91.63, H: 4.85, N: 1.64, O: 1.88; found value C: 91.53, H: 4.90, N: 1.65, O: 1.92.

Embodiment 19: Preparation of Compound G19

First prepare intermediate C according to the following synthetic route:

4.12g (0.01mle) of intermediate A-7, 2.54g (0.01mole) of a-iodonnaphthalene, 4.14g (0.03mole) of potassium carbonate, 0.064g (0.001mloe) of copper powder, 0.198g (0.001 mole) mixed with 50ml of xylene, heated to reflux for reaction, monitored by pointing plate until the reaction was complete, lowered the temperature, added 100ml of toluene to filter, the filtrate was spin-dried, and recrystallized with ethanol-toluene system to obtain solid intermediate C with a yield of 75 %. MS (m/e): _563.12 , elemental analysis: _C37H26BrN , C: 78.72, H: 4.64, Br: 14.15, N: 2.48.

The compound G19 to be prepared in this example has a structural formula and a synthetic route as follows:

Specifically, the preparation of compound G19 includes the following steps

(1) Preparation of intermediate G19-1:

Intermediate G1-2 is provided, and the intermediate G1-2 is prepared according to the method of Example 1;

Mix 5.38g (0.01mole) of intermediate C, 4.11g (0.01mole) of intermediate G1-2 and 50ml of toluene, and add 0.18g (0.0002mole) of Pd2(dba) ₃ , 1.44g (0.015mole ) Potassium tert-butoxide and 0.809g (0.0004mole, 10% by mass toluene solution) tri-tert-butylphosphine, heated to 70°C for reaction, spot plate monitoring, after the reaction was complete, cooled to room temperature, added 100ml toluene, passed through a silica gel funnel to obtain The filtrate was extracted three times with water to obtain an organic phase, which was spin-dried and passed through a silica gel column to obtain a solid intermediate G19-1 with a yield of 75%.

(2) Preparation of intermediate G19-2:

Add 8.69g (0.01mole) of intermediate G19-1 into 100ml of DMF to dissolve it completely, add 1.78g (0.01mole) of NBS solution in DMF (30% by mass) dropwise under stirring at room temperature for 30 minutes, and continue the reaction after dropping After 1 hour, the reaction was stopped. The solid was precipitated by adding water, filtered, rinsed with ethanol, and the crude product was recrystallized with a toluene-ethanol system to obtain a solid intermediate G19-2 with a yield of 70%.

(3) Preparation of compound G19:

Mix 9.48g (0.01mole) of compound G19-2, 2.46g (0.01mole) of fluoranthene-3-boronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, and add Tetrakis(triphenylphosphine)palladium 0.23g (0.0002mole), heat up to reflux for reaction, point the plate to monitor until the reaction is complete, end the reaction, spin dry, add 100ml of dichloromethane to dissolve completely and pass through a silica gel column, the filtrate Add 100ml of water, wash with water, separate the organic phase, spin it dry, boil it twice with ethanol, and filter to obtain white solid compound G19 with a yield of 73%. MS (m/e): 1068.44, elemental analysis: C ₈₂ H ₅₆ N ₂ , theoretical value C: 92.10, H: 5.28, N: 2.62; found value C: 92.10, H: 5.30, N: 2.60.

Embodiment 20: Preparation of compound G20

The preparation of the target compound G20 of this embodiment, its structural formula and synthetic route are as follows:

Specifically, the preparation of compound G20 includes the following steps:

(1) Preparation of intermediate G20-1:

Intermediate C is provided, which is prepared according to the method of Example 19;

Mix 2.28g (0.01mole) of dibenzothiophene-2-boronic acid, 5.38g (0.01mole) of intermediate C, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, under nitrogen atmosphere, Add tetrakis(triphenylphosphine)palladium 0.23g (0.0002mole), raise the temperature to reflux for reaction, point the plate to monitor until the reaction is complete, end the reaction, spin dry, add 100ml of dichloromethane to dissolve completely and pass through the silica gel column, Add 100ml of water to the filtrate, wash with water, separate the organic phase, spin it to dryness, boil it twice with ethanol, and filter to obtain a white solid intermediate G20-1 with a yield of 70%.

(2) Preparation of intermediate G20-2:

Add 6.42g (0.01mole) of intermediate G20-1 into 100ml of DMF to dissolve it completely, add 1.78g (0.01mole) of NBS solution in DMF (30% by mass) dropwise under stirring at room temperature for 30 minutes, and continue the reaction after dropping After 1 hour, the reaction was stopped. The solid was precipitated by adding water and filtered, rinsed with ethanol, and the crude product was recrystallized with a toluene-ethanol system to obtain a solid intermediate G20-2 with a yield of 72%.

(3) Preparation of compound G20:

Mix 6.7g (0.01mole) of compound G20-2, 2.46g (0.01mole) of fluoranthene-3-boronic acid, 4.15g (0.03mole) of potassium carbonate, 50ml of toluene, 30ml of ethanol and 30ml of water, and add Tetrakis(triphenylphosphine)palladium 0.23g (0.0002mole), heat up to reflux for reaction, point the plate to monitor until the reaction is complete, turn off the heating, spin dry, add 100ml of dichloromethane to dissolve completely and pass through a silica gel column, the filtrate Add 100ml of water, wash with water, separate the organic phase, spin it dry, boil it twice with ethanol, and filter to obtain a white solid compound G20 with a yield of 70%. MS (m/e): 841.28, elemental analysis: C ₆₃ H ₃₉ NS, theoretical value C: 89.86, H: 4.67, N: 1.66, S: 3.81; found value C: 89.81, H: 4.70, N: 1.63, S: 3.86.

application example

Example 21:

(1) Device design

In order to compare the hole injection properties of materials, the structure of the electroluminescent device designed in the present invention is as follows: substrate/anode/hole injection layer (HIL)/hole transport layer (HTL)/light emitting layer (EL)/electron transport layer ( ETL)/cathode.

The substrate can be a traditional glass substrate or a plastic substrate, and a glass substrate is selected in this embodiment.

The anode can use indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO ₂ ), etc. In this embodiment, indium tin oxide (ITO) is selected as the anode.

As the hole injection material, TDATA, 2-TNATA, TCTA, etc. that have been reported so far can be used as the reference material. In this embodiment, 2-TNATA is selected as the reference material for hole injection.

The hole transport material can be NPB, TPD and the like commonly used in the prior art. In this embodiment, NPB is selected as the hole transport material.

The host material of the light-emitting layer can be CBP, ADN, etc., and the dopant material can be Ir(ppy) ₃ , TBPe, etc. In this embodiment, CBP doped Ir(ppy) ₃ is selected as the material of the light-emitting layer.

The electron transport material can use BPhen, Alq ₃ , TPBi, etc., and Alq ₃ is selected as the electron transport material in this embodiment.

The cathode can use Mg (magnesium), Al (aluminum), Ag (silver), etc. In this embodiment, Al is selected as the cathode material.

The material structure mentioned above is as follows:

(2) Preparation of devices

Preparation of comparative device 1:

Clean the ITO-coated glass substrate with ultrasonic cleaning agent for 5 minutes, then use ionized water for 5 minutes, isopropanol solvent for 5 minutes, take it out and bake until the water is completely removed, then use ultraviolet light and Ozone cleaning for 20 minutes.

The above-mentioned glass substrate with the anode is placed in a vacuum evaporation device, and 2-TNATA is vacuum-deposited on the anode layer film as a hole injection layer, and the evaporation thickness is 80nm;

Vacuum-evaporating NPB on the above-mentioned hole-injection layer film as a hole-transport layer, and the evaporation thickness is 20nm;

Vacuum-deposit the luminescent layer on the above-mentioned hole transport layer, evaporate CBP and Ir(ppy) ₃ , and evaporate the total film thickness to 30nm;

On the above-mentioned light-emitting layer, vacuum evaporate Alq ₃ as the electron transport layer, and the total thickness of evaporation is 80nm;

An Al layer was vacuum evaporated on the electron transport layer as the cathode of the device with a thickness of 150 nm.

Preparation of devices using compounds of the present invention as hole-injecting materials:

The preparation method is the same as the above method, only the compound of the hole injection layer is changed, please refer to Table 1 for details.

The performance of the prepared device is shown in Table 1 (device structure: ITO/hole injection layer (80nm)/NPB (20nm)/CBP:5%Ir(ppy) ₃ (30nm)/Alq ₃ (80nm)/Al (150nm) .

Table 1

The results of Example 21 show that when the compound of the present invention is used as the material of the hole injection layer, it can improve the electrical characteristics and charge transport capability of the device, and devices 1 to 10 respectively adopt the compound of the present invention as the material of the organic electroluminescent device. Compared with the comparative device 1, the material of the hole injection layer obviously reduces the start-up voltage of the device, improves the current efficiency of the device, and makes the device have a longer half-life at the same time.

Example 22:

Preferred embodiment of the device:

A device was prepared according to the method of Example 21, except that the material of the hole transport layer in the device was changed. Please refer to Table 2 for details.

The device preparation method of the test material is the same as Example 2, only the compound of the hole transport layer is changed. See Table 2 for specific device performance.

Table 2

The results of Example 22 show that when the compound of the present invention is used as the material of the hole transport layer, it can improve the electrical characteristics and charge transport capacity of the device, and devices 11 to 20 respectively adopt the novel material of the present invention as an organic electroluminescent device Compared with Comparative Example 2, the material of the hole transport layer obviously reduces the start-up voltage of the device, improves the current efficiency of the device, and makes the device have a longer half-life at the same time.

Example 23:

(1) Design of comparative device 3

In order to compare the performance of the material optical coupling layer (CPL), the structure of the electroluminescent device designed by the present invention is shown in Figure 1, including: substrate/reflective anode/hole injection layer (HIL)/hole transport layer (HTL)/ Emitting layer (EL)/electron transport layer (ETL)/transparent cathode/optical coupling layer (CPL).

The substrate can be a traditional glass substrate or a plastic substrate, and a glass substrate is selected in this embodiment.

The reflective anode can use Mg (magnesium), Al (aluminum), Ag (silver), etc. In this embodiment, Ag is selected as the transparent cathode material.

As the hole injection material, TDATA, 2-TNATA, TCTA, etc. that have been reported so far can be used, and 2-TNATA is selected as the hole injection material in this embodiment.

The hole transport material can be NPB, TPD and the like commonly used in the prior art. In this embodiment, NPB is selected as the hole transport material.

The host material of the light-emitting layer can be CBP, ADN, etc., and the dopant material can be Ir(ppy) ₃ , TBPe, etc., and ADN-doped TBPe is selected as the material of the light-emitting layer in this embodiment.

The electron transport material can use BPhen, Alq ₃ , TPBi, etc., and this embodiment selects BPhen as the electron transport material.

Mg (magnesium), Al (aluminum), Ag (silver), Mg·Ag, etc. can be used for the transparent cathode, and Mg·Ag is selected as the transparent cathode material in this embodiment.

The material of the optical coupling layer can be Alq ₃ , NPB, etc., and NPB is selected as the material of the optical coupling layer in this embodiment.

The structure of the above material is as shown in Example 21.

(2) Preparation of comparative device 3

Clean the glass substrate coated with reflective anode with cleaning agent under ultrasonic for 5 minutes, then use ionized water for 5 minutes, and isopropanol solvent for 5 minutes, take it out and bake until the water is completely removed, and then use ultraviolet light and ozone cleaning for 20 minutes.

The above-mentioned glass substrate with reflective anode is placed in a vacuum evaporation equipment, and 2-TNATA is vacuum-deposited on the anode layer film as a hole injection layer, and the evaporation thickness is 80nm;

Vacuum-evaporating NPB on the above-mentioned hole-injection layer film as a hole-transport layer, and the evaporation thickness is 20nm;

Vacuum-deposit the luminescent layer on the above-mentioned hole transport layer, evaporate AND and TBPe, and the total film thickness of the evaporation is 30nm;

BPhen was vacuum-evaporated on the above-mentioned light-emitting layer as an electron transport layer, and the total thickness of the evaporation was 80nm;

A Mg·Ag layer was vacuum-evaporated on the electron transport layer as the transparent cathode of the device with a thickness of 5 nm.

An optical coupling layer NPB is vacuum evaporated on the transparent cathode layer with a thickness of 150 nm.

Preparation of devices using compounds of the present invention as hole-injecting materials:

The preparation method of devices 31-40 is the same as that of comparative device 3, only the compound of the optical coupling layer material is changed. Please refer to Table 3 for details

The device performance is shown in Table 3 (device structure: reflective anode/2-TNATA (80nm)/NPB (20nm)/AND:5%TBPe(30nm)/BPhen (80nm)/Mg·Ag (5nm)/optical coupling layer (150nm ).

table 3

The results of Example 23 show that using the compound of the present invention as an optical coupling layer material not only improves the electrical characteristics and charge transport capability of the device, but also significantly improves the purity of light. Devices 31 to 40 use the novel materials of the present invention as Compared with the comparative device 3, the optical coupling layer material of the organic electroluminescent device not only reduces the starting voltage of the device, improves the current efficiency of the device, makes the device have a longer half-life, but also improves the purity of light.

Although the above embodiments have described the present invention, the present invention is not limited to the above embodiments. It should be understood that within the scope of the present invention, those skilled in the art can make various modifications and improvements.

Claims (8)

1. an organic compound, described compound is selected from the compound with the structure shown in G1-G20:

2. an electroluminescent device, comprises and uses at least one in compound described in claim 1 as hole injection layer and/or hole transmission layer.

3. electroluminescent device according to claim 2, is characterized in that, described device comprises substrate and is cascadingly set on anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the negative electrode on substrate.

4. electroluminescent device according to claim 3, is characterized in that, described device also comprises optically coupled layers, and it is arranged on described negative electrode.

5. electroluminescent device according to claim 4, is characterized in that, the material of described optically coupled layers is selected from least one in compound according to claim 1.

6. electroluminescent device according to claim 3, is characterized in that, the material of described anode is selected from least one in tin indium oxide, indium zinc oxide and tindioxide.

7. electroluminescent device according to claim 3, is characterized in that, the material of described luminescent layer is selected from two carbazole biphenyl, 9,10-bis-(2-naphthyl) anthracene, Ir (ppy ₃) or TPBi doping two carbazole biphenyl and Ir (ppy ₃) or TPBi doping 9,10-bis-(2-naphthyl) anthracene at least one.

8. electroluminescent device according to claim 3, is characterized in that, the material of described electron transfer layer is selected from least one in 4,7-phenylbenzene-1,10-phenanthroline and three (oxine) aluminium.