CN105924438A - Organic optoelectronic material with indeno-phenanthroline structure and preparing method and application thereof - Google Patents

Abstract

The invention discloses an organic photoelectric material containing an indenophenanthroline structure, a preparation method and application thereof, and belongs to the technical field of organic photoelectric materials. It has the molecular structure shown in Formula 1: Wherein, R ₁ and R ₂ are one of hydrogen, phenyl or dibenzofuryl, R ₃ is hydrogen, phenyl, polycyclic conjugated aryl groups with 10-60 carbon atoms, and containing N, One of the aromatic heterocyclic groups in S and O atoms. Because the material of the invention contains an indeno-phenanthroline structure, it forms a larger rigid planar structure, provides high electron mobility and large electron affinity, and greatly improves the transmission of injected electrons.

Description

A kind of organic photoelectric material containing indenophenanthroline structure and its preparation method and application

technical field

The invention relates to an organic photoelectric material containing an indenophenanthroline structure and a preparation method and application thereof, belonging to the technical field of organic photoelectric materials.

Background technique

In recent years, organic light emitting diodes (organic light emitting diode, OLED) have become a very popular emerging flat-panel display at home and abroad, because OLED displays have self-illumination, wide viewing angle (up to 175°C or more), short response time, high luminous efficiency, Wide color gamut, low operating voltage (3-10V), thin panel, large-size and flexible panel can be produced, and simple manufacturing process, and it has the potential of low cost. It is considered to be the star of the next generation of ultra-thin flat panel display devices. Although many research institutions and companies around the world have invested a lot of energy in the research and development of organic electroluminescent devices, compared with people's expectations, the degree of industrialization is still far behind, and there are still many key issues that have not been truly solved. Solving, such as color purity, luminous stability, active driving technology and packaging technology, there are still certain problems, which make the life of the organic electroluminescent device short and the efficiency low.

An organic light-emitting device mainly consists of positive and negative electrode layers, and one or more layers sandwiched between the two electrode layers, such as a light-emitting layer, a hole transport layer, and an electron transport layer. The materials corresponding to the functional layers applied to organic electroluminescent devices can be referred to as luminescent materials, hole transport materials and electron transport materials, respectively. In organic electroluminescence, the organic molecules excited by the recombination of electrons and holes are not limited by the law of spin selection. Theoretically, according to the statistical distribution, the ratio of excited triplet state to excited singlet state is 3:1. Thus in fluorescence electroluminescence, 75% of the excited state energy is lost. However, if phosphorescent electroluminescent materials are used, all excited states can be fully utilized, thereby promoting a substantial increase in OLED efficiency. In the field of full-color display, blue light, as one of the three primary colors, is not only an important part of white light, but also can be used as excitation light to realize the display of green light and red light. However, compared with green and red phosphorescent materials, blue phosphorescent materials have a wider energy band, making carrier injection and exciton confinement relatively difficult, resulting in lower efficiency.

In order to improve the performance of organic electroluminescent devices, the research on electron transport materials is very important. The selection of electron transport materials must meet the following requirements: (1) have reversible electrochemical reduction and sufficient reduction potential, because the process of electron conduction in the organic film is a series of redox reactions; (2) good electron transport Mobility, so that the charge can be recombined with the region; (3) good film formation and thermal stability; (4) good light stability.

Although there are already many electron transport materials for organic light-emitting devices, there are not many electron transport materials that can meet the above conditions.

Contents of the invention

One of the objectives of the present invention is to provide an organic photoelectric material containing an indenophenanthroline structure. The material of the present invention has high thermal stability and high glass transition temperature, and can be used as an electron transport material of OLED, so that the power efficiency of OLED is greatly improved, and the driving voltage is also reduced, thereby significantly improving the organic electrical efficiency. The lifetime of the luminescent device.

The technical solution of the present invention to solve the above-mentioned technical problems is as follows: an organic photoelectric material containing an indenophenanthroline structure, which has a molecular structure shown in formula 1:

Wherein, R ₁ and R ₂ are one of hydrogen, phenyl or dibenzofuryl, R ₃ is hydrogen, phenyl, polycyclic conjugated aryl groups with 10-60 carbon atoms, and containing N, One of the aromatic heterocyclic groups in S and O atoms.

The organic optoelectronic material of the present invention has high thermal stability and high glass transition temperature. As an electron transport material of OLED, the power efficiency of OLED is greatly improved, and the driving voltage is also reduced, thereby significantly improving the efficiency of OLED. The lifetime of electroluminescent devices.

On the basis of the above technical solutions, the present invention can also be improved as follows.

Further, the specific structural formula of the _R3 is:

The organic photoelectric material containing the above-mentioned indenophenanthroline structure of the present invention has a specific structural formula as follows:

Experimental results show that the organic optoelectronic material provided by the invention has high thermal stability and high glass transition temperature, and is used in OLED as an electron transport material of OLED, and the OLED comprising the organic optoelectronic material provided by the invention can obtain good The performance of the device, such as the power efficiency of the OLED is greatly improved; at the same time, the driving voltage can be greatly reduced and the life of the OLED can be greatly improved. It can be known from this that the organic photoelectric material provided by the present invention has a good application effect in OLEDs and has a good industrialization prospect.

The second object of the present invention is to provide the above-mentioned organic photoelectric material containing indenophenanthroline structure. method of preparation. The preparation method of the invention is simple, convenient, easy to operate, and low in cost, which is beneficial to large-scale popularization.

The technical scheme of the present invention to solve the above-mentioned technical problems is as follows: a preparation method of an organic photoelectric material containing an indenophenanthroline structure, comprising the following steps:

Step 1: Under the protection of an inert gas and at a temperature of -100 to 0°C, add 2.0 to 2.4 molar equivalents of n-butyllithium to 1.0 molar equivalents of 4,7-dibromophenanthroline THF solution, carry out the reaction, and then add 2.0-2.2 molar equivalents of trimethylchlorosilane for reaction, after obtaining the reaction system containing intermediate 1, slowly warm the above reaction system containing intermediate 1 to room temperature, and then pour Pour into water, stir and react for 10 to 50 minutes, then add ethyl acetate to carry out layering and washing with water in sequence, and then desolventize the organic phase under reduced pressure until there is no fraction, and intermediate 1 is obtained;

Step 2: Under the protection of an inert gas and at a temperature of -100 to 0°C, add 1.0 to 1.1 molar equivalents of n-butyllithium to a THF solution containing 1.0 molar equivalents of aryl halide R ₁ -Br In the _first step reaction, the lithium salt solution of R1 is obtained, and then the lithium salt solution of R1 is added dropwise to the organic solution containing the intermediate one obtained in step ₁ at a temperature of -60 to 10°C , carry out the second step reaction, then add water to quench the reaction, then extract with dichloromethane, treat the extract with 4 to 10.0 molar equivalents of manganese dioxide to obtain a reaction system containing intermediate 2, and then extract the above-mentioned The reaction system of intermediate 2 was filtered under reduced pressure, and the resulting filtrate was concentrated under reduced pressure, then concentrated under reduced pressure with a mixture of petroleum ether and dichloromethane, and the obtained product was purified by column chromatography, wherein the mixture of petroleum ether and dichloromethane The volume ratio is petroleum ether: dichloromethane = 5 ~ 60: 1, to obtain intermediate 2;

Step 3: Under the protection of an inert gas and at a temperature of -100 to 0°C, add 1.0 to 1.1 molar equivalents of n-butyllithium to an organic solution containing 1.0 molar equivalents of aryl halide R ₂ -Br , carry out the first step reaction to obtain the lithium salt solution of R2, and then add the above-mentioned lithium salt solution of R2 dropwise to the organic solution containing intermediate ₂ obtained in step ₂ at a temperature of -60 to 10°C, Carry out the second step reaction, then add water to quench the reaction, then extract with dichloromethane, and treat the extract with 4 to 10.0 molar equivalents of manganese dioxide to obtain a reaction system containing intermediate three. The reaction system of the reaction system is filtered under reduced pressure, and the obtained filtrate is concentrated under reduced pressure, and then the above-mentioned concentrated under reduced pressure is concentrated with a mixture of petroleum ether and methylene chloride, and the product obtained is purified by column chromatography, wherein the volume ratio of petroleum ether and methylene chloride is Petroleum ether: dichloromethane = 5 ~ 60: 1, to obtain intermediate three;

Step 4: Under the protection of an inert gas and at a temperature of 0-60°C, add 2.1-3.0 molar equivalents of NBS to the organic solution containing intermediate 3 obtained in step 3 to obtain a reaction containing intermediate 4 system, adding the above reaction system containing intermediate 4 to a sodium bisulfite solution with a mass percent concentration of 2% to quench the reaction, then adding chloroform, after layering, adding water to wash, and after the washing is completed, the organic phase is decompressed Desolvation until there is no fraction, after desolventization, recrystallize with toluene-ethanol mixed solvent, wherein the volume ratio of toluene to ethanol is 2:3-8; or use petroleum ether and dichloromethane mixture to concentrate the above-mentioned The residue was purified by column chromatography, wherein the volume ratio of petroleum ether to dichloromethane was 5-60:1 to obtain intermediate four;

Step 5: Add intermediate IV, arylboronic acid R ₃ -B(OH) ₂ and basic substances obtained in step 4 to toluene, xylene, N,N-dimethylformamide or dimethylacetamide , under the protection of an inert gas, add a catalyst, and then react at 60-150°C for 2-24 hours to obtain a reaction system containing intermediate 5, layer the above-mentioned reaction system containing intermediate 4, wash with water, The organic phase is desolvated under reduced pressure until there is no fraction, and then purified by column chromatography, and the purification is eluted with a mixed solution of petroleum ether and dichloromethane or a mixed solution of petroleum ether and ethyl acetate, wherein petroleum ether The volume ratio to dichloromethane is 2 to 60:1, and the volume ratio to petroleum ether and ethyl acetate is 2 to 35:1 to obtain Intermediate V;

Step 6: Add intermediate V, o-bromophenylboronic acid and basic substances obtained in step 5 to toluene, xylene, N,N-dimethylformamide or dimethylacetamide, under the protection of inert gas, Add a catalyst, then react at 60-150°C for 2-24 hours to obtain a reaction system containing intermediate 6, layer the above-mentioned reaction system containing intermediate 5, wash with water, and desolventize the organic phase under reduced pressure To no fraction, then purify by column chromatography, the above purification is eluted with a mixture of petroleum ether and dichloromethane or a mixture of petroleum ether and ethyl acetate, wherein the volume ratio of petroleum ether to dichloromethane is 2 ～60:1, the volume ratio of petroleum ether and ethyl acetate is 2～35:1, obtain intermediate six;

Step 7: Add the intermediate VI and the basic substance obtained in step 6 to toluene, xylene, N,N-dimethylformamide or dimethylacetamide, add a catalyst under the protection of an inert gas, and then , after reacting at 60-170° C. for 2-24 hours, the organic photoelectric material containing the structure of indenophenanthroline is obtained.

The reaction formula of above-mentioned preparation method is as follows:

In the preparation method of the present invention, the involved reaction processes are all conventional organic reaction types, the reaction process is simple, safe, easy to operate, and the raw materials are cheap, easy to purchase, and conducive to large-scale promotion. Wherein, in step 1, 4,7-dibromophenanthroline is dispersed in tetrahydrofuran, and n-butyllithium exists in the form of being dispersed in n-hexane, that is to say, n-hexane containing n-butyllithium is added dropwise Into the organic solution containing 4,7-dibromophenanthroline for lithium halide exchange.

In step 2, the aryl halide R ₁ -Br is dispersed in tetrahydrofuran, and n-butyllithium exists in the form of being dispersed in n-hexane, that is, the n-hexane containing n-butyllithium is added dropwise to the n-hexane containing aryl Lithium halide exchange is carried out in the organic solution of halide R ₁ -Br.

In step 3, the aryl halide R ₂ -Br is dispersed in tetrahydrofuran, and n-butyllithium exists in the form of being dispersed in n-hexane, that is, the n-hexane containing n-butyllithium is added dropwise to the n-hexane containing aryl Lithium halide exchange is carried out in the organic solution of halide R ₂ -Br.

On the basis of the above technical solutions, the present invention can also be improved as follows.

Further, in step 5, the alkaline substance is one or more of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide; the catalyst is palladium acetate, tetrakis(triphenylphosphine), bistriphenylphosphine One or more of phenylphosphorous palladium dichloride and tris(dibenzylideneacetone) dipalladium; the temperature of the reaction is 60-90°C, and the time is 4-8 hours; the alkaline substance and The molar ratio of intermediate four is 1.3-3.0:1.

Further, in step 6, the alkaline substance is one or more of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide; the catalyst is palladium acetate, tetrakis(triphenylphosphine), bistriphenylphosphine One or more of phenylphosphorous palladium dichloride and tris(dibenzylideneacetone) dipalladium; the temperature of the reaction is 60-90°C, and the time is 4-8 hours; the alkaline substance and The molar ratio of intermediate 4 is 1.3-3.0:1; the molar ratio of the catalyst to intermediate 5 is 0.001-0.1:1.

The further beneficial effect of adopting the above is that the alkaline substance provides an alkaline environment, which is beneficial to complete the reaction.

Further, in step 7, the alkaline substance is one or more of triethylamine, DBU, sodium ethylate; the catalyst is selected from palladium acetate, tetrakis(triphenylphosphine), bistriphenylphosphine One or more of palladium chloride and tris(dibenzylideneacetone) dipalladium; the reaction temperature is preferably 100 to 170°C, and the reaction time is preferably 6 to 12 hours; the basic substance and intermediate six The molar ratio is 1.3-3.0:1; the molar ratio of the catalyst to the intermediate six is 0.001-0.1:1.

Further, in step 5, step 6 and step 7, phosphine ligands are added when the catalyst is added, and the phosphine ligands are 1,3-bis(diphenylphosphine)propane, 4,5-bisdiphenyl One or more of phosphine-9,9-dimethylxanthene, 2-bicyclohexylphosphine-2',6'-dimethoxybiphenyl or tri-tert-butylphosphine tetrafluoroborate.

The further beneficial effect of adopting the above is: when adding the catalyst, add the phosphine ligand, because the phosphine ligand can be better complexed with the above-mentioned palladium catalyst in the CC coupling catalytic reaction, thereby forming zero-valent palladium The complex further participates in the cross-coupling of intermediate four and aryl boronic acid R ₃ -B(OH) ₂ , thereby improving the purity and yield of intermediate five.

While adding the catalyst, add the phosphine ligand, because the phosphine ligand can be better complexed with the above-mentioned palladium catalyst in the CC coupling catalytic reaction, thereby forming a zero-valent palladium complex, and further participating in the intermediate Pentahexo-bromophenylboronic acid The cross-coupling, thereby improving the purity and yield of intermediate six.

While adding the catalyst, add the phosphine ligand, because the phosphine ligand can be better complexed with the above-mentioned palladium catalyst in the C-C coupling catalytic reaction, thereby forming a zero-valent palladium complex, and further participating in the intermediate Six molecules are cyclized, thereby improving the purity and yield of the target compound.

Furthermore, the molar ratio of the catalyst to the intermediate 4 or the intermediate 5 or the intermediate 6 is 0.001-0.1:1.

Further, in step 7, the inert gas is one or more of nitrogen, argon, and helium.

Furthermore, the inert gas is nitrogen.

The third object of the present invention is to provide the application of the above-mentioned organic photoelectric material containing the structure of indenophenanthroline.

The technical scheme of the present invention to solve the above-mentioned technical problems is as follows: an application of an organic photoelectric material containing indenophenanthroline structure, in an organic electroluminescence device, at least one functional layer contains the above-mentioned indenophenanthroline Organic optoelectronic materials with phylloline structure.

An organic electroluminescent device, as shown in FIG. 1 , includes at least one light emitting layer 5 and an electron transport layer 6 made of a material containing the organic photoelectric material provided by the present invention. When the organic electroluminescent device only contains the light-emitting layer 5 and the electron-transport layer 6 , the electron-transport layer 6 is sandwiched between the light-emitting layer 5 and the cathode 8 . The OLED light-emitting device structure includes at least one light-emitting layer 5 and an electron-transporting layer 6 .

In the above organic electroluminescent device, as shown in FIG. 1, one or more of the following film layers may also be included: a hole injection layer 3, a hole transport layer 4 and an electron injection layer 7, wherein the hole Both the hole injection layer 3 and the hole transport layer 4 are disposed between the anode 2 and the light-emitting layer 5 , and the electron transport layer 6 and the electron injection layer 7 are both disposed between the light-emitting layer 5 and the cathode 8 . When containing one or more of the above-mentioned film layers, the structure of the organic electroluminescent device can be as follows, but not limited to the following:

(1) anode 2/organic luminescent layer 5/electron transport layer 6/cathode 8, that is to say, organic luminescent layer 5 and electron transport layer 6 are arranged between anode 2 and cathode 8, wherein, on anode 2, An organic light emitting layer 5 and an electron transport layer 6 are provided.

(2) Anode 2/hole injection layer 3/organic luminescent layer 5/electron transport layer 6/cathode 8, that is to say, between anode 2 and cathode 8, hole injection layer 3, organic luminescent layer 5 and An electron transport layer 6 , wherein a hole injection layer 3 , an organic light-emitting layer 5 and an electron transport layer 6 are sequentially disposed on the anode 2 .

(3) anode 2/hole transport layer 4/organic luminescent layer 5/electron transport layer 6/cathode 8, that is to say, between anode 2 and cathode 8, hole transport layer 4, organic luminescent layer 5 and An electron transport layer 6 , wherein a hole transport layer 4 , an organic light-emitting layer 5 and an electron transport layer 6 are sequentially disposed on the anode 2 .

(4) Anode 2/hole injection layer 3/hole transport layer 4/organic light-emitting layer 5/electron transport layer 6/cathode 8, that is, a hole injection layer 3 is provided between the anode 2 and the cathode 8 , a hole transport layer 4, an organic light-emitting layer 5 and an electron transport layer 6, wherein a hole injection layer 3, a hole transport layer 4, an organic light-emitting layer 5 and an electron transport layer 6 are sequentially arranged on the anode 2.

In the production of OLED displays, each layer can be formed by making the material into a thin film by evaporation, spin coating, or casting. The film thickness of each layer formed in this manner is not particularly limited, and can be appropriately set according to the properties of the material, and is usually in the range of 2 to 5000 nm. Furthermore, the method of thinning the luminescent material is easy to obtain a uniform film layer and is not easy to generate pinholes, and the vapor deposition method is preferred. The evaporation conditions are generally preferred to be in a boat, with a heating temperature of ^50-400 °C, a vacuum degree of ^10-6-10-3 Pa, an evaporation rate of 0.01-50nm/s, a substrate temperature of -150-300°C, and a film thickness of 5-5μm. Appropriate setting within the range.

The anode has the function of injecting holes into the hole transport layer 4, and the anode is usually composed of the following substances: metals such as aluminum, gold, silver, nickel, palladium or platinum; such as indium oxide, tin oxide, zinc oxide, indium tin composite Metal oxides such as oxides and indium-zinc composite oxides; metal halides such as copper iodide; carbon black; or some conductive polymers, etc.

The hole transport layer is a material with high efficiency of injecting holes from the anode and capable of effectively transporting the injected holes. Therefore, the material needs to have low ionization potential, high permeability to visible light, high hole mobility, and stable properties, and it is also required that light that is not easily generated during preparation or use becomes a trap impurity. In addition, because it is in contact with the light-emitting layer 5, it is required that the hole-transport layer 4 does not extinction the light from the light-emitting layer 5, and does not form an exciplex with the light-emitting layer 5 to reduce the efficiency. Common hole-transport materials include Represented by N4,N4'-di(naphthalene-1-yl)-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (NPB) containing two Aromatic diamines and triphenylamines of the above tertiary amines, aromatic amine compounds having a star-shaped radial structure, carbazole derivatives, and the like. These compounds may be used alone or in combination of two or more.

As the functional material for the hole injection material, any material can be selected from known materials for the hole transport layer of OLED light-emitting devices.

The light-emitting layer is formed of a light-emitting substance that is excited by recombination of holes and electrons between electrodes to which an electric field is applied, thereby exhibiting strong light emission. Usually, the light-emitting layer 5 contains a dopant material and a host material as a light-emitting substance. In order to obtain a high-efficiency OLED light-emitting device, one doping material or multiple doping materials can be used for the light-emitting layer. The doping material can be a pure fluorescent or phosphorescent material, or a combination of different fluorescent and phosphorescent materials, and the light-emitting layer can be a single light-emitting layer material, or a composite light-emitting layer material stacked together.

The host material of the light-emitting layer not only needs to have bipolar charge transport properties, but also needs an appropriate energy level to effectively transfer the excitation energy to the guest light-emitting material. Such materials can include distyrylaryl derivatives , stilbene derivatives, carbazole derivatives, triarylamine derivatives, anthracene derivatives, pyrene derivatives, hexabenzocene derivatives, and the like.

The blending amount of the guest material is preferably 0.01% by weight or more and 20% by weight or less with respect to the host material. Examples of such materials include metal complexes of iridium, ruthenium, platinum, rhenium, and palladium.

Composition of the material of the electron transport layer of the OLED light-emitting device, using the electron transport material of the present invention as the electron transport layer of the OLED device, can be selected such as 1,3,5-tris(1-naphthyl-1H-benzimidazole-2- Benzimidazole derivatives such as base) benzene (TPBI), metal complexes such as tris (8-hydroxyquinophosphine) aluminum (Alq3), 2-(4,-tert-butylphenyl)-5-(4,-linked Phenyl)-1,3,4-oxadiazole (PBD) and other oxadiazole derivatives, 4,7-diphenyl-1,10-phenanthroline (BPhen), 2,9-dimethyl- phenanthroline derivatives such as 4,7-diphenyl-1,10-phenanthroline (BCP), triazole derivatives, quinophosphine derivatives, quinoxaphosphine derivatives, etc.

The cathode materials that can be used in the above-mentioned OLED light-emitting device can be selected from metals, alloys, conductive compounds and mixtures thereof that have a work function of less than 4eV. Specific examples thereof include aluminum, calcium, magnesium, lithium, magnesium alloys, aluminum alloys, and the like. In order to efficiently obtain the light emission of the OLED, it is desirable to set the transmittance of at least one of the electrodes to 10% or more. The cathode can be formed by a dry method such as vacuum evaporation, vapor deposition or sputtering.

The beneficial effects of the present invention are:

The organic photoelectric material containing indenophenanthroline structure synthesized by the present invention is applied in organic electroluminescent devices to obtain high-efficiency electroluminescent performance, and its main advantages are as follows:

1. Due to the indeno-phenanthroline structure, the material of the present invention forms a larger rigid planar structure, provides high electron mobility and large electron affinity, and greatly improves the transmission of injected electrons.

2. The material of the present invention has good thermal stability, high glass transition temperature and decomposition temperature, and is easy to form a good amorphous film. It can be used in electroluminescent devices to obtain more stable effects and longer service life.

3. The material of the present invention has a higher excited state energy level, which can effectively avoid the energy transfer of the excited state, so that the exciton recombination region is formed in the light-emitting layer instead of the electron transport layer.

4. In the organic electroluminescent device provided by the present invention, due to containing the organic photoelectric material provided by the present invention, the power efficiency of the organic electroluminescent device can be greatly improved, and at the same time, the driving voltage is also reduced, thereby significantly improving life of organic electroluminescent devices.

Description of drawings

Fig. 1 is the structural representation of the organic electroluminescence device prepared by the present invention, from lower layer to upper layer, successively be transparent substrate layer (1), anode (2), hole injection layer (3), hole transport layer (4) ), light emitting layer (5), electron transport layer (6), electron injection layer (7) and cathode (8), wherein, electron transport layer (6) relates to the organic electroluminescent material prepared by the present invention.

detailed description

The principles and features of the present invention are described below in conjunction with the accompanying drawings, and the examples given are only used to explain the present invention, and are not intended to limit the scope of the present invention.

Compound Preparation Example:

Example 1: Preparation of the aforementioned compound E01

Preparation of intermediate one (a):

At -78°C and under the protection of nitrogen, take 67.6g of 4,7-dibromophenanthroline (200.0mmol) and disperse it in 500g of tetrahydrofuran, then add dropwise 176mL of 2.5mol/L containing n-butyl Lithium n-hexane solution, after the dropwise addition, keep it warm for 2.0 hours, then add 33.0g of trimethylchlorosilane dropwise at -78°C, keep it warm for 2.0 hours after the drop, and then slowly warm the reaction system to room temperature , then poured the system into 200g of water, stirred and reacted for 30min, then added 500g of ethyl acetate for extraction, the system was layered, washed with water, and finally the organic phase was desolvated under reduced pressure until there was no fraction, and 64.7g of intermediate- (a), without further purification.

Preparation of intermediate one (b):

At -78°C and under the protection of nitrogen, take 33.1g of bromobenzene (211.0mmol) and disperse it in 300g of tetrahydrofuran, then add dropwise 93mL of n-hexane solution containing n-butyllithium with a concentration of 2.5mol/L, dropwise After the addition, keep the reaction for 2.0 hours, and then slowly raise the temperature to -10°C for storage until use.

Take 32.5g of intermediate one (100.0mmol) and dissolve it in 300g of tetrahydrofuran, add the above-mentioned phenyllithium solution dropwise at a temperature of -10°C, and keep it warm for 2.0 hours after dropping, then slowly warm the reaction system to room temperature, and then After the system was poured into 200g of water, stirred and reacted for 30min, then 500g of dichloromethane was added for extraction, the system was layered, washed with water, and dried over anhydrous sodium sulfate.

Add 146.8 g of manganese dioxide (1.69 mol) to the above dichloromethane solution, stir and react at 25° C. for 5.5 hours, filter under reduced pressure, and desolventize the filtrate until there is no fraction. Then use petroleum ether and dichloromethane mixed solution to carry out column chromatography purification to the product that above-mentioned vacuum desolvation obtains, and wherein the volume ratio of petroleum ether and dichloromethane is petroleum ether: dichloromethane=20:1, obtains 28.6g Intermediate one (b), yield 71.50%.

Preparation of intermediate one (c):

At -78°C and under the protection of nitrogen, take 16.6g of bromobenzene (105.0mmol) and disperse it in 150g of tetrahydrofuran, then add dropwise 47mL of n-hexane solution containing n-butyllithium with a concentration of 2.5mol/L, dropwise After the addition, keep the reaction for 2.0 hours, and then slowly raise the temperature to -10°C for storage until use.

Take 20.0g of intermediate two (50.0mmol) and dissolve in 150g of tetrahydrofuran, add the above-mentioned phenyllithium solution dropwise at a temperature of -10°C, and keep the reaction for 2.0 hours after the dropping, then slowly warm the reaction system to room temperature, and then After the system was poured into 150g of water, stirred and reacted for 30min, then 300g of dichloromethane was added for extraction, the system was layered, washed with water, and dried over anhydrous sodium sulfate.

Add 73.9 g of manganese dioxide (850.0 mmol) to the above dichloromethane solution, stir and react at 25° C. for 6 hours, filter under reduced pressure, and desolventize the filtrate until there is no fraction. Then use petroleum ether and dichloromethane mixed solution to carry out column chromatography purification to the product that above-mentioned vacuum desolvation obtains, wherein the volume ratio of petroleum ether and dichloromethane is petroleum ether: dichloromethane=15:1, obtains 17.9g Intermediate one (c), yield 75.21%.

Preparation of intermediate one (d):

At 60°C and under the protection of nitrogen, 14.3g of intermediate three (30.0mmol) was dispersed in 200g of chloroform, and then 11.7g of NBS (66.0mmol) was added. Track reaction progress. After the reaction is over, add 200g of 2% sodium bisulfite aqueous solution to quench the reaction, separate layers, wash with water, and then desolventize the organic phase under reduced pressure until there is no fraction, and finally select toluene and ethanol mixed solvent for recrystallization to obtain 13.1g Intermediate one (d), the yield is 89.11%.

Preparation of intermediate one (e):

Take 12.3g of intermediate four (25.0mmol), 2.6g of 1-naphthalene boronic acid (15.0mmol), 3.2g of potassium carbonate (23.0mmol) and 30g of water, dissolve them in 60mL of toluene and 30mL of ethanol, and stir for 1 hour under nitrogen to remove Oxygen in the reaction flask. Then, 0.115 g (1.0 mmol) of Pd(PPh ₃ ) ₄ was added and refluxed under vigorous stirring. The reaction process was tracked and detected by TLC. After the completion of the reaction, extract the aqueous phase with 200 mL of ethyl acetate, and desolvate the organic phase under reduced pressure until there is no distillate. The volume ratio to dichloromethane is petroleum ether:dichloromethane=7:1, and 4.5g of intermediate one (e) is obtained with a yield of 55.6%.

Preparation of intermediate one (f):

Take 4.3g of intermediate five (8.0mmol), 1.8g of o-bromophenylboronic acid (9.0mmol), 1.7g of potassium carbonate (12.0mmol) and 15g of water, dissolve them in 30mL of toluene and 15mL of ethanol, and stir for 1 hour under nitrogen to remove Oxygen in the reaction flask. Then add 0.046g (0.04mmol) of Pd(PPh ₃ ) ₄ , and reflux under vigorous stirring. The reaction process is tracked and detected by TLC. After the completion of the reaction, 100mL of ethyl acetate extracted the aqueous phase, and the organic phase was desolvated under reduced pressure until there was no distillate. The volume ratio to dichloromethane is petroleum ether:dichloromethane=8:1, and 3.4g of intermediate one (f) is obtained with a yield of 69.4%.

Preparation of E01:

Take 3.1g of intermediate six (5.0mmol), 1.5g of DBU (12.0mmol) and 30g of DMF, and stir with nitrogen for 1 hour to remove the oxygen in the reaction flask. Then 0.35 g (0.05 mmol) of Pd(PPh ₃ ) ₂ Cl ₂ was added and refluxed under vigorous stirring. The reaction process was tracked and detected by TLC. After the reaction was completed, it was poured into 100g of ice water, and the aqueous phase was extracted with 200mL of ethyl acetate. The organic phase was desolvated under reduced pressure until there was no fraction. Compound E01, yield 71.4%. The crude product was further sublimated and purified in a chemical vapor deposition system at 300° C. to obtain 1.7 g of off-white solid powder with a yield of 90.0%. The compound was identified by DEI-MS, molecular formula C ₄₀ H ₂₄ N ₂ , detected value [M+1] ⁺ = 533.17, calculated value 532.19.

Example 2: Preparation of the aforementioned compound E26

The preparation of intermediate two (a):

At -78°C and under the protection of nitrogen, 52.1 g of 4-bromodibenzofuran (211.0 mmol) was dispersed in 400 g of tetrahydrofuran, and then 93 mL of n-butyllithium containing 2.5 mol/L was added dropwise. After the addition of the n-hexane solution is complete, keep it warm for 2.0 hours, and then slowly raise the temperature to -10°C for storage until use.

Take 32.5g of intermediate one (c) (100.0mmol) and dissolve it in 300g of tetrahydrofuran, add the above-mentioned phenyllithium solution dropwise at -10°C, keep the reaction for 2.0 hours after dropping, and then slowly raise the temperature of the reaction system to room temperature , and then poured the system into 200g of water, stirred and reacted for 30min, then added 500g of dichloromethane for extraction, the system was layered, washed with water, and dried over anhydrous sodium sulfate.

Add 146.8 g of manganese dioxide (1.69 mol) to the above dichloromethane solution, stir and react at 25° C. for 4.5 hours, filter under reduced pressure, and desolventize the filtrate until there is no fraction. Then use petroleum ether and dichloromethane mixed solution to carry out column chromatography purification to the product that above-mentioned vacuum desolvation obtains, and wherein the volume ratio of petroleum ether and dichloromethane is petroleum ether: dichloromethane=10:1, obtains 33.4g Intermediate 2 (a), the yield is 68.06%.

Preparation of intermediate two (b):

At -78°C and under the protection of nitrogen, 25.9g of 4-bromodibenzofuran (105.0mmol) was dispersed in 180g of tetrahydrofuran, and then 47mL of n-butyl lithium containing 2.5mol/L was added dropwise. After the addition of the n-hexane solution is complete, keep it warm for 2.0 hours, and then slowly raise the temperature to -10°C for storage until use.

Take 24.5g of intermediate bis(a) (50.0mmol) and dissolve it in 120g of tetrahydrofuran, add the above-mentioned phenyllithium solution dropwise at -10°C, keep the reaction for 2.0 hours after dropping, and then slowly raise the temperature of the reaction system to room temperature , and then poured the system into 150g of water, stirred and reacted for 30min, then added 300g of dichloromethane for extraction, the system was layered, washed with water, and dried over anhydrous sodium sulfate.

Add 73.9 g of manganese dioxide (850.0 mmol) to the above dichloromethane solution, stir and react at 25° C. for 6 hours, filter under reduced pressure, and desolventize the filtrate until there is no fraction. Then use petroleum ether and dichloromethane mixture to carry out column chromatography purification to the product obtained by the above-mentioned vacuum desolventization, wherein the volume ratio of petroleum ether and dichloromethane is petroleum ether: dichloromethane=5:1, obtain 23.0g Intermediate 2 (b), yield 70.0%.

The preparation of intermediate two (c):

At 60°C and under the protection of nitrogen, take 19.7g of intermediate bis(b) (30.0mmol) and disperse it in 250g of chloroform, then add 11.7g of NBS (66.0mmol), after the dropwise addition, keep the reaction for 12.0 hours, At the same time, TLC was used to track the progress of the reaction. After the reaction is over, add 200g mass percent concentration of 2% sodium bisulfite aqueous solution to quench the reaction, separate layers, wash with water, then desolventize the organic phase under reduced pressure until there is no fraction, and finally select toluene ethanol mixed solvent for recrystallization to obtain 17.0g Intermediate 2 (c), the yield is 84.58%.

Preparation of intermediate two (d):

Take 16.7g of intermediate two (c) (25.0mmol), 1.8g of phenylboronic acid (15.0mmol), 3.2g of potassium carbonate (23.0mmol) and 30g of water, dissolve them with 60mL of toluene and 30mL of ethanol, and stir for 1 hour with nitrogen gas to Oxygen was removed from the reaction flask. Then, 0.115 g (1.0 mmol) of Pd(PPh ₃ ) ₄ was added and refluxed under vigorous stirring. The reaction process was tracked and detected by TLC. After the completion of the reaction, extract the aqueous phase with 200 mL of ethyl acetate, and desolvate the organic phase under reduced pressure until there is no distillate. The volume ratio to dichloromethane is petroleum ether:dichloromethane=15:1, and 5.4g of intermediate bis(d) is obtained with a yield of 53.95%.

The preparation of intermediate two (e):

Take 5.3g of intermediate bis(d) (8.0mmol), 1.8g of o-bromophenylboronic acid (9.0mmol), 1.7g of potassium carbonate (12.0mmol) and 15g of water, dissolve them in 30mL of toluene and 15mL of ethanol, and stir for 1 hour under nitrogen gas , to remove the oxygen in the reaction flask. Then add 0.046g (0.04mmol) of Pd(PPh ₃ ) ₄ , and reflux under vigorous stirring. The reaction process is tracked and detected by TLC. After the completion of the reaction, 100mL of ethyl acetate extracted the aqueous phase, and the organic phase was desolvated under reduced pressure until there was no distillate. The volume ratio to dichloromethane is petroleum ether:dichloromethane=20:1, and 3.8g of intermediate bis(e) is obtained with a yield of 64.3%.

Preparation of E26:

Take 3.7g of intermediate two (e) (5.0mmol), 1.5g of DBU (12.0mmol) and 30g of DMF, and stir with nitrogen for 1 hour to remove the oxygen in the reaction flask. Then 0.35 g (0.05 mmol) of Pd(PPh ₃ ) ₂ Cl ₂ was added and refluxed under vigorous stirring. The reaction process was tracked and detected by TLC. After the reaction was completed, it was poured into 100g of ice water, and the aqueous phase was extracted with 200mL of ethyl acetate. The organic phase was desolvated under reduced pressure until there was no fraction, and then purified by column chromatography with pure toluene to obtain 2.2g Compound E26, yield 66.67%. The crude product was further sublimated and purified in a chemical vapor deposition system at 320° C. to obtain 2.0 g of off-white solid powder with a yield of 90.91%. Using DEI-MS to identify the compound, the molecular formula is C ₄₈ H ₂₆ N ₂ O ₂ , the detected value [M+1] ⁺ = 663.86, and the calculated value is 662.75.

Example 3: Preparation of the aforementioned compound E38

Preparation of intermediate three (a):

At -78°C and under the protection of nitrogen, take 16.6g of bromobenzene (105.0mmol) and disperse it in 150g of tetrahydrofuran, then add dropwise 47mL of n-hexane solution containing n-butyllithium with a concentration of 2.5mol/L, dropwise After the addition, keep the reaction for 2.0 hours, and then slowly raise the temperature to -10°C for storage until use.

Take 24.5g of intermediate bis(a) (50.0mmol) and dissolve it in 120g of tetrahydrofuran, add the above-mentioned phenyllithium solution dropwise at -10°C, keep the reaction for 2.0 hours after dropping, and then slowly raise the temperature of the reaction system to room temperature , and then poured the system into 150g of water, stirred and reacted for 30min, then added 300g of dichloromethane for extraction, the system was layered, washed with water, and dried over anhydrous sodium sulfate.

Add 73.9 g of manganese dioxide (850.0 mmol) to the above dichloromethane solution, stir and react at 25° C. for 6 hours, filter under reduced pressure, and desolventize the filtrate until there is no fraction. Then use petroleum ether and dichloromethane mixed solution to carry out column chromatography purification to the product that above-mentioned vacuum desolvation obtains, wherein the volume ratio of petroleum ether and dichloromethane is petroleum ether: dichloromethane=12:1, obtains 21.5g Intermediate 3 (a), the yield is 75.97%.

Preparation of intermediate three (b):

At 60°C and under the protection of nitrogen, take 17.0g of intermediate three (a) (30.0mmol) and disperse it in 200g of chloroform, then add 11.7g of NBS (66.0mmol), after the dropwise addition, keep the reaction for 10.0 hours, At the same time, TLC was used to track the progress of the reaction. After the reaction is over, add 200g mass percentage concentration of 2% sodium bisulfite aqueous solution to quench the reaction, separate layers, wash with water, then desolventize the organic phase under reduced pressure until there is no fraction, finally select toluene ethanol mixed solvent for recrystallization to obtain 15.3g Intermediate 3 (b), the yield is 87.93%.

The preparation of intermediate three (c):

Take 14.5g of intermediate three (b) (25.0mmol), 1.8g of phenylboronic acid (15.0mmol), 3.2g of potassium carbonate (23.0mmol) and 30g of water, dissolve them with 60mL of toluene and 30mL of ethanol, and stir for 1 hour under nitrogen gas, to Oxygen was removed from the reaction flask. Then, 0.115 g (1.0 mmol) of Pd(PPh ₃ ) ₄ was added and refluxed under vigorous stirring. The reaction process was tracked and detected by TLC. After the completion of the reaction, extract the aqueous phase with 200 mL of ethyl acetate, and desolvate the organic phase under reduced pressure until there is no distillate. The volume ratio to dichloromethane is petroleum ether:dichloromethane=22:1, and 4.5g of intermediate three (c) is obtained with a yield of 31.25%, and 3.0g of intermediate three (d) is obtained with a yield of 20.83%.

Preparation of intermediate three (e):

Take 3.5g of intermediate three (c) (6.0mmol), 1.4g of o-bromophenylboronic acid (7.0mmol), 1.7g of potassium carbonate (12.0mmol) and 15g of water, dissolve them in 30mL of toluene and 15mL of ethanol, and stir for 1 hour under nitrogen gas , to remove the oxygen in the reaction flask. Then, 0.035 g (0.03 mmol) of Pd(PPh ₃ ) ₄ was added and refluxed under vigorous stirring. The reaction process was tracked and detected by TLC. After the completion of the reaction, 100mL of ethyl acetate extracted the aqueous phase, and the organic phase was desolvated under reduced pressure until there was no distillate. The volume ratio to dichloromethane is petroleum ether:dichloromethane=20:1, and 2.7g of intermediate three (e) is obtained with a yield of 69.23%.

Preparation of E38:

Take 3.3g of intermediate three (d) (5.0mmol), 1.5g of DBU (12.0mmol) and 30g of DMF, and stir with nitrogen for 1 hour to remove the oxygen in the reaction flask. Then 0.35 g (0.05 mmol) of Pd(PPh ₃ ) ₂ Cl ₂ was added and refluxed under vigorous stirring. The reaction process was tracked and detected by TLC. After the reaction was completed, it was poured into 100g of ice water, and the aqueous phase was extracted with 200mL of ethyl acetate. The organic phase was desolvated under reduced pressure until there was no fraction, and then purified by column chromatography with pure toluene to obtain 2.2g Compound E38, yield 76.92%. The crude product was further sublimated and purified in a chemical vapor deposition system at 300° C. to obtain 1.9 g of off-white solid powder with a yield of 86.36%. The compound was identified by DEI-MS, molecular formula C ₄₂ H ₂₄ N ₂ O, detection value [M+1] ⁺ = 573.43, calculated value 572.67.

Example 4: Preparation of the aforementioned compound E53

The preparation of intermediate four (a):

Take 2.4g of intermediate three (d) (4.0mmol), 0.9g of o-bromophenylboronic acid (4.4mmol), 1.1g of potassium carbonate (8.0mmol) and 10g of water, dissolve them in 30mL of toluene and 15mL of ethanol, and stir for 1 hour under nitrogen gas , to remove the oxygen in the reaction flask. Then, 0.023 g (0.02 mmol) of Pd(PPh ₃ ) ₄ was added and refluxed under vigorous stirring. The reaction process was tracked and detected by TLC. After the completion of the reaction, 100mL of ethyl acetate extracted the aqueous phase, and the organic phase was desolvated under reduced pressure until there was no distillate. The volume ratio to dichloromethane is petroleum ether:dichloromethane=15:1, and 1.9 g of intermediate four (a) is obtained with a yield of 73.08%.

Preparation of E53:

Take 1.6g of intermediate four (a) (2.5mmol), 0.9g of DBU (5.5mmol) and 30g of DMF, and stir with nitrogen for 1 hour to remove the oxygen in the reaction flask. Then, 0.18 g (0.025 mmol) of Pd(PPh ₃ ) ₂ Cl ₂ was added and refluxed under vigorous stirring. The reaction process was tracked and detected by TLC. After the reaction was completed, it was poured into 100 g of ice water, and the aqueous phase was extracted with 200 mL of ethyl acetate. The organic phase was desolvated under reduced pressure until there was no fraction, and then purified by column chromatography with pure toluene to obtain 1.0 g of Compound E53, yield 71.43%. The crude product was further sublimated and purified in a chemical vapor deposition system at 320° C. to obtain 0.9 g of off-white solid powder with a yield of 90.0%. The compound was identified by DEI-MS, the molecular formula was C ₄₂ H ₂₄ N ₂ O, the detected value [M+1] ⁺ =573.62, and the calculated value was 572.67.

Compound 1-60 was prepared according to the method described in Example 1-4 of compound sample preparation, and DEI-MS was used to detect the compound, and the detection value [M+1] ⁺ and the calculated value obtained by detecting each compound were as follows in Table 1 shown.

Table 1 Mass spectral data of some compounds of the present invention

It can be known from the data in Table 1 above that the present invention has successfully obtained the organic optoelectronic material represented by formula I.

The compounds according to the invention are used in light-emitting devices as hole-blocking layer or electron-transporting layer materials. The thermal properties of the compound E01, compound E26, compound E38, compound E53 of the present invention and the existing material BPhen were tested, and the test results are shown in Table 2.

Table 2 Thermal Stability Test

Note: The glass transition temperature Tg is measured by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter of NETZSCH, Germany), and the heating rate is 10°C/min; the thermal weight loss temperature Td is the temperature at which the weight loss is 0.5% in a nitrogen atmosphere, Measured on the TGA-50H thermogravimetric analyzer of Shimadzu Corporation, Japan, the nitrogen flow rate is 20mL/min; PESA), and ultraviolet spectrophotometer (UV) test calculation, the test is the atmospheric environment.

From the data in the above table, it can be seen that the compounds provided by the present invention have suitable HOMO and LUMO energy levels and are suitable for use as hole blocking layer or electron transport layer materials in OLED devices; the compounds provided by the present invention in the above table have higher thermal stability properties, so that the life of the manufactured OLED device containing the compound of the invention is improved.

Examples of organic electroluminescent devices:

In the following examples of preparing organic electroluminescent devices, the reagent materials used are as follows:

In the organic electroluminescent device embodiment, the test system formed by the PR655 spectral scanning radiometer and the U.S. KeithleySoure Meter 2400 is used to carry out synchronous measurement and detection of the obtained device to obtain the driving voltage, quantum efficiency, current efficiency, power efficiency and Brightness, where all measurements above are made in room temperature atmosphere.

Embodiment 1: the preparation of device 1

(a) cleaning the anode on the transparent substrate layer: ultrasonic cleaning with deionized water, acetone, and ethanol for 15 minutes respectively, and then processing in a plasma cleaner for 2 minutes;

(b) Vacuum-evaporating a hole injection layer on the anode, the material used is Hat-CN, and the thickness is 50nm;

(c) On the hole injection layer 3, NPB is evaporated by vacuum evaporation, and its film thickness is 10nm, and this layer of organic material is used as the hole transport layer 4;

(d) co-evaporating the light-emitting layer 5 on the hole transport layer 4, the material is Alq3, and the thickness is 30nm;

(e) On the light-emitting layer compound, the vacuum-evaporated electron transport layer 6 is the compound E01 provided by the present invention, with a thickness of 30nm;

(f) On the electron transport layer 6, vacuum evaporate the electron injection layer LiF, the thickness is 0.5nm, this layer is the electron injection layer 7;

(g) On the electron injection layer 7, a cathode Al is vacuum evaporated to a thickness of 100 nm, and this layer is the cathode 8.

After the electroluminescent device was completed as above, the driving voltage, quantum efficiency, current efficiency, power efficiency and brightness of the device were measured, and the results are shown in Table 3.

Embodiment 2: Preparation of device 2

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E02 provided by the present invention. Device 2 The results of the fabricated organic electroluminescent device are in Table 3.

Embodiment 3: the preparation of device 3

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E03 provided by the present invention. Device 3 The results of the fabricated organic electroluminescent device are in Table 3.

Embodiment 4: Preparation of device 4

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E04 provided by the present invention. Device 4 The results of the fabricated organic electroluminescent device are in Table 3.

Embodiment 5: the preparation of device 5

The difference between the device of this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E05 provided by the present invention. Device 5 The results of the fabricated organic electroluminescent device are in Table 3.

Embodiment 6: the preparation of device 6

The difference between the device of this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E06 provided by the present invention. Device 6 The results of the fabricated organic electroluminescent device are in Table 3.

Embodiment 7: Preparation of device 7

The difference between the device of this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E07 provided by the present invention. Device 7 The results of the fabricated organic electroluminescent device are in Table 3.

Embodiment 8: Preparation of device 8

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E08 provided by the present invention. Device 8 The results for the fabricated electroluminescent device are in Table 3.

Embodiment 9: Preparation of device 9

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E09 provided by the present invention. Device 9 The results for the fabricated electroluminescent device are in Table 3.

Embodiment 10: Preparation of device 10

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E10 provided by the present invention. The results for the fabricated electroluminescent device of device 10 are in Table 3.

Embodiment 11: Preparation of device 11

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E11 provided by the present invention. Device 11 The results for the fabricated electroluminescent device are in Table 3.

Embodiment 12: Preparation of device 12

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E12 provided by the present invention. Device 12 The results for the fabricated electroluminescent device are in Table 3.

Embodiment 13: Preparation of device 13

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E13 provided by the present invention. Device 13 The results for the fabricated electroluminescent device are in Table 3.

Embodiment 14: Preparation of device 14

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescence device is made of the compound E14 provided by the present invention. Device 14 The results for the fabricated electroluminescent device are in Table 3.

Embodiment 15: Preparation of device 15

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E15 provided by the present invention. The results for the fabricated electroluminescent device of device 15 are in Table 3.

Embodiment 16: Preparation of device 16

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E16 provided by the present invention. Device 16 The results for the fabricated electroluminescent device are given in Table 3.

Embodiment 17: Preparation of device 17

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E17 provided by the present invention. Device 17 The results for the fabricated electroluminescent device are in Table 3.

Embodiment 18: Preparation of device 18

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E18 provided by the present invention. Device 18 The results for the fabricated electroluminescent device are in Table 3.

Embodiment 19: Preparation of device 19

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E19 provided by the present invention. Device 19 The results for the fabricated electroluminescent device are in Table 3.

Embodiment 20: Preparation of device 20

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E20 provided by the present invention. The results for the fabricated electroluminescent device of Device 20 are given in Table 3.

Embodiment 21: Preparation of device 21

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E21 provided by the present invention. The results for the fabricated electroluminescent device of Device 21 are given in Table 3.

Example 22: Preparation of device 22

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E22 provided by the present invention. Device 22 The results for the fabricated electroluminescent device are in Table 3.

Embodiment 23: Preparation of device 23

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E23 provided by the present invention. Device 23 The results for the fabricated electroluminescent device are in Table 3.

Example 24: Preparation of device 24

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E24 provided by the present invention. The results for the fabricated electroluminescent device of Device 24 are given in Table 3.

Embodiment 25: Preparation of device 25

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E25 provided by the present invention. The results for the electroluminescent device fabricated with device 25 are given in Table 3.

Embodiment 26: Preparation of device 26

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E26 provided by the present invention. Device 26 The results for the fabricated electroluminescent device are given in Table 3.

Example 27: Preparation of device 27

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E27 provided by the present invention. Device 27 The results for the fabricated electroluminescent device are in Table 3.

Example 28: Preparation of device 28

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E28 provided by the present invention. The results for the fabricated electroluminescent device of device 28 are shown in Table 3.

Embodiment 29: Preparation of device 29

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E29 provided by the present invention. Device 29 The results for the fabricated electroluminescent device are in Table 3.

Embodiment 30: Preparation of device 30

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E30 provided by the present invention. The results for the fabricated electroluminescent device of device 30 are shown in Table 3.

Example 31: Preparation of device 31

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E31 provided by the present invention. The results for the fabricated electroluminescent device of device 31 are in Table 3.

Example 32: Preparation of device 32

The difference between this example and device 1 lies in that the electron transport layer of the prepared organic electroluminescent device is made of the compound E32 provided by the present invention. The results for the fabricated electroluminescent device of device 32 are shown in Table 3.

Example 33: Preparation of device 33

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E33 provided by the present invention. The results for the fabricated electroluminescent device of device 33 are in Table 3.

Example 34: Preparation of device 34

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E34 provided by the present invention. The results for the fabricated electroluminescent device of Device 34 are given in Table 3.

Example 35: Preparation of device 35

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E35 provided by the present invention. The results for the fabricated electroluminescent device of Device 35 are given in Table 3.

Example 36: Preparation of device 36

The difference between this example and device 1 lies in that the electron transport layer of the prepared organic electroluminescent device is made of the compound E36 provided by the present invention. The results for the fabricated electroluminescent device of Device 36 are given in Table 3.

Example 37: Preparation of device 37

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E37 provided by the present invention. Device 37 The results for the fabricated electroluminescent device are in Table 3.

Example 38: Preparation of device 38

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E38 provided by the present invention. Device 39 The results for the fabricated electroluminescent device are in Table 3.

Example 39: Preparation of device 39

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescence device is made of the compound E39 provided by the present invention. Device 39 The results for the fabricated electroluminescent device are in Table 3.

Example 40: Preparation of device 40

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E40 provided by the present invention. The results for the fabricated electroluminescent device of Device 40 are shown in Table 3.

Example 41: Preparation of device 41

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E41 provided by the present invention. The results for the fabricated electroluminescent device of Device 41 are shown in Table 3.

Example 42: Preparation of device 42

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E42 provided by the present invention. The results for the fabricated electroluminescent device of Device 42 are shown in Table 3.

Example 43: Preparation of device 43

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E43 provided by the present invention. The results for the fabricated electroluminescent device of Device 43 are shown in Table 3.

Example 44: Preparation of device 44

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E44 provided by the present invention. The results for the fabricated electroluminescent device of Device 44 are shown in Table 3.

Example 45: Preparation of device 45

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E45 provided by the present invention. The results for the fabricated electroluminescent device of device 45 are shown in Table 3.

Example 46: Preparation of device 46

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E46 provided by the present invention. The results for the fabricated electroluminescent device of Device 46 are shown in Table 3.

Example 47: Preparation of device 47

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E47 provided by the present invention. The results for the fabricated electroluminescent device of Device 47 are shown in Table 3.

Example 48: Preparation of Device 48

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E48 provided by the present invention. The results for the fabricated electroluminescent device of Device 48 are shown in Table 3.

Example 49: Preparation of device 49

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescence device is made of the compound E49 provided by the present invention. The results for the fabricated electroluminescent device of device 49 are shown in Table 3.

Example 50: Preparation of device 50

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E50 provided by the present invention. The results for the electroluminescent device fabricated with device 50 are shown in Table 3.

Example 51: Preparation of device 51

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E51 provided by the present invention. The results for the fabricated electroluminescent device of device 51 are in Table 3.

Example 52: Preparation of device 52

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E52 provided by the present invention. The results for the fabricated electroluminescent device of device 52 are given in Table 3.

Example 53: Preparation of device 53

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E53 provided by the present invention. The results for the fabricated electroluminescent device of device 53 are shown in Table 3.

Example 54: Preparation of device 54

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E54 provided by the present invention. The results for the fabricated electroluminescent device of device 54 are shown in Table 3.

Example 55: Preparation of device 55

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E55 provided by the present invention. The results for the fabricated electroluminescent device of device 55 are in Table 3.

Example 56: Preparation of device 56

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E56 provided by the present invention. The results for the fabricated electroluminescent device of device 56 are shown in Table 3.

Example 57: Preparation of device 57

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E57 provided by the present invention. The results for the fabricated electroluminescent device of device 57 are shown in Table 3.

Example 58: Preparation of device 58

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E58 provided by the present invention. The results for the fabricated electroluminescent device of device 58 are shown in Table 3.

Example 59: Preparation of device 59

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E59 provided by the present invention. The results for the fabricated electroluminescent device of device 59 are shown in Table 3.

Embodiment 60: Preparation of device 60

The difference between this example and device 1 is that the electron transport layer of the prepared organic electroluminescent device is made of the compound E60 provided by the present invention. The results for the fabricated electroluminescent device of device 60 are shown in Table 3.

Comparative Example 1: Preparation of Device 1#

The difference between Device Comparative Example 1 and Device 1 is that the electron transport layer of the organic electroluminescent device uses BPhen as the electron transport material.

Comparative example 2: preparation of device 2#

The difference between Device Comparative Example 2 and Device 1 is that the electron transport layer of the organic electroluminescent device uses BCP as the electron transport material.

The relevant results obtained from the detection of devices 1-60, device 1# and device 2# are shown in Table 3 below:

Table 3 Device Data

It can be seen from Table 3 that the photoelectric material of the present invention can be applied to the manufacture of electroluminescent devices, and can obtain good performance. The material of the present invention is used as an electron transport material of an electroluminescent device, and its driving voltage is lower than that of device 1# and device 2# using conventional BPhen and BCP as electron transport materials. In addition, compared with device 1# and device 2#, the power and lifetime of device examples 1-60 are significantly improved.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within range.

Claims (8)

1. the organic photoelectrical material containing indeno phenanthrene quinoline structure, it is characterised in that there is molecular structure shown in formula 1:

Wherein, R₁And R₂For the one in hydrogen, phenyl or dibenzofuran group, R₃It is that 10-60 is many for hydrogen, phenyl, carbon number Ring is conjugated aryl and containing the one in the aromatic heterocyclic radical in N, S, O atom.

A kind of organic photoelectrical material containing indeno phenanthrene quinoline structure the most according to claim 1, it is characterised in that described R₃Concrete structure formula be:

3. the preparation method of the organic photoelectrical material containing indeno phenanthrene quinoline structure, it is characterised in that comprise the steps:

Step 1: under the protection of noble gas and under the temperature conditions of-100～0 DEG C, by 2.0～2.4 molar equivalents N-BuLi joins 4 containing 1.0 molar equivalents, in the THF solution of 7-dibromo-o phenanthrene quinoline, reacts, adds 2.0 ～2.2 the trim,ethylchlorosilane of molar equivalent react, after obtaining the reaction system containing intermediate one, then by above-mentioned containing The reaction system of intermediate one is to slowly warm up to room temperature, then pours in water, stirring reaction 10～50min, is subsequently adding acetic acid Ethyl ester carries out being layered, washing successively, then to organic facies decompression desolventizing to without fraction, obtains intermediate one；

Step 2: under the protection of noble gas and under the temperature conditions of-100～0 DEG C, by 1.0～1.1 molar equivalents N-BuLi joins aryl halides R containing 1.0 molar equivalents₁In the THF solution of-Br, carry out first step reaction, obtain R₁Lithium salt solution, then under the temperature conditions of-60～10 DEG C, by above-mentioned R₁Lithium salt solution be added dropwise to containing 1 obtaining in steps Intermediate one organic solution in, carry out second step reaction, then add water and carry out cancellation reaction, then with dichloromethane extract, The extract manganese dioxide of 4～10.0 molar equivalents is processed, after obtaining the reaction system containing intermediate two, then by above-mentioned Reaction system containing intermediate two carries out filtration under diminished pressure, gained filtrate reduced in volume, then mixes with petroleum ether and dichloromethane Conjunction liquid is to above-mentioned concentrating under reduced pressure, and the product obtained carries out column chromatography purification, and wherein petroleum ether is stone with the volume ratio of dichloromethane Oil ether: dichloromethane=5～60:1, obtains intermediate two；

Step 3: under the protection of noble gas and under the temperature conditions of-100～0 DEG C, by 1.0～1.1 molar equivalents N-BuLi joins aryl halides R containing 1.0 molar equivalents₂The organic solution of-Br, carries out first step reaction, obtains R₂ Lithium salt solution, then under the temperature conditions of-60～10 DEG C, by above-mentioned R₂Lithium salt solution be added dropwise to containing 2 obtaining in steps Intermediate two organic solution in, carry out second step reaction, then add water and carry out cancellation reaction, then with dichloromethane extract, The extract manganese dioxide of 4～10.0 molar equivalents is processed, obtains the reaction system containing intermediate three, by above-mentioned containing The reaction system of intermediate three carries out filtration under diminished pressure, and gained filtrate reduced in volume, then with petroleum ether and dichloromethane mixed liquor To above-mentioned concentrating under reduced pressure, the product obtained carries out column chromatography purification, and wherein petroleum ether is petroleum ether with the volume ratio of dichloromethane: Dichloromethane=5～60:1, obtain intermediate three；

Step 4: under the protection of noble gas and under the temperature conditions of 0～60 DEG C, by the NBS of 2.1～3.0 molar equivalents Join in the organic solution containing the intermediate three that 3 obtain in steps, obtain the reaction system containing intermediate four, contain above-mentioned There is the reaction system of intermediate four, add the sodium sulfite solution that mass percent concentration is 2% and carry out cancellation reaction, then Adding chloroform, after layering, add water washing, after having washed, to organic facies decompression desolventizing to without fraction, after desolventizing, uses Toluene alcohol mixed solvent carries out recrystallization, and wherein toluene is 2:3～8 with the volume ratio of ethanol；Or with petroleum ether and dichloromethane Alkane mixed liquor carries out column chromatography purification to the residue after above-mentioned concentrating under reduced pressure, and wherein petroleum ether with the volume ratio of dichloromethane is 5～60:1, obtain intermediate four；

Step 5: intermediate four that step 4 is obtained, aryl boric acid R₃-B(OH)₂And alkaline matter, join toluene, diformazan In benzene, DMF or dimethyl acetylamide, under inert gas shielding, add catalyst, then, 60～ After reacting 2～24 hours at 150 DEG C, obtain the reaction system containing intermediate five, by the above-mentioned reactant containing intermediate four System's layering, washes with water, then to organic facies decompression desolventizing to without fraction, is then purified with column chromatography, and described purification is used The mixed liquor of petroleum ether and the mixed liquor of dichloromethane or petroleum ether and ethyl acetate carries out eluting, wherein petroleum ether and dichloro The volume ratio of methane is 2～60:1, and petroleum ether is 2～35:1 with the volume ratio of ethyl acetate, obtains intermediate five；

Step 6: the intermediate five, bromophenyl boric acid and the alkaline matter that step 5 are obtained join toluene, dimethylbenzene, N, N- In dimethylformamide or dimethyl acetylamide, under inert gas shielding, add catalyst, then, anti-at 60～150 DEG C After answering 2～24 hours, obtain the reaction system containing intermediate six, the above-mentioned reaction system containing intermediate five is layered, use Water washs, then to organic facies decompression desolventizing to without fraction, is then purified with column chromatography, above-mentioned purification petroleum ether and two The mixed liquor of the mixed liquor of chloromethanes or petroleum ether and ethyl acetate carries out eluting, wherein petroleum ether and the volume of dichloromethane Ratio is 2～60:1, and petroleum ether is 2～35:1 with the volume ratio of ethyl acetate, obtains intermediate six；

Step 7: the intermediate six obtained in step 6 and alkaline matter are joined toluene, dimethylbenzene, N, N-dimethyl formyl In amine or dimethyl acetylamide, under inert gas shielding, add catalyst, then, at 60～170 DEG C, react 2～24 little Shi Hou, i.e. obtains the described organic photoelectrical material containing indeno phenanthrene quinoline structure.

The preparation method of a kind of organic photoelectrical material containing indeno phenanthrene quinoline structure the most according to claim 3, it is special Levying and be, in step 5, described alkaline matter is the one in sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide or many Kind；Described catalyst is in palladium, four (triphenylphosphines), bi triphenyl phosphorus palladium chloride and three (dibenzalacetone) two palladium One or more；The temperature of described reaction is 60～90 DEG C, and the time is 4～8 hours；Described alkaline matter and intermediate four Mol ratio is 1.3～3.0:1.

The preparation method of a kind of organic photoelectrical material containing indeno phenanthrene quinoline structure the most according to claim 3, it is special Levying and be, in step 6, described alkaline matter is the one in sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide or many Kind；Described catalyst is in palladium, four (triphenylphosphines), bi triphenyl phosphorus palladium chloride and three (dibenzalacetone) two palladium One or more；The temperature of described reaction is 60～90 DEG C, and the time is 4～8 hours；Described alkaline matter and intermediate four Mol ratio is 1.3～3.0:1；Described catalyst is 0.001～0.1:1 with the mol ratio of intermediate five.

The preparation method of a kind of organic photoelectrical material containing indeno phenanthrene quinoline structure the most according to claim 3, it is special Levying and be, in step 7, described alkaline matter is one or more in triethylamine, DBU, Sodium ethylate；Described catalyst is selected from vinegar One or more in acid palladium, four (triphenylphosphines), bi triphenyl phosphorus palladium chloride, three (dibenzalacetone) two palladium；Reaction Temperature is preferably 100～170 DEG C, and the response time is preferably 6～12 hours；Described alkaline matter with the mol ratio of intermediate six is 1.3～3.0:1；Described catalyst is 0.001～0.1:1 with the mol ratio of intermediate six.

The preparation method of a kind of organic photoelectrical material containing indeno phenanthrene quinoline structure the most according to claim 3, it is special Levying and be, in step 5, step 6 and step 7, add phosphine system part when adding catalyst, described phosphine system part is 1, and 3-is double (diphenylphosphine) propane, 4,5-double diphenylphosphine-9,9-dimethyl xanthene, 2-dicyclohexyl phosphine-2', 6'-dimethoxy joins One or more in benzene or tri-butyl phosphine tetrafluoroborate.

8. the application of the organic photoelectrical material containing indeno phenanthrene quinoline structure, it is characterised in that at organic electroluminescence In part, at least a functional layer contains the organic photoelectrical material containing indeno phenanthrene quinoline structure described in claim 1 or 2.