Silicon-containing compounds and uses thereof

Abstract

The application provides a silicon-containing compound and application thereof, and the silicon-containing compound has a structure shown in formula I. The silicon-containing compound has good light emitting performance, can be used for preparing an organic electroluminescent device, and especially can be used as an electron transport layer material in the organic electroluminescent device, so that the current efficiency of the organic electroluminescent device can be effectively improved, and the service life of the organic electroluminescent device can be improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic optoelectronic materials, and particularly relates to a silicon-containing compound and application thereof. BACKGROUND

[0002] Organic Light-Emitting Diode (OLED) has the advantages of light weight, small volume, wide viewing angle, fast response, wide temperature range, low energy consumption, high efficiency, good color purity, high definition, good flexibility, etc., and can meet the new needs of consumers for display technology, and has good application prospects in the fields of lighting and display.

[0003] An organic electroluminescent element is a self-light-emitting element that utilizes the following principle: by applying an electric field, a fluorescent substance is made to emit light using recombination energy of holes injected from an anode and electrons injected from a cathode. It has the following structure: an anode, a cathode, and an organic material layer interposed therebetween. In order to improve the efficiency and stability of the organic electroluminescent element, the organic material layer usually includes multiple layers having different materials, such as a hole injection layer HIL, a hole transport layer HTL, a light-emitting layer, an electron transport layer ETL, and an electron injection layer EIL. In such an organic light-emitting element, when a voltage is applied between the anode and the cathode, holes from the anode and electrons from the cathode are injected into the organic material layer, and the generated excitons produce light having a specific wavelength when migrating to the ground state. The hole transport layer can change the hole transport efficiency of holes to the light-emitting layer, the light-emitting efficiency, the lifetime, and the like.

[0004] At present, the research on organic electroluminescent materials has been widely carried out in academia and industry. Designing and finding a compound as a new type of OLED material to overcome the deficiencies in the practical application process is the focus and future research and development trend of OLED material research work. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a silicon-containing compound and application thereof,

[0006] To achieve this purpose, the present application adopts the following technical solutions:

[0007] On the one hand, the present application provides a silicon-containing compound, which has the following structure shown in formula I:

[0008]

[0009] wherein, R1, R2 are independently selected from any one or a combination of at least two of C1-C12 alkyl, C1-C12 alkoxy, C6-C30 aryl or C3-C30 heteroaryl;

[0010] L1 is selected from any one of C6-C30 arylene or C3-C30 heteroarylene;

[0011] n is selected from an integer of 0-1.

[0012] In the present application, the C1-C12 alkyl group is selected from methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, tert-pentyl, n-hexyl, cyclohexyl, and the like.

[0013] In the present application, the C1-C12 alkoxy group is selected from methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, and the like.

[0014] The C6-C30 aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, anthryl, indenyl fluorenyl, perylenyl, phenanthryl, pyrenyl, fluoranthene, or triphenylene, and the like.

[0015] The C6-C30 arylene group is selected from phenylene, biphenylene, terphenylene, naphthylene, anthrylene, indenylene, fluorenylene, perylenylene, phenanthrylene, pyrenylene, fluoranthene, or triphenylylene, and the like.

[0016] The heteroatom in the C3-C30 heteroaryl group is oxygen, sulfur, and nitrogen atom.

[0017] The C3-C30 heteroaryl group is selected from benzofuran, benzothiophene, pyridine, dibenzofuran, pyrimidine, dibenzothiophene, carbazole, diarylamino, benzofuran carbazole, benzofuran thiophene, or triazine, and the like.

[0018] The C3-C30 heteroaryl group is selected from benzofuran, benzothiophene, pyridine, dibenzofuran, pyrimidine, dibenzothiophene, carbazole, diarylamino, benzofuran carbazole, benzofuran thiophene, or triazine, and the like.

[0019] The following is a preferred technical solution of the present application, but not as a limitation on the technical solutions provided by the present application, through the following preferred technical solution, the purpose and beneficial effects of the present application can be better achieved and realized.

[0020] As a preferred technical solution of the present application, the silicon-containing compound includes any one of the following compounds:

[0021]

[0022]

[0023] Preferably, the compound represented by formula I is selected from any one of compounds 1-12:

[0024]

[0025] The present application lists some specific structural forms of the silicon-containing compound, but the silicon-containing compound of the present application is not limited to the listed chemical structures, and any structure based on the structure shown in formula I, R1, R2, L1 satisfying the above defined conditions should be included.

[0026] In a second aspect, the present application provides an organic electroluminescent device comprising the silicon-containing compound according to the first aspect.

[0027] Preferably, the organic electroluminescent device comprises a first electrode, a second electrode and an organic layer disposed between the first electrode and the second electrode; the material of the organic layer comprises the silicon-containing compound according to the first aspect.

[0028] Preferably, the organic layer comprises an electron transport layer; the material of the electron transport layer comprises the silicon-containing compound according to the first aspect.

[0029] In a third aspect, the present application provides a display device comprising the organic electroluminescent device according to the second aspect.

[0030] Compared with the prior art, the present application has the following beneficial effects:

[0031] The silicon-containing compound obtained by designing the structure of the silicon-containing compound can effectively improve the current efficiency of the organic electroluminescent device and prolong the service life of the organic electroluminescent device as the electron transport layer material in the organic electroluminescent device. DETAILED DESCRIPTION

[0032] The technical solutions of the present application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.

[0033] Synthesis Example 1

[0034] This embodiment provides a synthesis method of compound 1, which is as follows:

[0035]

[0036] (1) Synthesis of intermediate 1-a

[0037] Into a flask, 2-bromo-9-(4-chlorophenyl)-9-phenyl-9H-fluorene (100 mmol), 2-nitrophenylboronic acid pinacol ester (100 mmol), tetrakis(triphenylphosphine)palladium (1 mmol), potassium carbonate (120 mmol), water 50 mL, dioxane 300 mL, reflux for 4 h under nitrogen protection. After the reaction is completed, cool down, add toluene to separate, wash with water, and dry the organic layer. The obtained solid is recrystallized with a mixed solvent of toluene and ethanol to obtain intermediate 1-a.

[0038] The mass spectrometry data of intermediate 1-a is tested, and the mass spectrometry m / z is 473.12.

[0039] (2) Synthesis of intermediate 1-b

[0040] Into a flask, intermediate 1-a (40 mmol), (triphenylsilyl)boronic acid (40 mmol), dichlorobis-(4-dimethylaminophenyl) palladium (II) (0.4 mmol), potassium carbonate (60 mmol), toluene 300 mL, heat to reflux for 8 h. TLC is used to monitor the completion of the reaction. After filtration with diatomite, water is added to wash to neutral. The organic phase is concentrated, and the obtained solid is recrystallized with a mixed solvent of toluene and ethanol to obtain intermediate 1-b.

[0041] The mass spectrometry data of intermediate 1-b is tested, and the mass spectrometry m / z is 697.24.

[0042] (3) Synthesis of intermediate 1-c

[0043] Into a flask, intermediate 1-b (50 mmol), triphenylphosphine (100 mmol), o-dichlorobenzene 150 mL, reflux for 6 h under nitrogen protection. After the reaction is completed, o-dichlorobenzene is directly distilled off. The residue is dissolved with toluene, purified by column chromatography, and the obtained solid is recrystallized with a mixed solvent of toluene and ethanol to obtain 1-c.

[0044] The mass spectrometry data of intermediate 1-c is tested, and the mass spectrometry m / z is 665.25.

[0045] (4) Synthesis of compound 1

[0046] Into a flask, intermediate 1-c (30 mmol), 2-bromo-4,6-diphenyl-1,3,5-triazine (30 mmol), cesium carbonate (60 mmol), DMF (300 mL), heat to reflux for 12 h. TLC is used to monitor the completion of the reaction. The reaction liquid is poured into water, and the obtained solid is filtered. After washing with ethanol, toluene is used for recrystallization to obtain compound 1.

[0047] The mass spectrometry data of compound 1 was tested, and the mass spectrometry m / z was 896.33.

[0048] Synthesis Example 2

[0049] Synthesis of compound 4:

[0050]

[0051] (1) Synthesis of intermediate 4-a

[0052] 4-bromo-9-(3-chlorophenyl)9-phenyl-9H-fluorene (100 mmol), 2-nitrophenylboronic acid pinacol ester (100 mmol), tetrakis(triphenylphosphine)palladium 1 mmol, potassium carbonate (120 mmol), water 50 mL, dioxane 300 mL, were added to a reaction bottle, and refluxed under nitrogen protection for 4 h. After the reaction was completed, toluene was added for liquid separation, and the organic layer was washed with water and dried. The obtained solid was recrystallized with a mixed solvent of toluene and ethanol to obtain intermediate 4-a.

[0053] The mass spectrometry data of intermediate 4-a was tested, and the mass spectrometry m / z was 473.12.

[0054] (2) Synthesis of intermediate 4-b

[0055] Intermediate 4-a (40 mmol), (triphenylsilyl)boric acid (40 mmol), dichlorobis-(4-dimethylaminophenyl) palladium (II) (0.4 mmol), potassium carbonate (60 mmol), toluene 300 mL, were added to a reaction bottle and heated to reflux for 8 h. The reaction was monitored by TLC, and after filtration with diatomite, pure water was added for washing until neutral. The organic phase was concentrated, and the obtained solid was recrystallized with a mixed solvent of toluene and ethanol to obtain intermediate 4-b.

[0056] The mass spectrometry data of intermediate 4-b was tested, and the mass spectrometry m / z was 697.24.

[0057] (3) Synthesis of intermediate 4-c

[0058] Intermediate 4-b (50 mmol), triphenylphosphine (100 mmol), o-dichlorobenzene 150 mL were added to a reaction bottle, and refluxed under nitrogen protection for 6 h. After the reaction was completed, o-dichlorobenzene was directly distilled off, and the residue was dissolved with toluene and purified by column chromatography. After the column liquid was dried and concentrated, the obtained solid was recrystallized with a mixed solvent of toluene and ethanol to obtain 4-c.

[0059] The mass spectrometry data of intermediate 4-c was tested, and the mass spectrometry m / z was 665.25.

[0060] (4) Synthesis of compound 4

[0061] Intermediate 4-c (30 mmol), 2-bromo-4,6-diphenyl-1,3,5-triazine (30 mmol), cesium carbonate (60 mmol), DMF (300 mL) were added into a reaction flask, heated to reflux for 12 h, TLC monitored the completion of the reaction, the reaction liquid was poured into water and filtered, the filter cake was washed with ethanol and recrystallized from toluene to obtain compound 4.

[0062] The mass spectrometry data of compound 4 was tested, and the mass spectrometry m / z was 896.33.

[0063] Synthesis Example 3

[0064] Synthesis of compound 6:

[0065]

[0066] Referring to the synthesis method of compound 1, 2-bromo-4-(dibenzofuran-4-yl)-6-phenyl-1,3,5-triazine was used to replace 2-bromo-4,6-diphenyl-1,3,5-triazine in synthesis example 1, and compound 6 could be obtained under the same conditions.

[0067] The mass spectrometry data of compound 6 was tested, and the mass spectrometry m / z was 986.34.

[0068] Synthesis Example 4

[0069] Synthesis of compound 9:

[0070]

[0071] Referring to the synthesis method of compound 1, 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine was used to replace 2-bromo-4,6-diphenyl-1,3,5-triazine in synthesis example 1, and compound 9 could be obtained under the same conditions.

[0072] The mass spectrometry data of compound 9 was tested, and the mass spectrometry m / z was 972.36.

[0073] Synthesis Example 5

[0074] Synthesis of compound 10:

[0075]

[0076] Referring to the synthesis method of compound 1, 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine was used to replace 2-bromo-4,6-diphenyl-1,3,5-triazine in synthesis example 1, and compound 10 could be obtained under the same conditions.

[0077] The mass spectrometry data of compound 10 were tested, and the mass spectrum m / z was measured to be 972.36.

[0078] Synthesis example 6

[0079] Synthesis of compound 11:

[0080]

[0081] Following the synthetic method of compound 1, compound 11 was obtained by replacing 2-bromo-4,6-diphenyl-1,3,5-triazine in synthetic example 1 with 2-[4-(4-bromophenyl)phenyl]-4,6-diphenyl-1,3,5-triazine, while keeping other conditions unchanged.

[0082] The mass spectrometry data of compound 11 were tested, and the mass spectrum m / z was measured to be 1048.40.

[0083] Synthesis Example 7

[0084] Synthesis of compound 12:

[0085]

[0086] Following the synthetic method of compound 1, compound 12 was obtained by replacing 2-bromo-4,6-diphenyl-1,3,5-triazine in synthetic example 1 with 2-(6-bromonaphth-2-yl)-4,6-diphenyl-1,3,5-triazine, while keeping other conditions unchanged.

[0087] The mass spectrometry data of compound 12 were tested, and the mass spectrum m / z was measured to be 1022.38.

[0088] Other compounds for which specific synthesis steps are not listed can be prepared using common knowledge in the art, in conjunction with the above examples.

[0089] Device Example 1

[0090] The examples selected compounds of this application as electron transport materials in organic electroluminescent devices, while the comparative examples selected E1 to E3 as electron transport materials in organic electroluminescent devices.

[0091] The structure of the organic electroluminescent device is: ITO / NPB (40nm) / EM1 (30nm) / electron transport material (30nm) / LiF (0.5nm) / Al (150nm).

[0092] The fabrication process of organic electroluminescent devices is as follows:

[0093] The glass substrate coated with ITO transparent conductive layer (as an anode) is subjected to ultrasonic treatment in a cleaning agent, then washed in deionized water, then subjected to ultrasonic oil removal in a mixed solvent of acetone and ethanol, then baked to complete water removal in a clean environment, washed with ultraviolet light and ozone, and the surface is bombarded with a low-energy cation beam to improve the surface properties and improve the binding ability with the hole injection layer;

[0094] The above glass substrate is placed in a vacuum chamber, vacuumed to 1 x 10 -6 ~ 9 x 10 -5 Pa, and NPB is vacuum evaporated on the anode as a hole transport layer, with an evaporation rate of 0.1 nm / s and a total film thickness of 40 nm;

[0095] EM1 is vacuum evaporated on the hole transport layer as an organic light-emitting layer of the device, with an evaporation rate of 0.1 nm / s and a total film thickness of 30 nm;

[0096] The comparative compound and the compound of the present application are vacuum evaporated on the organic light-emitting layer as an electron transport layer of the organic electroluminescent device, respectively, with an evaporation rate of 0.1 nm / s and a total film thickness of 30 nm;

[0097] 0.5 nm of LiF and 150 nm of Al are vacuum evaporated on the electron transport layer as an electron injection layer and cathode.

[0098] The material structure used in the device is as follows:

[0099]

[0100] The brightness, driving voltage, current efficiency, and lifetime test LT90 of the prepared organic electroluminescent device are measured.

[0101] Device Examples 2-7

[0102] Device Examples 2-7 each provide an organic electroluminescent device, which differs from Device Example 1 only in that the electron transport material is different (see Table 1 below for details), and other conditions are the same as those of Device Example 1.

[0103] Device Comparative Examples 1-3

[0104] Device Comparative Examples 1-3 each provide an organic electroluminescent device, which differs from Device Example 1 only in that the electron transport material is different (see Table 1 below for details), and other conditions are the same as those of Device Example 1.

[0105] Performance Test

[0106] Test method: test the driving voltage, current efficiency and lifetime LT90 of the OLED device provided above; wherein, LT90 refers to the time required for the luminance to drop to 90% of the original luminance while keeping the current density unchanged at the initial luminance of 1000 nit, and the test items include the luminance, driving voltage, current efficiency of the organic electroluminescent device, the driving voltage and current efficiency, and LT90 data are all relative values (based on the comparative example E1) when the luminance is 1000 cd / m 2 The performance test results of the organic electroluminescent device are shown in Table 1 below.

[0107] Table 1

[0108] Electron transport material Requesting luminance cd / m 2 ]] Current efficiency cd / A LT90 / h Device comparative example 1 E1 1000 1 1 Device comparative example 2 E2 1000 0.97 0.99 Device comparative example 3 E3 1000 1.03 0.98 Device example 1 1 1000 1.31 1.59 Device example 2 4 1000 1.14 2.87 Device example 3 6 1000 1.17 2.97 Device example 4 9 1000 1.09 2.58 Device example 5 10 1000 1.22 2.17 Device example 6 11 1000 1.28 1.32 Device example 7 12 1000 1.18 1.45

[0109] From the content of Table 1, it can be seen that the silicon-containing compound is obtained by molecular design. The silicon-containing compound provided by the present application can be used as an electron transport material of an OLED light-emitting device, so that the OLED light-emitting device has high current efficiency and long service life.

[0110] The applicant declares that the silicon-containing compound and its application of the present application are illustrated by the above examples, but the present application is not limited to the above examples, that is, it does not mean that the present application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A silicon-containing compound characterized in that, The silicon-containing compound has a structure shown in Formula I: Formula I wherein R1, R2 are independently selected from any one or a combination of at least two of C6-C30 aryl or C3-C30 heteroaryl; L1 is selected from any one of C6-C30 arylene or C3-C30 heteroarylene; n is selected from an integer of 0-1.

2. The silicon-containing compound of claim 1, wherein The C6-C30 aryl is selected from phenyl, biphenyl, terphenyl, naphthyl, anthryl, indenyl fluorenyl, perylenyl, phenanthryl, pyrenyl, fluoranthene, or triphenylene.

3. The silicon-containing compound of claim 1, wherein The C6-C30 arylene is selected from phenylene, biphenylene, terphenylene, naphthylene, anthrylene, indenylene, fluorenylene, perylenylene, phenanthrylene, pyrenylene, fluoranthene, or triphenylylene.

4. The silicon-containing compound of claim 1, wherein The heteroatom in the C3-C30 heteroaryl is oxygen, sulfur, and nitrogen atom.

5. The silicon-containing compound of claim 1, wherein The C3-C30 heteroaryl is selected from benzofuran, benzothiophene, pyridine, dibenzofuran, pyrimidine, dibenzothiophene, carbazole, diarylamino, benzofuran carbazole, benzofuran thiophene, or triazine.

6. The silicon-containing compound of claim 1, wherein The C3-C30 heteroaryl is selected from benzofuran, benzothiophene, pyridine, dibenzofuran, pyrimidine, dibenzothiophene, carbazole, diarylamino, benzofuran carbazole, benzofuran thiophene, or triazine.

7. The silicon-containing compound of claim 1, wherein The silicon-containing compound includes any one of the following compounds: 。 8. The silicon-containing compound of claim 1, wherein The silicon-containing compound is selected from any one of compounds 1-12: 。 9. An organic electroluminescent device, characterized by The organic electroluminescent device includes the silicon-containing compound of any one of claims 1-8.

10. The organic electroluminescent device according to claim 9, characterized in that, The organic electroluminescent device includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode; the material of the organic layer includes the silicon-containing compound of any one of claims 1-8.

11. The organic electroluminescent device according to claim 10, characterized in that The organic layer includes an electron transport layer; the material of the electron transport layer includes the silicon-containing compound of any one of claims 1-8.

12. A display device, characterized by comprising: The display device includes the organic electroluminescent device of any one of claims 9-11.

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