A heterocyclic compound containing selenium and its application

Abstract

The present invention provides a heterocyclic compound containing selenium and its application, belonging to the technical field of organic electroluminescent materials. The heterocyclic compound containing selenium has a structure of Formula I or Formula II. In the present invention, by designing a heterocyclic compound containing selenium and using such a heterocyclic compound containing selenium as a doping material for a light-emitting layer of an organic electroluminescent device, an OLED light-emitting device has a lower driving voltage, a higher current efficiency and a longer life.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic electroluminescent materials, and specifically relates to a heterocyclic compound containing selenium and application thereof, and more specifically relates to a heterocyclic compound containing selenium, an organic electroluminescent device and a display device. Background Art

[0002] Currently, organic electroluminescent (OLED) display technology has been applied in smart phones, tablet computers and other fields, and will be further expanded to large-size application fields such as televisions. In the past 30 years of development, people have developed a variety of OLED materials with excellent performance, and through different designs of device structures and optimization of device life, efficiency and other performance, the commercialization process of OLED has been accelerated, making OLED widely used in the display and lighting fields.

[0003] The selection of materials for the hole layer, light-emitting layer and other organic functional layers also has a significant impact on the current efficiency, driving voltage and life of the device. Currently, we are still exploring functional layer materials with higher performance.

[0004] Therefore, in order to meet people's higher requirements for OLED devices, the field is in urgent need of developing more types of OLED materials with higher performance. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention aims to provide a heterocyclic compound containing selenium and its application. In the present invention, the heterocyclic compound containing selenium is designed and used as a doping material for the light-emitting layer of an organic electroluminescent device, so that the OLED light-emitting device has a lower driving voltage, higher current efficiency and longer life.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a heterocyclic compound containing selenium, wherein the heterocyclic compound has a structure shown in Formula I or Formula II:

[0008] ;

[0009] Wherein, in the compounds of formula I and II, X is selected from O, S, or Any of the above, the dotted line indicates the connection site;

[0010] R 81 , R 82 are each independently selected from C1-C10 alkyl or C6-C15 aryl, and R 81 , R 82Can be connected into rings by single bonds;

[0011] R 83 Any one selected from C1-C10 alkyl, C6-C15 aryl or C6-C20 heteroaryl;

[0012] In the compounds of formula I and II, R1 to R 18 Each is independently selected from -H, -D, -F, -CN, C1-C10 alkyl, C1-C10 alkoxy, C6-C15 aryl, Any of the above, the dotted line indicates the connection site;

[0013] R 84 , R 85 are each independently selected from any one of C1-C10 alkyl, C6-C15 aryl or C6-C20 heteroaryl, and R 84 , R 85 Can be connected into rings by single bonds;

[0014] R1~R 18 When each is independently selected from C1-C10 alkyl, any two adjacent R1~R 18 They can be connected to form a ring through single bonds;

[0015] R1~R 18 When each is independently selected from C6-C15 aryl, the R1~R 17 Each of the benzene rings that can be connected to it independently can be connected to it through -O-, -S-, , Bridge, dotted lines indicate connection sites;

[0016] R 86 , R 87 are each independently selected from any one of C1-C10 alkyl, C6-C15 aryl or C6-C20 heteroaryl, and R 86 , R 87 Can be connected into rings by single bonds;

[0017] R 88 Any one selected from C1-C10 alkyl, C6-C15 aryl or C6-C20 heteroaryl;

[0018] The hydrogen atoms in the compound of formula I and the compound of formula II can each independently be substituted by -D, -F, -CN, C1-C10 alkyl, C6-C15 aryl or C6-C20 heteroaryl;

[0019] In the present invention, C1-C10 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10.

[0020] C6-C15 can be C6, C7, C8, C10, C12 or C15, etc.

[0021] C6-C20 can be C6, C7, C8, C10, C12, C15, C18 or C20, etc.

[0022] It should also be noted that, in the present invention, "-D" represents a deuterium atom, and the same applies hereinafter.

[0023] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0024] As a preferred technical solution of the present invention, the C1-C10 alkyl group is selected from any one of a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group or a cyclohexyl group.

[0025] Preferably, the C6-C15 aryl group is selected from any one of phenyl, naphthyl or biphenyl.

[0026] Preferably, the C6-C20 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothienyl, naphthobenzofuranyl, naphthobenzothienyl or carbazolyl.

[0027] Preferably, the C1-C10 alkoxy group is selected from any one of methoxy, ethoxy, propoxy or butoxy.

[0028] As a preferred technical solution of the present invention, the R 81 , R 82 Each is independently selected from any one of methyl, ethyl, propyl, butyl, phenyl, biphenyl or naphthyl.

[0029] Preferably, the R 83 At least one selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, naphthobenzofuranyl, and naphthobenzothienyl.

[0030] Preferably, the R 84 , R 85 Each is independently selected from any one of methyl, ethyl, propyl, tert-butyl, phenyl, naphthyl, biphenyl, dibenzofuranyl and dibenzothiophenyl.

[0031] Preferably, the R 86 , R 87 Each is independently selected from any one of methyl, ethyl, propyl, butyl, phenyl, biphenyl or naphthyl.

[0032] Preferably, the R 88At least one selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl, naphthyl, biphenyl, dibenzofuranyl, dibenzothienyl, naphthobenzofuranyl, and naphthobenzothienyl.

[0033] As a preferred technical solution of the present invention, the X is selected from O, S, or The dotted line indicates the connection site.

[0034] Preferably, in the compounds of formula I and formula II, R1 to R 18 Each is independently selected from -H, methyl, ethyl, propyl, tert-butyl, cyclohexyl, methoxy, ethoxy, or The dotted line indicates the connection site.

[0035] Preferably, the hydrogen atoms in the compound of formula I or formula II can be independently substituted by any one of -D, -F, -CN, methyl, ethyl, propyl, tert-butyl or phenyl.

[0036] As a preferred technical solution of the present invention, the heterocyclic compound containing selenium has a structure shown in the following formula I-1, formula I-2, formula II-1 or formula II-2:

[0037] ;

[0038] Among them, X, R1~R 18 Has the same definition as above.

[0039] As a preferred technical solution of the present invention, the heterocyclic compound containing selenium has a structure shown in the following formula I-1A, formula I-2A, formula II-1A or formula II-2A:

[0040] ;

[0041] In the compounds of formula I-1A and I-2A, R3, R7, R 12 , R 16 , R 17 Each is independently selected from -H, methyl, ethyl, propyl, tert-butyl, cyclohexyl, methoxy, ethoxy, or Any one of R 16 , R 17 They can be connected by single bonds, and the dotted lines indicate the connection sites;

[0042] In the compound of formula II-1A and the compound of formula II-2A, R2, R7, R 12 , R 16 , R 17 Each is independently selected from -H, methyl, ethyl, propyl, tert-butyl, cyclohexyl, methoxy, ethoxy, or Any one of R 16 , R 17 They can be connected by a single bond, and the dotted line indicates the connection site.

[0043] As a preferred technical solution of the present invention, the heterocyclic compound containing selenium is selected from any one of the following substituted or unsubstituted compounds:

[0044] ;

[0045] The substitution means that the hydrogen atoms in the above-mentioned heterocyclic compound containing selenium can be substituted by deuterium atoms independently.

[0046] Preferably, the heterocyclic compound containing selenium is selected from any one of the following compounds:

[0047] , , , , , , , , .

[0048] It should also be noted that there is no special limitation on the preparation method of the heterocyclic compound containing selenium in the present invention, and the heterocyclic compound containing selenium can be prepared by conventional methods in the art.

[0049] In a second aspect, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode and an organic thin film layer disposed between the anode and the cathode;

[0050] The material of the organic thin film layer includes the heterocyclic compound containing selenium as described in the first aspect.

[0051] Preferably, the organic thin film layer includes a light-emitting layer;

[0052] The doping material of the light-emitting layer includes the heterocyclic compound containing selenium as described in the first aspect.

[0053] As a preferred technical solution of the present invention, the organic electroluminescent device is a blue light organic electroluminescent device.

[0054] In a third aspect, the present invention provides a display device, comprising the organic electroluminescent device as described in the second aspect.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] In the present invention, a heterocyclic compound containing selenium is designed and used as a doping material for a light-emitting layer of an organic electroluminescent device, so that the OLED light-emitting device has a lower driving voltage, a higher current efficiency and a longer lifespan. DETAILED DESCRIPTION

[0057] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0058] Synthesis Example 1

[0059] This synthesis example provides compound 3 and its synthesis method, and the synthesis method is as follows:

[0060]

[0061] (1) Synthesis of intermediate 3-1

[0062] Under nitrogen protection, add 40 mL of dry toluene, 0.01 mol 3-bromo-5-chloroiodobenzene, 0.01 mol diphenylamine, 0.0001 mol Pd(dba)2 (bis(dibenzylideneacetonepalladium), 0.4 g of 10% tri-tert-butylphosphine toluene solution (the amount of tri-tert-butylphosphine is 0.0002 mol) and 0.03 mol sodium tert-butoxide to a 100 mL three-necked flask, heat to reflux reaction for 12 h, cool to room temperature, add water to separate, then wash the organic layer with water until neutral, dry with magnesium sulfate, filter to remove magnesium sulfate, concentrate to dryness, and crystallize with ethanol to obtain intermediate 3-1;

[0063] The intermediate 3-1 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 357.

[0064] (2) Synthesis of intermediate 3-2

[0065] Referring to the synthesis method of the intermediate 3-1, the deuterated m-bromoiodobenzene is replaced with an equal amount of the intermediate 3-1, and the diphenylamine is replaced with an equal amount of N-phenylbenzo[b]thiophene-3-amine, and other conditions remain unchanged to obtain the intermediate 3-2;

[0066] The intermediate 3-2 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 502.1.

[0067] (3) Synthesis of intermediate 3-3

[0068] Under nitrogen protection and oil bath heating, add 200 mL of dry o-dichlorobenzene, 0.01 mol intermediate 3-2, and then add 0.006 mol of anhydrous nickel chloride into a 500 mL three-necked flask, stir evenly, maintain the temperature at 20℃-25℃, slowly drop 20 mL of 1.0 M BBr3 dichloromethane solution (containing BBr30.02mol), slowly heat to oil bath temperature 40℃ after addition, react for 2 h, then slowly heat to oil bath 100℃, distill out dichloromethane in the reaction system during the process, then maintain the oil bath at 100℃ for 4 h, then heat to oil bath 140℃ for 12 h, then cool to room temperature, slowly add 0.05 mol The reaction was terminated by N-ethyldiisopropylamine; water was then added to separate the organic layer, the organic layer was washed with water until neutral, dried over magnesium sulfate, filtered to remove the magnesium sulfate, concentrated to dryness, and separated by silica gel column chromatography, eluted with petroleum ether: ethyl acetate = 20: 0.5 (volume ratio) to obtain intermediate 3-3.

[0069] The obtained intermediate 3-3 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 510.1.

[0070] (4) Synthesis of compound 3

[0071] Under nitrogen protection, 40 mL of dry toluene, 0.01 mol of intermediate 3-3, 0.012 mol of 10H-phenoselenazine, 0.0001 mol of palladium acetate, 0.00012 mol of 2-dicyclohexylphosphine-2',6'-diisopropoxy-1,1'-biphenyl and 0.03 mol of sodium tert-butoxide were added to a 100 mL three-necked flask, and the mixture was kept at 110°C for 12 h, cooled to room temperature, and water was added to separate the organic layer. The organic layer was then washed with water until neutral, dried with magnesium sulfate, filtered to remove the magnesium sulfate, concentrated to dryness, and recrystallized from toluene to obtain compound 3.

[0072] The obtained compound 3 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 721.1.

[0073] Synthesis Example 2

[0074] This synthesis example provides compound 4 and its synthesis method, and the synthesis method is as follows:

[0075]

[0076] Referring to the synthesis method of compound 3 provided in Synthesis Example 1, N-phenylbenzo[b]thiophene-3-amine was replaced with an equal amount of N-phenylbenzo[b]thiophene-2-amine, and other conditions remained unchanged to obtain compound 4.

[0077] The obtained compound 4 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 721.1.

[0078] Synthesis Example 3

[0079] This synthesis example provides a synthesis method of compound 51, and the synthesis method is as follows:

[0080]

[0081] Referring to the synthesis method of Synthesis Example 1, diphenylamine was replaced with an equal amount of compound amine-1, and other conditions remained unchanged to obtain compound 51.

[0082] The obtained compound 51 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 888.2.

[0083] Synthesis Example 4

[0084] This synthesis example provides a synthesis method of compound 52, and the synthesis method is as follows:

[0085]

[0086] Referring to the synthesis method of Synthesis Example 2, diphenylamine was replaced with an equal amount of compound amine-1, and other conditions remained unchanged to obtain compound 52.

[0087] The obtained compound 52 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 888.2.

[0088] Synthesis Example 5

[0089] This synthesis example provides a synthesis method of compound 89, which is as follows:

[0090]

[0091] Referring to the synthesis method of Synthesis Example 1, diphenylamine was replaced by an equal amount of compound amine-2, and N-phenylbenzo[b]thiophene-3-amine was replaced by an equal amount of compound amine-3, while other conditions remained unchanged, to obtain Compound 89.

[0092] The obtained compound 89 was subjected to mass spectrometry detection: the mass-to-charge ratio (m / z) was measured to be 983.5.

[0093] Other compounds for which specific synthesis steps are not listed can be prepared by common knowledge in the art in combination with conventional means in the art and the above synthesis examples.

[0094] The specific structures of the compounds used in the device examples and device comparative examples are shown below:

[0095] , , , , , .

[0096] The compound provided by the present invention is selected as the doping material of the light-emitting layer in the device example, and BD-1 and BD-2 are selected as the doping materials of the light-emitting layer in the device comparison example.

[0097] Device Example 1

[0098] The device embodiment provides an organic electroluminescent device and a preparation method thereof. The structure of the organic electroluminescent device is: ITO / HIL02 (100nm) / HT (40nm) / BH (30nm): doping material 2% / TPBI (30nm) / LiF (0.5nm) / Al (150nm).

[0099] The preparation process of organic electroluminescent device is as follows:

[0100] The glass substrate coated with the ITO transparent conductive layer (as the anode) is ultrasonically treated in a cleaning agent, then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol, baked in a clean environment until the water is completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam to improve the properties of the surface and enhance the binding ability with the hole injection layer;

[0101] The glass substrate was placed in a vacuum chamber and evacuated to 5×10 -6 ~1×10 -5 Pa, vacuum evaporate HIL02 on the anode as a hole injection layer, the evaporation rate is 0.1 nm / s, and the evaporation film thickness is 100 nm;

[0102] HT was vacuum evaporated on the hole injection layer as a hole transport layer, with an evaporation rate of 0.1 nm / s and an evaporation film thickness of 40 nm;

[0103] A light-emitting layer is vacuum-deposited on the hole transport layer, the deposition rate is 0.1 nm / s, the total deposition film thickness is 30 nm, the main material of the light-emitting layer is BH, and the doping material is the compound provided by the present invention, 2% refers to the doping ratio of the doping material, that is, the volume ratio of the main material of the light-emitting layer to the doping material is 98:2.

[0104] TPBI was vacuum-deposited on the organic light-emitting layer as the electron transport layer of the organic electroluminescent device; the evaporation rate was 0.1 nm / s, and the total film thickness of the evaporation was 30 nm;

[0105] 0.5 m LiF and 150 nm Al were vacuum evaporated on the electron transport layer as the electron injection layer and cathode, respectively.

[0106] Device Examples 2-10

[0107] Device Examples 2-10 respectively provide an organic electroluminescent device, which differs from Device Example 1 only in that the doping materials of the light-emitting layer are different (see Table 1 below for details), and the other preparation steps and conditions are the same as those of Device Example 1.

[0108] Device Comparison Example 1-2

[0109] Device Comparative Examples 1-2 respectively provide an organic electroluminescent device, which differs from Device Example 1 only in that the doping materials of the light-emitting layer are different (see Table 1 below for details), and the other preparation steps and conditions are the same as those of Device Example 1.

[0110] Performance Test:

[0111] The brightness, driving voltage, current efficiency and life test LT90 of the prepared organic electroluminescent device were tested. The life test LT90 refers to the current density at room temperature (25~27℃) at the initial brightness (here 1000cd / m 2 ), the time required for the brightness to decrease to 90% of the initial brightness. In the following table, the driving voltage, efficiency, and LT90 life are all relative values ​​(with BD-1 as the comparison benchmark). The test results are detailed in Table 1 below.

[0112] Table 1

[0113]

[0114] It can be seen from the data in Table 1 that the voltage, efficiency and life of the organic electroluminescent device prepared by using the compound provided by the present invention are better than those of the device control example.

[0115] In summary, the present invention designs a heterocyclic compound containing selenium and uses the compound as a doping material for the light-emitting layer of an organic electroluminescent device, so that the OLED light-emitting device has a lower driving voltage, a higher current efficiency and a longer life.

[0116] The applicant declares that the present invention illustrates the detailed process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process flow to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A heterocyclic compound containing selenium, characterized in that The selenium-containing heterocyclic compound has a structure shown in the following formula I-1A, formula I-2A, formula II-1A or formula II-2A: ； In the compounds of formula I-1A and I-2A, R3, R7, R 12 , R 16 , R 17 Each is independently selected from -H, methyl, ethyl, propyl, tert-butyl, or Any of the above, the dotted line indicates the connection site, when R 16 , R 17 When R is methyl, ethyl, propyl or tert-butyl, 16 , R 17 They can be connected via a single key; In the compound of formula II-1A and the compound of formula II-2A, R2, R7, R 12 , R 16 , R 17 Each is independently selected from -H, methyl, ethyl, propyl, tert-butyl, or Any of the above, the dotted line indicates the connection site, when R 16 , R 17 When R is methyl, ethyl, propyl or tert-butyl, 16 , R 17 They can be connected via a single key; The hydrogen atoms in the compounds of formula I-1A, formula I-2A, formula II-1A or formula II-2A may each independently be replaced by deuterium.

2. The selenium-containing heterocyclic compound according to claim 1, characterized in that The selenium-containing heterocyclic compound is selected from any one of the following substituted or unsubstituted compounds: ； ； ； ； ； The substitution means that the hydrogen atoms in the above-mentioned heterocyclic compound containing selenium can be substituted by deuterium atoms independently.

3. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode, a cathode and an organic thin film layer arranged between the anode and the cathode; The material of the organic thin film layer includes the heterocyclic compound containing selenium as claimed in claim 1 or 2.

4. The organic electroluminescent device according to claim 3, characterized in that: The organic thin film layer includes a light-emitting layer; The doping material of the light-emitting layer includes the heterocyclic compound containing selenium as claimed in claim 1 or 2.

5. The organic electroluminescent device according to claim 3, characterized in that: The organic electroluminescent device is a blue light organic electroluminescent device.

6. A display device, characterized in that: The display device comprises the organic electroluminescent device according to any one of claims 3 to 5.

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