Dibenzofuranfuran compound, application thereof and luminescent device

Abstract

The invention belongs to the technical field of organic photoelectric materials, and relates to a dibenzofuranfuran compound, application thereof and a light-emitting device. The invention provides a dibenzofuranfuran compound, the dibenzofuranfuran compound has a structure as shown in formula I. The dibenzofuranfuran compound provided by the invention has excellent transmission performance and luminescence performance, and when the dibenzofuranfuran compound is used as a luminescent layer material, especially a blue light luminescent layer material, the transmission performance of the dibenzofuranfuran compound is greatly improved. The driving voltage of the organic light-emitting device can be reduced, the efficiency of the device is improved, and the service life of the device is prolonged.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic optoelectronic materials, and relates to dibenzofuranfuran compounds and their applications, and light-emitting devices. More specifically, the present invention relates to dibenzofuranfuran compounds suitable for organic electroluminescent devices (especially blue light organic electroluminescent devices) and light-emitting devices using the dibenzofuranfuran compounds. Background Art

[0002] As a new type of display technology, organic electroluminescent devices have unique advantages such as self-luminescence, wide viewing angle, low energy consumption, high efficiency, thinness, rich colors, fast response speed, wide applicable temperature range, low driving voltage, the ability to produce flexible, bendable and transparent display panels, and environmental friendliness. They can be used in flat-panel displays and new generation lighting, and can also be used as LCD backlight sources.

[0003] Currently, organic electroluminescence has become the mainstream display technology, and accordingly, various new materials have been developed to prepare organic thin film layers. However, with the development of society and technology, people have put forward higher requirements for the various performances of organic electroluminescent devices, especially in terms of efficiency, life, voltage, etc. Therefore, the field is in urgent need of developing more types of organic thin film materials with higher performance to meet people's higher requirements for organic electroluminescent devices. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention aims to provide dibenzofuranfuran compounds and their applications and light-emitting devices. The present invention designs the structure of dibenzofuranfuran compounds and uses the dibenzofuranfuran compounds as the main material of the light-emitting layer, so that the organic electroluminescent device has a lower driving voltage, higher current efficiency and longer life.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides a dibenzofuranfuran compound as shown in Formula 1,

[0007]

[0008] Wherein, ring A represents dibenzofuran, R 1 , R 2 , R 3 Independently selected from any one of -H, substituted or unsubstituted C6-C40 aryl, and substituted or unsubstituted C12-C40 heteroaryl;

[0009] m is 0 or 1.

[0010] Preferably, the C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthofluorenyl, pyrenyl, perylenyl, spirofluorenyl, triphenylene, fluoranthenyl, hydrobenzanthryl, indeno[1,2-b]fluorene, benzo[1,2-b]indeno[1,2-b]fluorene, dibenzo[1,2-b]indeno[1,2-b]fluorene, naphthofluorenyl or benzo[naphtho[1,2-b]fluorene;

[0011] The C12-C40 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothiophenyl, benzodibenzofuranyl, benzodibenzothiophenyl, dinaphthofuranyl or dinaphthothiophenyl.

[0012] Preferably, the dibenzofuranofuran compound is represented by any one of Formula I to Formula V:

[0013]

[0014] Preferably, the R 1 , R 2 are independently selected from any one of -H, substituted or unsubstituted C6-C40 aryl group, substituted or unsubstituted C12-C40 heteroaryl group; the C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthofluorenyl, pyrenyl, perylenyl, spirofluorenyl, triphenylene, fluoranthenyl, hydrobenzanthryl, indeno[1,2-b]fluorene, benzo[1,2-b]indeno[1,2-b]fluorene, dibenzo[1,2-b]indeno[1,2-b]fluorene, naphthofluorenyl or benzo[naphtho[1,2-b]fluorene; the C12-C40 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothiophenyl, benzodibenzofuranyl, benzodibenzothiophenyl, dinaphthofuranyl or dinaphthothiophenyl.

[0015] Preferably, the dibenzofuranofuran compound is selected from any one of the following compounds:

[0016]

[0017]

[0018]

[0019]

[0020] Preferably, the dibenzofuranofuran compound is selected from any one of the following compounds:

[0021]

[0022] In a second aspect, the present invention provides a light-emitting device, which comprises the dibenzofuranofuran compound described in the first aspect.

[0023] Preferably, the light emitting device is an organic electroluminescent device.

[0024] Preferably, the organic electroluminescent device is a blue organic electroluminescent device.

[0025] Preferably, the light-emitting device includes a first electrode, a second electrode disposed opposite to the first electrode, and at least one organic layer sandwiched between the first electrode and the second electrode, and the at least one organic layer includes a dibenzofuranofuran compound.

[0026] Preferably, the at least one organic layer is a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer or an electron transport layer.

[0027] Preferably, the at least one organic layer is a light-emitting layer.

[0028] In a third aspect, the present invention provides a use of the dibenzofuranfuran compound described in the first aspect as a light-emitting material in a light-emitting device, wherein the light-emitting material is a blue light-emitting material.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] The present invention designs the structure of dibenzofuranfuran compounds, and the dibenzofuranfuran compounds have excellent film-forming properties and thermal stability, and can be used to prepare organic electroluminescent devices, especially blue light organic electroluminescent devices, and can be used as constituent materials of hole transport layers, electron blocking layers, light-emitting layers, and hole blocking layers. More importantly, the dibenzofuranfuran compounds of the present invention have excellent transport properties and light-emitting properties, and when used as light-emitting layer materials, especially blue light-emitting layer materials, can reduce the driving voltage of organic electroluminescent devices, improve the efficiency of the devices, and extend the life of the devices. DETAILED DESCRIPTION

[0031] 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.

[0032] Intermediate Preparation Example 1

[0033] This intermediate preparation example provides a method for synthesizing an intermediate M-1, and the specific synthesis steps are as follows:

[0034]

[0035] (1) Synthesis of intermediate M-1-1

[0036] Under nitrogen protection, 200 mL of THF was added to a 500 mL three-necked flask in sequence, and then raw material A (60.0 mmol) was added, the temperature was lowered to -78 ° C, stirred to dissolve, 2.5 M n-BuLi (1 eq) was slowly added dropwise, and stirred at low temperature for 1 h. N-bromosuccinimide (60.0 mmol) was added, and the temperature was slowly raised to 25 ° C for 4 h. 100 ml of 1 mol / L hydrochloric acid was added and stirred for 1 h. 200 ml of water was added, and a large amount of solid precipitated. Filter with suction, add 500 ml of water to the filter cake, wash twice, dry, and purify by chromatography to obtain intermediate M-1-1.

[0037] The intermediate M-1-1 was detected by mass spectrometry, and the mass-to-charge ratio (m / z) was 285.96.

[0038] (2) Synthesis of intermediate M-1-2

[0039] Under nitrogen protection, 150 mL of toluene, 80 ml of ethanol and 80 mL of water were added to a 500 mL three-necked flask in sequence, and then intermediate M-1-1 (60.0 mmol), phenylboric acid (72.0 mmol), potassium carbonate (90.0 mmol) and tetrakistriphenylphosphine palladium (0.6 mmol) were added, and the temperature was slowly raised to reflux for reaction for 12 h. After the reaction was completed, the temperature was lowered to room temperature, and water was added to separate the mixture. The aqueous phase was extracted once with toluene, and the organic phases were combined. The organic phases were washed with water, dried over magnesium sulfate, filtered to remove the magnesium sulfate, and the solvent was removed under reduced pressure. The mixture was separated by silica gel column chromatography and eluted with petroleum ether to obtain intermediate M-1-2.

[0040] The intermediate M-1-2 was detected by mass spectrometry, and the mass-to-charge ratio (m / z) was 284.08.

[0041] (3) Synthesis of intermediate M-1

[0042] Under nitrogen protection, 300 mL of DMF was added to a 500 mL three-necked flask in sequence, and then the intermediate M-1-2 (70.0 mmol) and NBS (105.0 mmol) were added. The temperature was controlled at 25 °C for 6 h. After the reaction was completed, 800 ml of water was added to a 2 L beaker, and the reaction solution was slowly added to the beaker. The mixture was stirred for 30 min and filtered. The filter cake was recrystallized with toluene ethanol to obtain the intermediate M-1.

[0043] The intermediate M-1 was detected by mass spectrometry, and the mass-to-charge ratio (m / z) was 361.99.

[0044] The intermediate M-1 was subjected to nuclear magnetic resonance detection: 1H-NMR (Bruker, Switzerland, AvanceⅡ400MHz nuclear magnetic resonance spectrometer, CDCl3), δ8.05 (m, 2H), δ7.99 (m, 1H), 7.64~7.60 (m, 4H), δ7.50 (m, 1H), δ7.38 (m, 1H), δ7.30 (m, 1H), 7.18 (d, 1H).

[0045] Intermediate Preparation Examples 2 to 8

[0046] Intermediate Preparation Examples 2 to 8 respectively provide an intermediate, and the synthesis method thereof refers to the synthesis method of intermediate M-1, with the only difference being that the raw material A in step (1) of intermediate Preparation Example 1 is replaced by other dibenzofuranfuran compounds (see Table 1 for details) of the corresponding amount, and the phenylboric acid in step (2) is replaced by other boronic acid compounds (see Table 1 for details) of the corresponding amount. The other conditions are the same as the synthesis method of intermediate M-1. The intermediate is subjected to mass spectrometry detection, and the test data are shown in Table 1 below.

[0047] Table 1 Types of raw material compounds and intermediate structures of intermediate preparation examples 2 to 8

[0048]

[0049]

[0050] Synthesis Example 1

[0051] This synthesis example provides a method for synthesizing compound 1, comprising the following steps:

[0052]

[0053] Under nitrogen protection, 150 mL of toluene and 80 mL of water were added to a 500 mL three-necked flask in sequence, and then 80 mL of ethanol was added, and intermediate M-1 (10.0 mmol), raw material B (12.0 mmol), potassium carbonate (15.0 mmol), tetrakistriphenylphosphine palladium (0.3 mmol) were added, and the temperature was slowly raised to reflux for 12 h. After the reaction was completed, the temperature was lowered to room temperature, and water was added to separate the organic layer, and the organic layer was washed with water and dried with magnesium sulfate. After the magnesium sulfate was removed by filtration, the solvent was removed under reduced pressure, and the compound 1 was crystallized with a mixed solvent of toluene and ethanol to obtain compound 1.

[0054] The mass spectrometry of compound 1 showed a mass-to-charge ratio (m / z) of 586.19.

[0055] Synthesis Examples 2 to 16

[0056] Synthesis Examples 2 to 16 provide compounds 2 to 16 respectively. The synthesis method thereof refers to the synthesis method of compound 1, with the only difference that the intermediate M-1 is replaced by other intermediates of equal amount (see Table 2 for details), and [10-(1-naphthyl)-9-anthracene]boric acid is replaced by other boronic acid compounds of equal amount (see Table 2 for details). The other conditions are the same as those of the synthesis method of compound 1. The synthesized compounds are subjected to mass spectrometry detection, and the test data are shown in Table 2 for details.

[0057] Table 2 Structures of intermediates, boronic acid compounds and synthesized compounds in Synthetic Examples 2 to 16

[0058]

[0059]

[0060]

[0061]

[0062]

[0063] Other compounds whose specific synthesis methods are not listed can be synthesized by referring to the above embodiments in combination with common knowledge in the art.

[0064] The specific structures of some of the substances used in the following application examples and comparative application examples are as follows:

[0065]

[0066] Application Example 1

[0067] This application example provides an organic electroluminescent device, using the compound 1 provided in Synthesis Example 1 of the present invention as the main material of the light-emitting layer;

[0068] The structure of the organic electroluminescent device is: ITO / HT (40 nm) / luminescent layer main material: BD-23% (30 nm) / TPBI (30 nm) / LiF (0.5 nm) / Al (150 nm).

[0069] The preparation method of the organic electroluminescent device is as follows:

[0070] The glass substrate coated with an ITO transparent conductive layer (as an anode) was ultrasonically treated in a cleaning agent, then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol, and then baked in a clean environment until the water was completely removed. It was cleaned with ultraviolet light and ozone, and the surface was bombarded with a low-energy cation beam to improve the surface properties and enhance the bonding ability with the hole layer.

[0071] The material was placed in a vacuum chamber and evacuated to 1×10 -5 ~1×10 -6 Pa, and then vacuum evaporated onto the cleaned ITO substrate. Among them, the main material of the light-emitting layer: BD-2 3% (30nm) means that in the device, the main material of the light-emitting layer and BD-2 are co-evaporated in a volume ratio of 97:3 to form a light-emitting layer, and the thickness of the light-emitting layer is 30nm.

[0072] Application Examples 2 to 16

[0073] Application Examples 2 to 16 respectively provide an organic electroluminescent device, which differs from Application Example 1 only in that the main material of the light-emitting layer is different (see Table 3 for details), and other conditions are the same as those of Application Example 1.

[0074] Application Comparative Examples 1 to 3

[0075] Comparative Application Examples 1 to 3 respectively provide an organic electroluminescent device, which is different from Application Example 1 only in that the main material of the light-emitting layer is different (see Table 3 for details), and other conditions are the same as those of Application Example 1.

[0076] Performance Testing

[0077] Test the driving voltage, current efficiency and life LT90 of the OLED devices provided above; LT90 refers to the time required for the brightness to drop to 90% of the original brightness while maintaining the current density at the initial brightness of 1000nit. The test items include the brightness, driving voltage and current efficiency of the organic electroluminescent device. The driving voltage, current efficiency and LT90 data are all based on a brightness of 1000cd / m 2 The relative value when (based on the test data of comparative example 1).

[0078] The performance test results of the organic electroluminescent device are shown in Table 3.

[0079] Table 3 Test results of main materials and device performance of light-emitting layers in application examples 1 to 16 and comparative examples 1 to 3

[0080]

[0081] As can be seen from Table 3, the present invention obtains anthracene compounds with specific structures by designing the structures of anthracene compounds. The anthracene compounds provided by the present invention can be used as the main material of the light-emitting layer of an organic electroluminescent device, so that the organic electroluminescent device has a lower driving voltage, higher current efficiency and longer life.

[0082] 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 dibenzofuranfuran compound, characterized in that: The dibenzofuranfuran compound has a structure as shown in Formula 1: Wherein, ring A represents dibenzofuran, and R1, R2, and R3 are each independently selected from any one of -H, substituted or unsubstituted C6-C40 aryl, and substituted or unsubstituted C12-C40 heteroaryl; m is 0 or 1.

2. The dibenzofuranofuran compound according to claim 1, characterized in that The C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthfluoroenyl, pyrenyl, peryl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthfluoroenyl or benzonaphthfluoroenyl; The C12-C40 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothiophenyl, benzodibenzofuranyl, benzodibenzothiophenyl, dinaphthofuranyl or dinaphthothiophenyl.

3. The dibenzofuranofuran compound according to claim 1, characterized in that: The dibenzofuranofuran compound is selected from any one of the compounds of formula I to formula V:

4. The dibenzofuranofuran compound according to claim 3, characterized in that: The R1 and R2 are each independently selected from any one of -H, substituted or unsubstituted C6-C40 aryl, and substituted or unsubstituted C12-C40 heteroaryl; The C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthfluoroenyl, pyrenyl, peryl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthfluoroenyl or benzonaphthfluoroenyl; The C12-C40 heteroaryl group is selected from any one of dibenzofuranyl, dibenzothiophenyl, benzodibenzofuranyl, benzodibenzothiophenyl, dinaphthofuranyl and dinaphthothiophenyl.

5. The dibenzofuranofuran compound according to claim 1, characterized in that: The dibenzofuranfuran compound is selected from any one of the following compounds:

6. A light emitting device, characterized in that: The light-emitting device comprises the dibenzofuranofuran compound according to any one of claims 1 to 5.

7. The light emitting device according to claim 6, characterized in that: The light emitting device is an organic electroluminescent device.

8. The light emitting device according to claim 6, characterized in that: The light-emitting device includes a first electrode, a second electrode disposed opposite to the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer includes a dibenzofuranofuran compound.

9. The light emitting device according to claim 8, characterized in that: The at least one organic layer is a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer or an electron transport layer; Preferably, the at least one organic layer is a light-emitting layer.

10. Use of the dibenzofuranofuran compound according to any one of claims 1 to 5 in preparing a luminescent material, characterized in that: The luminescent material is a blue light luminescent material.

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