TWI624465B - A?novel organic electroluminescent compound and an organic electroluminescent device comprising the same. - Google Patents

Abstract

The invention relates to an organic optoelectronic material and an organic electroluminescent device including the organic material. The organic optoelectronic material is represented by the following formula I, wherein R1 and R2 are independently selected from the group consisting of hydrogen, cyano, isothiocyano and One of phenyl groups, R3, R4, R5, R6, R7, and R8 are each independently selected from a hydrogen group, a halogen group, and an aromatic heterocyclic group having 10 to 50 carbon atoms and containing at least one of N, S, and O One of the ring groups. The organic photoelectric material can be used as a luminescent material in an organic electroluminescent device, thereby improving the maximum current efficiency of the organic electroluminescent device, reducing the turn-on voltage of the organic electroluminescent device, and making the organic electroluminescent device The spectrum of visible light emitted covers a wide range.

Description

Organic photoelectric material and organic electroluminescent device including the organic material

The invention relates to the field of optoelectronic technology, in particular to an organic optoelectronic material and an organic electroluminescent device including the organic optoelectronic material.

Organic electroluminescence devices (OLEDs for short) were produced in the 1980s. Compared with liquid crystal displays, OLEDs have many advantages, such as self-luminescence, wide viewing angle, fast response speed, and flexible display.

Organic electroluminescent devices are a kind of current-driven light-emitting devices. According to different light-emitting mechanisms, they can be divided into two types: fluorescent devices and phosphorescent devices. The proportion of excitons is only 25%, and the other 75% are triplet excitons. In general, fluorescent devices can only emit light using singlet excited state excitons, while phosphorescent devices can use singlet excitons and triplet excitons at the same time. The energy, therefore, the efficiency of phosphorescent devices is much greater than fluorescent devices.

The efficiency of phosphorescent devices is higher than that of fluorescent devices. However, phosphorescent devices also have their deficiencies. For example, phosphorescent materials are mainly complexes containing precious metals, especially the complexes of metal iridium and platinum. Because metal iridium and platinum are expensive, Therefore, the price of phosphorescent materials is extremely expensive, which also limits the application space of phosphorescent materials.

Therefore, the development of OLED devices that use fluorescent materials as light-emitting molecules and can achieve high-efficiency light emission is very attractive.

In 2012, C. Adachi published a paper on Nature (Nature., 2012, 492, 234), reporting a fluorescent device based on thermally activated delayed fluorescence (TADF) mechanism to achieve efficient light emission, which is high-efficiency fluorescent The production of devices has brought new directions. Within the scope of existing knowledge, TADF materials need to have an electron donor (abbreviated as D) and an electron acceptor (abbreviated as A). The DA-type structure formed by this can achieve the molecular structure requirements of delayed fluorescence.

One of the objects of the present invention is to provide a liquid crystal aligning agent. The liquid crystal aligning agent of the present invention is formed by polymerizing a diamine monomer containing t-butylphenol fragments and other tetracarboxylic dianhydride monomers; since the diamine monomer contains t-butylphenol fragments, the polymerized material is UV resistant The performance is more prominent. Therefore, the liquid crystal alignment film of the present invention can enlarge its working window when performing the photo-alignment exposure process of the present invention. It has the dual advantages of complete exposure of the exposed area and excellent UV resistance in the non-exposed area. , Which can improve the display effect and service life of the LCD.

In order to solve the above problems, the present invention provides an organic optoelectronic material, which can be used as a luminescent material in an organic electroluminescent device, thereby improving the maximum current efficiency of the organic electroluminescent device and reducing the lighting of the organic electroluminescent device Voltage, and makes the visible light emitted by the organic electroluminescent device have a wider spectral coverage.

The object of the present invention is to provide an organic photoelectric material, which is represented by the following formula I.

In the above formula I, R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, cyano (-CN), isothiocyano (-NCS) and phenyl ( ), R ₃ , R ₄ , R ₅ , R ₆ , R _7, and R ₈ are each independently selected from a hydrogen group, a halogen group, and a carbon atom having 10 to 50 carbon atoms and containing at least N, S, and O One of an aromatic heterocyclic group. Among them, the halogen group can be selected according to actual needs, preferably a fluorine group, a chlorine group, or a bromine group, and further preferably a fluorine group. Among the substituents, it is preferred that R ₁ and R _{2 are the} same, and R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be the same as each other, or may be different from each other, and may be any two of them or The two are the same and are not subject to specific restrictions.

In the above formula I, as examples of the aromatic heterocyclic group, fused heterocyclic group, monocyclic aromatic heterocyclic group, polycyclic aromatic heterocyclic group and the like can be given. Cyclic aromatic or non-aromatic heterocycles (heterocycles can be different) are obtained by condensation, in addition, the aromatic heterocyclic group can also be the above-mentioned condensed heterocyclic group, monocyclic aromatic heterocyclic group or polycyclic aromatic The heterocyclic group is obtained by bonding to at least one group of an aryl group, a halogenated aryl group and an arylamine group, wherein the aryl group may include a phenyl group, an aralkyl group, and an aryl group containing at least one phenyl group For example, biphenyl, halogenated aryl is a group formed by the substitution of an aryl group with at least one of F, Cl, Br. Among them, it is preferred that F be substituted with an aryl group, and the arylamine group may be a diphenylamine group. Of course It is pointed out here that a few typical groups are cited and are not subject to specific restrictions. When containing N, S, O heteroatoms, the number of heteroatoms is not subject to specific restrictions, for example, can be 1, 2, 3, 4, 5, 6, or 7, in addition, In one substituent, any one of the above heteroatoms may be selected, or any two or three of the above heteroatoms. Preferably, an aromatic heterocyclic group having 11 to 40 carbon atoms is selected, and further preferably, an aromatic heterocyclic group having 11 to 36 carbon atoms is selected.

Preferably, the aromatic heterocyclic group is selected from one or more of the groups represented by the following formula (1) to formula (21):

In the above formula (1), formula (4), formula (9), formula (12) and formula (17), R9 and R10 are each independently selected from a hydrogen group, an alkyl group having 1 to 10 carbon atoms, One of an aryl group having 6 to 10 carbon atoms, an arylamine group having 6 to 20 carbon atoms, and a fused heterocyclic group containing N and 12 to 20 carbon atoms, R11 is selected from a hydrogen group or An alkyl group having 1 to 10 carbon atoms; in the above formulas (1) to (16), L represents a bonded group, L is selected from an arylene group having 6 to 20 carbon atoms, and the carbon atom number is One of 6-20 halogenated arylene groups and arylene cyano groups, wherein the halogen atom is F, Cl, Br, preferably F; in the above formula (17) to formula (21), M represents a bonded group The group, M is one selected from the group consisting of a hypoaryl group having 6 to 20 carbon atoms, a halogenated hypoaryl group, and a hypoaromatic cyano group, wherein the halogen atom is F, Cl, Br, preferably F.

In R9, R10 and R11, the substituents are as follows.

The alkyl group having 1 to 10 carbon atoms may be a chain alkyl group or a cycloalkyl group. The chain alkyl group includes a linear alkyl group and a branched alkyl group. In addition, the hydrogen on the chain alkyl group may also be It is substituted by cycloalkyl. Similarly, the hydrogen on cycloalkyl can also be substituted by alkyl. Preferably, an alkyl group having 1 to 6 carbon atoms is selected, and further preferably, a chain alkyl group having 1 to 4 carbon atoms and a cycloalkyl group having 5 to 6 carbon atoms are selected. Examples of the alkyl group specifically include methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl.

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and an aralkyl group. Preferably, an aryl group having 6 to 9 carbon atoms is selected, and still more preferably, an aryl group having 6 to 8 carbon atoms is selected.

An arylamine group having 6 to 20 carbon atoms may be a group formed by replacing hydrogen on ammonia (NH3) with an aryl group such as a phenyl group, specifically a diphenylamine group, in which the number of aryl groups is substituted It may be 1, 2 or 3, and the aryl group mentioned above is preferably the aryl group mentioned above, so it will not be repeated one by one. Preferably, an arylamine group having 12 to 20 carbon atoms is selected, and further preferably, an arylamine group having 12 to 16 carbon atoms is selected.

Examples of the fused heterocyclic group containing N and having 12 to 20 carbon atoms include oxazolyl. Preferably, a fused heterocyclic group containing N and having 12 to 16 carbon atoms is selected.

In the above formula (1) to formula (16), the L group is as follows.

The arylene group having 6 to 20 carbon atoms can be, for example, a phenylene group, a phenylene alkyl group such as a phenyl group containing methyl or tert-butyl groups, an arylene group containing at least one phenyl group such as biphenylene, A condensed ring aromatic hydrocarbon group, wherein the carbon on the biphenylene group and the condensed ring aromatic hydrocarbon group may be bonded to an alkyl group and / or an alkenyl group, where the alkyl group is, for example, methyl or tert-butyl. Preferably, an arylene group having 6 to 14 carbon atoms is selected, further preferably, an arylene group having 6 to 12 carbon atoms is selected, and still more preferably, an arylene group having 6 to 8 carbon atoms is selected. . As examples of arylene groups, specific examples include:

A halogenated arylene group having 6 to 20 carbon atoms is a group formed by replacing an arylene group with a halogen atom, wherein the above-mentioned arylene group is preferably substituted by a halogen atom such as fluorine, and the preferred number of carbon atoms is 6-20 fluoroarylene groups. Preferably, the halogenated arylene group having 6 to 14 carbon atoms is selected, further preferably, the halogenated arylene group having 6 to 14 carbon atoms is selected, and still more preferably, the carbon atom number is 6 to 12 Halogenated arylene. As examples of halogenated arylene groups, specific examples include:

The arylene cyano group is a group formed by replacing an arylene group with a cyano group, and it is preferred that the above-mentioned arylene group is substituted with a cyano group.

In the above formula (17) to formula (21), the M group is as follows.

The secondary aryl group having 6 to 20 carbon atoms is an aromatic compound having three groups that can bond with other groups. Preferably, the sub-aryl group having 6 to 14 carbon atoms is selected, and further preferably, the sub-aryl group having 6 to 12 carbon atoms is selected. As examples of hypoaryl groups, specific examples include:

The above-mentioned halogenated hypoaryl groups and hypoaromatic cyano groups are groups formed by successive substitution of hypoaryl groups with halogen atoms or cyano groups, and are preferably substituted with F.

The organic photoelectric material provided by the present invention is a small molecule material containing an acenaphthopyrazine structure, which is modified by selecting other chemical groups on the structure containing an acenaphthopyrazine, the specific selected chemical groups are as described above, I will not repeat them one by one here, so that the organic optoelectronic material has DA-type or DAD-type molecular structural units. That is, the organic optoelectronic material provided by the present invention contains both an electron acceptor core and an electron donor. The material has excellent fluorescence emission ability, has a suitable molecular energy level, moderate molecular quality, and good film stability. It is suitable as a functional layer for small molecule organic electroluminescent devices and is used in the field of organic electroluminescence, especially Ground, the organic optoelectronic material can be used as a light-emitting material and is preferably applied to the light-emitting layer in small molecule organic electroluminescent devices.

The organic photoelectric material provided by the present invention is used as a luminescent material in an organic electroluminescent device, so that the organic electroluminescent device can emit visible light of different colors, such as sky blue, cyan, green, orange, etc., with a wide spectrum coverage, And improve the performance of organic electroluminescent devices, such as greatly increasing the maximum current efficiency of the device, while reducing the turn-on voltage.

As examples of organic optoelectronic materials, the following compounds C001 ~ C372 can be specifically mentioned. Among them, the following compounds are representative structures that conform to the spirit and principles of the present invention. It should be understood that the specific structures of the following compounds are listed only for the purpose of A better explanation of the invention is not a limitation of the invention.

The specific preparation method of the organic electroluminescent material provided in the present invention will be described in detail in the following examples. The related synthetic routes and preparation processes are conventional steps and routine choices in the field of organic synthesis. This will not be repeated here.

Another object of the present invention is to provide an organic electroluminescent device comprising a cathode, an anode and a light-emitting layer, the light-emitting layer is located between the anode and the cathode, wherein the light-emitting layer is prepared by including the organic photoelectric material provided by the present invention obtain.

In addition, the above organic electroluminescent device may further include a hole transport layer, an electron transport layer, and an electron injection layer, wherein the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer are all located between the cathode and the anode In between, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer are sequentially stacked on the anode.

In the above organic electroluminescent device, the anode is preferably indium tin oxide (ITO) conductive glass, the hole transport layer is preferably prepared from NPB, the light emitting layer is preferably prepared from the material provided by the present invention and mCP, and the electron transport layer is obtained from TPBI The preparation is obtained, the electron injection layer is prepared by LiF, and the cathode is preferably Al, where NPB, mCP and TPBI are as shown below.

In the above organic electroluminescent device, each functional layer is not limited to the use of the above-mentioned materials, these materials can be replaced with other materials, such as hole transport layer can be prepared by TAPC, electron transport layer can be obtained by TpPYPB , Where TAPC and TpPYPB are as follows:

In the above-mentioned organic electroluminescent device, each of the above-mentioned film layers, that is, the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer can be separated by evaporation, spin coating, or casting methods. The material corresponding to the layer is made of a thin film. In addition, in order to make the material of each film layer thin and to obtain a uniform film layer, at the same time, it is difficult to generate pinholes, and the vacuum evaporation method is preferable. When the vacuum evaporation method is selected, the heating temperature, vacuum degree, evaporation speed and temperature of the substrate can be routinely selected according to actual needs. It is easy to obtain a uniform film layer when the corresponding material is thinned by vacuum evaporation method, and it is not easy to generate pinholes.

The organic electroluminescent device provided by the present invention can be prepared by a conventional method without special requirements.

The organic electroluminescent device provided by the present invention, because it contains the organic photoelectric material provided by the present invention, can greatly improve the maximum current efficiency of the organic electroluminescent device, at the same time, it also reduces the turn-on voltage and significantly improves the organic electroluminescence The lifetime of the luminescent device.

101‧‧‧Anode

102‧‧‧hole transport layer

103‧‧‧luminous layer

104‧‧‧Electronic transmission layer

105‧‧‧Electron injection layer

106‧‧‧Cathode

FIG. 1 is a schematic structural diagram of an organic electroluminescent device provided by an embodiment of the present invention.

The following describes the present invention in detail, and the features and advantages of the present invention will become more clear and unambiguous with these descriptions.

Examples

The present invention is further described below by specific examples. However, these examples are only exemplary and do not limit the protection scope of the present invention.

In the following examples, the reagents, materials and instruments used are all conventional reagents, conventional materials and conventional instruments, and are commercially available unless otherwise specified. The reagents involved can also be synthesized by conventional synthetic methods obtain.

Example 1 Preparation of compounds

Example 1 Preparation of Compound 1

Add 5-bromoacenaphthoquinone (26.1g, 0.1mol), ethylenediamine (13g, 0.12mol) and glacial acetic acid (300mL) to a 1L three-necked bottle, warm up to reflux, under an air atmosphere, keep the reaction for 12h After reaching room temperature, pour the reaction solution into 1000 mL of deionized water, stir the reaction for 0.5 h, filter with suction, and rinse the filter cake with 500 mL of deionized water, then rinse the filter cake with 150 mL of absolute ethanol, and collect the filter cake The obtained compound 1 was 22.2g, and the calculated yield was 78%. Mass spectrometry (abbreviated as MS) (m / z): 281.9.

Example 2-Example 11 Preparation of Compound 2 to Compound 11

Compounds 2 to 11 were prepared according to the following methods:

According to the method and the ratio of raw materials given in Example 1, wherein different types of substrates are used as raw materials, the ring closure reaction is carried out with ethylenediamine. In each example, the raw materials selected and the corresponding compounds are obtained and The yield and mass spectrum detection results are shown in Table 1 below.

Table 1

Example 12 Preparation of Compound 12

In a 1L three-necked bottle, add 5-bromoacenaphthoquinone (26.1g, 0.1mol), diaminomaleonitrile (13g, 0.12mol) and glacial acetic acid (300mL), warm to reflux, and after 6h of incubation reaction, reduce to At room temperature, the reaction solution was poured into 1000 mL of deionized water, stirred for 0.5 h, and then filtered with suction, then the filter cake was rinsed with 500 mL of deionized water, and then the filter cake was rinsed with 150 mL of absolute ethanol, and the filter cake was collected to obtain the compound 12 is 28.6g, the calculated yield is 86%, mass spectrometry (MS) (m / z): 331.9.

Example 13-Example 22 Preparation of compound 13 to compound 22

Compounds 13 to 22 were prepared according to the following methods:

According to the method and raw material ratio given in Example 12, wherein different types of substrates are used as raw materials, they are subjected to ring-closure reaction with diaminomaleonitrile. In each example, the raw materials selected and the corresponding The compound, yield and mass spectrometry detection results are shown in Table 2 below.

Table 2

Example 23 Preparation of the aforementioned compound C001

In a 100mL three-necked flask, add compound 1 (2.83g, 0.01mol), dyszole (2.0g, 0.012mol), sodium tert-butoxide (1.92g, 0.02mol), palladium acetate (0.044g, 0.0002mol), three Tert-butylphosphine (0.081g, 0.0004mol) and o-xylene (30g), the system was heated to reflux, after 8 hours of incubation reaction, the temperature was lowered to 25 ℃, then added 20g deionized water, stirred for 10min, then separated, collected The organic phase is then filtered with suction. After suction filtration, the filtrate is desolvated to obtain the crude product, and then the crude product is purified using silica gel column chromatography, in which the eluent is ethyl acetate, and then the crude product is further sublimed and purified using a chemical vapor deposition system Among them, the sublimation temperature is 320 ℃, and 1.7g of compound C001 is finally obtained, and the calculated yield is 46%.

After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound C001 is C26H15N3, the detected value is 369.1268, and the theoretical value is 369.1266; in addition, after elemental analysis of compound C001, it is detected that C: 84.54%, H: 4.11%, N: 11.35%, theoretical values are C: 84.53%, H: 4.09%, N: 11.37%.

Example 24-Example 61 Preparation of some compounds from compound C003 to compound C235

Some compounds from compound C003 to compound 235 were prepared according to the following methods:

According to the method and the raw material ratio given in Example 23, the CN coupling reaction was carried out, but the type of raw material was changed. In each example, the corresponding compound structure, the corresponding molecular formula, the yield of the prepared compound and the high The results of resolution mass spectrometry and elemental analysis are shown in Table 3 below.

table 3

Note: The wavy line in Table 3 above indicates the position where the C-N bond is generated.

Example 62 Preparation of Compound C265

In a 100 mL three-necked flask, add compound 7 (3.62 g, 0.01 mol), dyszole (4.0 g, 0.024 mol), sodium tert-butoxide (3.85 g, 0.04 mol), palladium acetate (0.088 g, 0.0004 mol), three Tert-butylphosphine (0.16g, 0.0008mol) and o-xylene (40g), warmed to reflux, after holding the reaction for 16h, the temperature was lowered to 25 ℃, then added 20g of deionized water, stirred for 10min, and then separated, then collected organic Phase, and then suction filtration, and then the solvent was removed from the filtrate to obtain the crude product, and then the crude product was purified using silica gel column chromatography, in which the eluent was ethyl acetate, and finally the crude product was further purified by sublimation using a chemical vapor deposition system, where the sublimation temperature was At 350 ° C, 2.9 g of compound C265 was obtained with a calculated yield of 54%.

After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound C265 is C38H22N4, the detection value is 534.1849, and the theoretical value is 534.1844; in addition, after elemental analysis of compound C265, the detection yields C: 85.34%, H: 4.19%, N: 10.47%, and the theoretical values are C: 85.37%, H: 4.15%, N: 10.48%.

Example 63-Example 86 Preparation of some compounds from compound C266 to compound C372

Some of the compounds C266 to C372 were prepared according to the following methods:

The CN coupling reaction was carried out according to the method given in Example 62 and the ratio of raw materials, but the type of raw materials was changed. In each example, the corresponding compound structure, corresponding molecular formula, yield of compound preparation and high The results of resolution mass spectrometry and elemental analysis are shown in Table 4 below.

Table 4

Note: The wavy line in Table 4 above indicates the location where the C-N bond is generated.

Example 87 Preparation of Compound C013

In a 100mL three-necked flask, add compound 1 (2.83g, 0.01mol), 4- (9H-oxazole) phenylboronic acid (3.44g, 0.012mol), potassium carbonate (5.5g, 0.04mol), palladium acetate (0.088g , 0.0004mol), triphenylphosphine (0.21g, 0.0008mol), toluene (40g) and deionized water (15g), the system was heated to reflux, after holding the reaction for 16h, the temperature was lowered to 25 ℃, then the liquid was separated, then The organic phase was collected, followed by suction filtration, the filtrate was collected, the solvent was removed to obtain the crude product, and then the crude product was purified using silica gel column chromatography, in which the eluent was ethyl acetate, and finally the crude product was further purified by sublimation using a chemical vapor deposition system, in which the sublimation temperature At 340 ° C, 1.9 g of compound C013 was obtained with a calculated yield of 43%.

After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the compound C013 molecular formula is C32H19N3, the detection value is 445.1573, and the theoretical value is 445.1579; in addition, after elemental analysis, the compound C013 is detected to obtain C: 86.23%, H: 4.29% , N: 9.48%, and the theoretical values are C: 86.27%, H: 4.30%, N: 9.43%.

Examples 88-Example 138 Preparation of some compounds from compound C014 to compound C239

Some compounds from compound C014 to compound 239 were prepared according to the following methods:

The CC coupling reaction was carried out according to the method given in Example 87 and the ratio of raw materials, but only the type of raw materials was changed. In each example, the corresponding compound structure, corresponding molecular formula, yield of compound preparation and high The results of resolution mass spectrometry and elemental analysis are shown in Table 5 below.

table 5

Note: The wavy line in Table 5 above indicates the position where the C-C bond is generated.

Example 139 Preparation of Compound C269

In a 250 mL three-necked bottle, add compound 7 (3.62 g, 0.01 mol), 4- (9H-oxazole) phenylboronic acid (6.9 g, 0.024 mol), potassium carbonate (11 g, 0.08 mol), and palladium acetate (0.088 g, 0.0004mol), triphenylphosphine (0.21g, 0.0008mol), toluene (80g) and deionized water (35g), warmed to reflux, after 28 hours of incubation reaction, the temperature was reduced to 25 ° C, and the liquid was separated again, and then the organic phase was collected Then, suction filtration, collect the filtrate, remove the solvent to obtain the crude product, and then use silica gel column chromatography to purify the crude product, wherein the eluent is ethyl acetate, and finally use a chemical vapor deposition system to further sublimate and purify the crude product, where the sublimation temperature is 370 ℃ Finally, 2.7g of compound C269 was obtained with a calculated yield of 39%.

After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound C269 is C50H30N4, the detection value is 686.2476, and the theoretical value is 686.2470; in addition, after elemental analysis of compound C269, the detection yields C: 87.46%, H: 4.41%, N: 8.13%, and the theoretical value is C: 87.44%, H: 4.40%, N: 8.16%.

Examples 140-Example 151 Preparation of some compounds from compound C270 to compound C329

Some of the compounds from compound C270 to compound C329 were prepared according to the following methods:

According to the method and the raw material ratio given in Example 139, the CC coupling reaction was carried out, but the type of raw material was changed. In each example, the corresponding compound structure, the corresponding molecular formula, the yield of the prepared compound and the high The results of resolution mass spectrometry and elemental analysis are shown in Table 6 below.

Table 6

Note: The wavy line in Table 6 above indicates the position where the C-C bond is generated.

Example 152 Preparation of Compound 27

Preparation of Compound 23: In a 1L three-necked bottle, add 5-bromoacenaphthoquinone (26.1g, 0.1mol), 2,3-diamino-1,4-butanediol (14.4g, 0.12mol) and glacial acetic acid ( 300mL), warm to reflux, then keep the reaction in the air atmosphere for 18h, then drop to room temperature, then pour the reaction solution into 1000mL of deionized water, stir for 0.5h, then filter with suction, then select 500mL of deionized water The filter cake was rinsed, and then 150 mL of absolute ethanol was used to rinse the filter cake, and the filter cake was collected to obtain 32.8 g of compound 23. The calculated yield was 95.6%, and the MS (m / z) detection value was 342.1.

Preparation of compound 24: In a 500mL three-necked flask, add compound 23 (32.5g, 0.095mol), manganese dioxide (35g, 0.4mol) and 1,2-dichloroethane (300g), warm to reflux, and keep the reaction warm After 32h, the temperature was lowered to 25 ° C, suction filtration was performed again, the filtrate was collected, and the solvent was removed to obtain 22.4g of compound 24. The calculated yield was 70%, and the MS (m / z) detection value was 337.9.

Preparation of compound 25: In a 500 mL three-necked flask, add compound 24 (22.2 g, 0.066 mol) and tetrahydrofuran (120 g), then cool to 5 ° C, and then add hydroxylamine hydrochloride (11.2 g, 0.16 mol), sodium acetate (13.1 g , 0.16mol) dissolved in 140g deionized water, and then added dropwise to a three-necked bottle, control the temperature in the bottle to be less than 25 ℃, after 0.5 hours of dropwise addition, incubate at 20 ℃ for 3 hours, and then warm to 60 ℃, keep warm React for 1 hour, then cool to 25 ° C, slowly pour the reaction solution into 500 mL of deionized water, then stir for 1 h, then filter with suction, then rinse with deionized water to neutrality, collect the filter cake, and dry to obtain the compound 25 is 23g, the calculated yield is 94%, and the MS (m / z) detection value is 368.1.

Preparation of compound 26: In a 500mL three-necked flask, compound 25 (22.5g, 0.061mol) and tetrahydrofuran (150g) were added to cool the system to 15 ° C, and then N-chloro-butanediimide (NCS for short) ( 16g, 0.12mol) dissolved in 80g N, N-dimethylformamide (DMF), and then slowly dropped into a three-necked bottle, maintaining the reaction temperature at 25 ~ 28 ℃, the dropwise addition was completed in 2 hours (reaction initiated After vigorously exothermic), keep the reaction at 25 ℃ for 2 hours, stop the reaction, and use.

Preparation of compound 27: In a 500 mL three-necked flask, add thiourea (10 g, 0.133 mol), triethylamine (14 g, 0.133 mol) and tetrahydrofuran (55 g), start stirring, and then slowly add the compound 26 prepared in one step Keep the reaction temperature below 30 ° C. After 1 hour of dropwise addition, incubate at 25 ° C for 3 hours, then suction filter, collect the filter cake to obtain the crude product, and then use silica gel column chromatography to purify the crude product. The reagent was ethyl acetate, and the obtained compound 27 was 18.9 g. The calculated yield was 78%. The MS (m / z) detection value was 395.9.

Example 153 Preparation of Compound 28

According to the method and the raw material ratio given in Example 152, except that 5,6-dibromoacenaphthoquinone was used as the raw material, the prepared compound 28 was 8.2 g, and the MS (m / z) detection value was 475.8.

Example 154 Preparation of Compound C081

In a 100mL three-necked flask, add compound 27 (1.58g, 0.004mol), dyszole (0.83g, 0.005mol), CuI (0.19g, 0.001mol), o-phenanthroline (0.36g, 0.002mol), potassium carbonate (1.38g, 0.01mol) and o-dichlorobenzene (32g), the system was heated to 150 ℃, after holding the reaction for 32h, cooled to room temperature, then added 50mL of toluene, then washed the organic phase twice with 20mL deionized water, Then, separate the liquid, collect the organic phase, and then remove the solvent under reduced pressure to obtain the crude product. The crude product is purified by silica gel column chromatography, in which the eluent is a mixed solvent of ethyl acetate and dichloromethane, and the volume of ethyl acetate and dichloromethane The ratio is ethyl acetate: dichloromethane = 2: 1, to obtain compound C081, and then use a chemical vapor deposition system to further sublimate and purify compound C081, in which the sublimation temperature is 310 ℃, to obtain 0.9g compound C081, the calculated yield 47%.

After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound C081 is C28H13N5S2, the detection value is 483.0618, and the theoretical value is 483.0612; in addition, after elemental analysis of compound C081, it is detected that C: 69.54%, H: 2.72%, N: 14.44%, S: 13.30%, and the theoretical values are C: 69.55%, H: 2.71%, N: 14.48%, S: 13.26%.

Examples 155-Example 158 Preparation of some compounds from compound C089 to compound C283

Some of the compounds C089 ~ C283 were prepared according to the following methods:

According to the method and the ratio of raw materials given in Example 154, the CN coupling reaction was carried out, but the type of raw materials was changed. In each example, the corresponding compound structure, corresponding molecular formula, yield of compound preparation and high The results of resolution mass spectrometry and elemental analysis are shown in Table 7 below.

Table 7

Note: The wavy line in Table 7 above indicates the location where the C-N bond is generated.

Example 159 Preparation of Compound C093

In a 50 mL three-necked flask, add compound 27 (1.58 g, 0.004 mol), 4- (9H-oxazole) phenylboronic acid (1.44 g, 0.005 mol), potassium carbonate (1.1 g, 0.008 mol), and palladium acetate (0.022 g , 0.0001mol), triphenylphosphine (0.052g, 0.0002mol), toluene (28g) and deionized water (12g), after the system was heated to reflux, the reaction was incubated for 16h, then the temperature was lowered to 25 ℃, and the liquid was separated, The organic phase was collected, then filtered by suction, the filtrate was collected, and the solvent was removed. The crude product was purified by silica gel column chromatography, where the eluent was ethyl acetate, and then further sublimed and purified using a chemical vapor deposition system, where the sublimation temperature was 330 At ℃, 1.1 g of compound C093 was obtained with a calculated yield of 49%.

By high resolution mass spectrometry, ESI source, positive ion mode detection, the molecular formula of compound C093 is C34H17N5S2, the detected value is 559.0921, and the theoretical value is 559.0925; in addition, after elemental analysis, the compound C093 is detected as C: 72.99%, H: 3.07% , N: 12.49%, S: 11.45%, and the theoretical values are C: 72.97%, H: 3.06%, N: 12.51%, S: 11.46%.

Examples 160-Example 164 Compound C099- Preparation of some compounds in Compound C117

Some compounds from compound C099 to compound C117 were prepared according to the following methods:

The CC coupling reaction was carried out according to the method given in Example 159 and the ratio of raw materials, but the type of raw materials was changed. In each example, the corresponding compound structure, corresponding molecular formula, yield of compound preparation and high The results of resolution mass spectrometry and elemental analysis are shown in Table 8 below.

Table 8

Note: The wavy line in Table 8 above indicates the position where the C-C bond is generated.

It can be known from the data in Tables 1 to 8 above that the present invention has successfully obtained the provided organic photoelectric material, that is, the organic photoelectric material shown in Formula I.

Example 2 Preparation of an organic electroluminescent device (hereinafter may be referred to as a device)

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

Anode: Indium tin oxide (ITO) conductive glass, hole transport material: NPB,

Luminescent material: mCP, electron transport material: TPBI, electron injection material: LiF, where the structural formulas of NPB, mCP, and TPBI are mentioned in the foregoing, and will not be repeated here.

Example 165 ~ Example 231 Preparation of devices 165 ~ 231

Organic electroluminescent devices are prepared according to the following methods:

a) Cleaning the anode: ultrasonically clean the ITO conductive glass with deionized water, acetone, and ethanol respectively, ultrasonically clean for 30 minutes in the above solvent, and then treat in the plasma cleaner for 5 minutes;

b) Vacuum evaporation of the hole transport material NPB on the anode obtained in step a) to obtain a hole transport layer with a thickness of 50 nm;

c) On the hole-transporting layer obtained in step b), vacuum-depositing a light-emitting material including the compound prepared in the foregoing Example 1 and mCP to obtain a light-emitting layer with a thickness of 30 nm, wherein the compound: mCP = 1:10 (W / W);

d) On the light-emitting layer obtained in step c), the electron transport material TPBI is vacuum-evaporated to obtain an electron transport layer with a thickness of 30 nm;

e) On the electron transport layer obtained in step d), the electron injection material LiF is vacuum-evaporated to obtain an electron injection layer with a thickness of 1 nm;

f) On the electron injection layer obtained in step e), the cathode Al is vacuum-evaporated, and the thickness of the cathode is 100 nm to obtain an organic electroluminescent device.

In the above-mentioned preparation of the organic electroluminescent device, the pressure during vacuum evaporation is less than 1.0 × 10-3Pa.

The organic electroluminescent device prepared by the above preparation process, as shown in FIG. 1, includes an anode 101, a hole transport layer 102, a light-emitting layer 103, an electron transport layer 104, an electron injection layer 105, and a cathode 106. The hole transport layer 102, the light emitting layer 103, the electron transport layer 104, and the electron injection layer 105 are all located between the cathode 106 and the anode 101, and the hole transport layer 102, the light emitting layer 103, and the electron transport layer 104 are sequentially stacked on the anode 101和 电子 含 层 105。 The electron injection layer 105.

Test example

The SR3 spectroradiometer from Topcon Japan was used to perform the following tests on the organic electroluminescent devices prepared in the above examples to obtain the turn-on voltage, maximum current efficiency and spectral color in each organic electroluminescent device.

In the above test example, the turn-on voltage, maximum current efficiency, and spectral color obtained by detecting each organic electroluminescent device are shown in Table 9 below.

Table 9

From the results of Table 9 above, it can be known that the organic optoelectronic material provided by the present invention can be applied to organic electroluminescent devices. In addition, through the detection results of the devices prepared in the examples, it can also be known that the organic optoelectronic material provided by the present invention enables the organic electroluminescent device to obtain excellent performance. The use of light-emitting materials of the light-emitting device makes the device have a larger maximum current efficiency, and the device has a lower turn-on voltage, and at the same time, the device can emit different colors of visible light, and the spectral coverage is wider.

According to the disclosure of the above description, those skilled in the art to which the present invention belongs can also make appropriate changes and modifications to the above-mentioned embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and changes to the present invention should also fall within the protection scope of the claims of the present invention.

Claims (4)

An organic photoelectric material, which is represented by the following formula I:

Wherein R1 and R2 are each independently selected from one of hydrogen, cyano, isothiocyanato and phenyl, and R3, R4, R5, R6, R7 and R8 are each independently selected from hydrogen, halo and carbon One of the aromatic heterocyclic groups having 10 to 50 atoms and containing at least one of N, S and O; wherein one of R1 and R2, R3, R4, R5, R6, R7 and R8 is not hydrogen Wherein the halogen group is a fluorine group, a chlorine group, or a bromine group; wherein the R1 and R2 are the same; wherein the aromatic heterocyclic group is selected from the groups represented by the following formula (1) to formula (21) One or more of:

Wherein R9 and R10 are each independently selected from a hydrogen group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylamine group having 6 to 20 carbon atoms, and containing N and One of the fused heterocyclic groups having 12 to 20 carbon atoms, R11 is selected from a hydrogen group or an alkyl group having 1 to 10 carbon atoms, and L is selected from an arylene group having 6 to 20 carbon atoms, One of a halogenated arylene group having 6 to 20 carbon atoms and an arylene cyano group, M is selected from a group consisting of a hypoarylene group having 6 to 20 carbon atoms, a halogenated aryl group and a cyano group , Where the halogen atoms are F, Cl, Br. The organic optoelectronic material as described in item 1 of the patent application range, wherein R9 and R10 are each independently selected from alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 8 carbon atoms, and carbon atoms are 12 to 16 aromatic amine groups and N-containing fused heterocyclic groups having 12 to 16 carbon atoms; R11 is selected from alkyl groups having 1 to 6 carbon atoms; L is selected from carbon atoms having 6 to 12 carbon atoms One of an arylene group and a fluorinated arylene group having 6 to 12 carbon atoms; M is selected from a hypoarylene group having 6 to 12 carbon atoms. The organic optoelectronic material as described in item 1 of the patent application scope, wherein the R9 and R10 are each independently selected from one of the following groups: methyl, tert-butyl, phenyl, diphenylamino, and oxazolyl, R11 is selected from one of the following groups: methyl and tert-butyl, and L is selected from one of the following groups:

M is

. The organic optoelectronic material as described in item 1 of the patent application scope, wherein the R3, R4, R5, R6, R7 and R8 are each independently selected from one of the following fluorine groups and the following groups: