Anthracene heterocyclic compound, organic electroluminescent device and display device

Abstract

The invention provides an anthracene heterocyclic compound, an organic electroluminescent device and a display device, and relates to the technical field of organic photoelectricity. The anthracene heterocyclic compound has a structure as shown in a formula I, has good luminescence performance, can be used for preparing the organic electroluminescent device, and can effectively reduce the driving voltage of the organic electroluminescent device and improve the current efficiency of the organic electroluminescent device especially as a luminescent layer material in the organic electroluminescent device.

Description

Technical Field

[0001] The present invention relates to the field of organic photoelectric technology, and in particular to an anthracene-heterocyclic compound, an organic electroluminescent device and a display device. Background Art

[0002] Organic light emitting diodes (OLEDs) are display components that utilize the phenomenon of self-luminescence and have a wide viewing angle. Compared with liquid crystal display components, OLED components are thinner and lighter, have a faster response speed, and can achieve flexible displays. Therefore, their application as full-color display components or lighting equipment is highly anticipated.

[0003] Generally, organic light emitting phenomenon refers to the phenomenon of converting electrical energy into light energy using organic substances. An organic light emitting element using the organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer interposed between the anode and the cathode.

[0004] Among them, the organic layer is composed of a multilayer structure composed of different substances in most cases in order to improve the efficiency and stability of the organic light-emitting element. For example, it can be composed of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. If a voltage is applied between the two electrodes in the structure of such an organic light-emitting element, the holes in the anode will be injected into the organic layer, and the electrons in the cathode will also be injected into the organic layer. When the injected holes and electrons meet, excitons are formed. When the excitons release energy and transition to the ground state, photons will be emitted, thereby generating light. Such organic light-emitting elements are widely recognized to have the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, high-speed responsiveness, etc.

[0005] At present, the research on organic electroluminescent materials has been widely carried out in academia and industry. Among them, luminescent materials are an important component of organic electroluminescent devices. The transmission performance and luminous efficiency of luminescent materials restrict the industrialization of luminescent devices. Therefore, designing and finding a compound as a new OLED material to overcome its shortcomings in practical applications is the focus of OLED material research and the future research and development trend. Summary of the invention

[0006] 1. Technical issues to be solved

[0007] In view of the shortcomings of the prior art, the present invention provides an anthracene-heterocyclic compound, an organic electroluminescent device and a display device, which solve the technical problems of high driving voltage and low current efficiency of organic electroluminescent devices prepared from existing luminescent materials.

[0008] (II) Technical solution

[0009] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0010] In a first aspect, the present invention provides an anthracene heterocyclic compound, wherein the anthracene heterocyclic compound has a structure as shown in the following formula I:

[0011]

[0012] Wherein, R1, R2 and R3 are each independently selected from substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C6~C 40 Any of the heteroaryl groups;

[0013] The hydrogen atoms in the compound of formula I can be replaced independently by deuterium atoms, F, CN, C6-C 30 Aryl or C6~C 40 The aromatic heterocyclic group is substituted with at least one of the following.

[0014] Preferably, the C6~C 30 The aromatic hydrocarbon group is at least one selected from phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, indenyl, fluorenyl, perylenyl, phenanthryl, pyrenyl, fluoranthenyl or triphenylenyl.

[0015] Preferably, the C6~C 40 The heteroatom in the aromatic heterocyclic group is at least one selected from oxygen, sulfur, silicon, boron and nitrogen atoms.

[0016] Preferably, the C6~C 40 The aromatic heterocyclic group is any one selected from benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, carbazole, diarylideneamine, benzofuranocarbazole, benzofuranothiophene, and triazine.

[0017] Preferably, the anthracene-heterocyclic compound is selected from any one of the following compounds:

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024] Preferably, the anthracene heterocyclic compound is selected from any one of compounds 1 to 25:

[0025]

[0026] In a second aspect, the present invention provides an organic electroluminescent device, wherein the organic electroluminescent device comprises the anthracene-heterocyclic compound as described in 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 anthracene-heterocyclic compound as described in the first aspect.

[0028] Preferably, the organic layer includes a light-emitting layer; the material of the light-emitting layer includes the anthracene-heterocyclic compound as described in the first aspect.

[0029] In a third aspect, the present invention provides a display device, comprising the organic electroluminescent device as described in the second aspect.

[0030] (III) Beneficial effects

[0031] The present invention provides an anthracene heterocyclic compound, an organic electroluminescent device and a display device. Compared with the prior art, the present invention has the following beneficial effects:

[0032] The present invention designs and searches for the structure of anthracene-heterocyclic compounds to obtain anthracene-heterocyclic compounds with good luminescence properties, which can be used to prepare organic electroluminescent devices, especially as light-emitting layer materials in organic electroluminescent devices, and can effectively reduce the driving voltage of organic electroluminescent devices and improve the current efficiency of organic electroluminescent devices. DETAILED DESCRIPTION

[0033] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] In order to better understand the above technical solution, the above technical solution will be described in detail below in conjunction with specific implementation methods.

[0035] Synthesis Example 1

[0036] This embodiment provides a method for synthesizing compound 1, which is as follows:

[0037]

[0038] Synthesis of intermediate 1-a

[0039] 0.1 mol 9-bromo-10-phenylanthracene, 0.12 mol (3-nitro-[1,1'-biphenyl]-4-yl) boronic acid, 0.15 mol potassium carbonate, 0.003 mol tetrakis(triphenylphosphine)palladium, 300 mL toluene, 100 ml ethanol, and 100 ml water were added to the reaction flask, heated to reflux under nitrogen protection, and reacted for 6 hours. After the reaction was completed, the reaction solution was naturally cooled to room temperature, separated, and the aqueous phase was extracted with 200 mL toluene. The organic phases were combined, dried with anhydrous magnesium sulfate, filtered to remove anhydrous magnesium sulfate, and the filtrate was passed through silica gel to remove the catalyst. After the column liquid was concentrated, it was recrystallized with toluene to obtain intermediate 1-a.

[0040] The mass spectrum data of intermediate 1-a was tested, and the mass spectrum m / z was measured to be 451.16.

[0041] Synthesis of intermediate 1-b

[0042] 0.1 mol of intermediate 1-a, 0.22 mol of triphenylphosphine and 300 mL of o-dichlorobenzene were added to a reaction flask. The temperature was controlled at 150°C under nitrogen protection and the reaction was carried out for 12 h. After the reaction was complete, o-dichlorobenzene was distilled off under reduced pressure. 500 ml of toluene was added to the product in the reaction flask, the temperature was raised and the solution was passed through a silica gel column. The column liquid was concentrated to 100 ml. 200 ml of ethanol was added, stirred for min, and filtered to obtain 1-b.

[0043] The mass spectrum data of intermediate 1-b was tested, and the mass spectrum m / z was measured to be 419.17.

[0044] Synthesis of compound 1

[0045] 0.1 mol of intermediate 1-b, 0.12 mol of bromobenzene, 3 mmol of tris(dibenzyl-BASE acetone)dipalladium, 6 mmol of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, 0.15 mol of sodium tert-butoxide and 300 ml of xylene were added to a reaction bottle, heated to 150 ° C, reacted for 12 h, and the reaction was completed after TLC monitoring. The reaction was cooled to room temperature, 300 ml of n-heptane was added, stirred for 30 min, filtered, the filter cake was washed with ethanol, and recrystallized from toluene to obtain compound 1.

[0046] The mass spectrum data of compound 1 was tested and the mass spectrum m / z was measured to be 495.20.

[0047] Synthesis Example 2

[0048] This embodiment provides a method for synthesizing compound 2, which is as follows:

[0049]

[0050] Synthesis of intermediate 2-a

[0051] Referring to the synthesis method of intermediate 1-a, (5-(naphthalene-2-yl)-2-nitrophenyl)boric acid was used instead of (3-nitro-[1,1'-biphenyl]-4-yl)boric acid, and other conditions remained unchanged to obtain intermediate 2-a.

[0052] The mass spectrum data of intermediate 2-a was tested, and the mass spectrum m / z was measured to be 501.17.

[0053] Synthesis of intermediate 2-b

[0054] Referring to the synthesis method of intermediate 1-b, intermediate 2-a is used to replace intermediate 1-a, and other conditions remain unchanged to obtain intermediate 2-b.

[0055] The mass spectrum data of intermediate 2-b was tested, and the mass spectrum m / z was measured to be 469.18.

[0056] Synthesis of compound 2

[0057] Referring to the synthesis method of compound 1, intermediate 2-b was used to replace intermediate 1-b, and other conditions remained unchanged to obtain compound 2.

[0058] The mass spectrum data of compound 2 was tested and the mass spectrum m / z was measured to be 545.21.

[0059] Synthesis Example 3

[0060] This embodiment provides a method for synthesizing compound 3, which is as follows:

[0061]

[0062] Synthesis of intermediate 3-a

[0063] Referring to the synthesis method of intermediate 1-a, (4-nitro-[1,1'-biphenyl]-3-yl)boric acid was used instead of (3-nitro-[1,1'-biphenyl]-4-yl)boric acid, and other conditions remained unchanged to obtain intermediate 3-a.

[0064] The mass spectrum data of intermediate 3-a was tested, and the mass spectrum m / z was measured to be 451.16.

[0065] Synthesis of intermediate 3-b

[0066] Referring to the synthesis method of intermediate 1-b, intermediate 3-a is used to replace intermediate 1-a, and other conditions remain unchanged to obtain intermediate 3-b.

[0067] The mass spectrum data of intermediate 3-b was tested, and the mass spectrum m / z was measured to be 419.17.

[0068] Synthesis of compound 3

[0069] Referring to the synthesis method of compound 1, intermediate 3-b was used to replace intermediate 1-b, 2-bromonaphthalene was used to replace bromobenzene, and other conditions remained unchanged to obtain compound 3.

[0070] The mass spectrum data of compound 3 was tested and the mass spectrum m / z was measured to be 545.21.

[0071] Synthesis Example 4

[0072] This embodiment provides a method for synthesizing compound 4, which is as follows:

[0073]

[0074] Synthesis of intermediate 4-a

[0075] 0.1 mol of dibenzo[b,d]thiophene-2-ylboronic acid, 0.11 mol of 4-bromo-1-chloro-2-nitrobenzene, 3 mmol of tetrakistriphenylphosphine palladium, 0.15 mol of potassium carbonate, 300 ml of toluene, 100 ml of ethanol and 100 ml of water were added to a reaction bottle, the temperature was controlled at 90°C, and the reaction was carried out for 8 hours. After the reaction was completed, the reaction solution was naturally cooled to room temperature, separated, and the aqueous phase was extracted with 200 mL of toluene. The organic phases were combined, anhydrous magnesium sulfate was added and dried, and the anhydrous magnesium sulfate was filtered to remove the catalyst. The filtrate was passed through silica gel to remove the catalyst. After the column liquid was concentrated, it was recrystallized with toluene to obtain intermediate 4-a.

[0076] The mass spectrum data of intermediate 4-a was tested, and the mass spectrum m / z was measured to be 339.01.

[0077] Synthesis of intermediate 4-b

[0078] 0.1 mol of intermediate 4-a, 0.15 mol of pinacol diboron, 3 mmol of tris(dibenzyl-BASE acetone)dipalladium, 6 mmol of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, 0.3 mol of potassium acetate and 300 ml of toluene were reacted at 120°C for 5 hours. After the reaction was completed, 300 ml of ethanol was added and stirred for 30 minutes. The filter cake was washed twice with water and once with ethanol, and recrystallized from toluene and ethanol to obtain intermediate 4-b.

[0079] The mass spectrum data of intermediate 4-b was tested, and the mass spectrum m / z was measured to be 431.14.

[0080] Synthesis of intermediate 4-c

[0081] Referring to the synthesis method of intermediate 1-a, intermediate 4-b was used to replace (3-nitro-[1,1'-biphenyl]-4-yl)boric acid, and 9-bromo-10-(naphthalene-1-yl)anthracene was used to replace 9-bromo-10-phenylanthracene, and other conditions remained unchanged to obtain intermediate 4-c.

[0082] The mass spectrum data of intermediate 4-c was tested, and the mass spectrum m / z was measured to be 607.16.

[0083] Synthesis of intermediate 4-d

[0084] Referring to the synthesis method of intermediate 1-b, intermediate 4-c was used to replace intermediate 1-a, and other conditions remained unchanged to obtain intermediate 4-d.

[0085] The mass spectrum data of intermediate 4-d was tested, and the mass spectrum m / z was measured to be 575.17.

[0086] Synthesis of compound 4

[0087] Referring to the synthesis method of compound 1, intermediate 4-d was used to replace intermediate 1-b, and other conditions remained unchanged to obtain compound 4.

[0088] The mass spectrum data of compound 4 was tested and the mass spectrum m / z was measured to be 651.20.

[0089] Other compounds whose specific synthesis steps are not listed can be prepared by common knowledge in the art in combination with the above embodiments.

[0090] The specific structures of the compounds used in the following device examples and device comparative examples are shown below:

[0091]

[0092] Device Example 1

[0093] This device embodiment provides an organic electroluminescent device, using the compound 1 provided in Example 1 of the present invention as a main material of the light-emitting layer.

[0094] The structure of the organic electroluminescent device is: ITO / HT (40 nm) / luminescent layer main material: BD 3% (30 nm) / TPBI (30 nm) / LiF (0.5 nm) / Al (150 nm).

[0095] The preparation method of the organic electroluminescent device is as follows:

[0096] (1) A transparent electrode indium tin oxide (ITO) film (15 Ω / sq) (Samsung Corning, South Korea) on a glass substrate for preparing an organic light emitting diode (OLED) device was ultrasonically cleaned with trichloroethylene, acetone, ethanol and distilled water in sequence, and then stored in isopropyl alcohol. Subsequently, the ITO substrate was mounted on a substrate fixture of a vacuum vapor deposition device;

[0097] (2) HT was introduced into the chamber of the vacuum vapor deposition apparatus, and the chamber pressure of the apparatus was then controlled to reach 10 -6 Support, deposit 40nm HT as a hole transport layer on the ITO substrate;

[0098] (3) transferring to another chamber, introducing the compound 1 provided by the present invention into one chamber of the vacuum vapor deposition equipment as a matrix material, and introducing the compound BD into another chamber as a dopant, evaporating the two materials at different rates, and depositing them at a doping amount of 3 wt % (based on the total weight of the matrix material and the dopant), thereby forming a light-emitting layer with a thickness of 30 nm on the hole transport layer;

[0099] (4) vacuum evaporating 30 nm of TPBI on the organic light-emitting layer as the electron transport layer of the organic electroluminescent device;

[0100] (5) On the electron transport layer, 0.5 nm of LiF and 150 nm of Al were vacuum-deposited in sequence as an electron injection layer and a cathode, respectively, to obtain an organic electroluminescent device.

[0101] Device Examples 2-25

[0102] Device Examples 2-25 respectively provide an organic electroluminescent device, which differs from Device Example 1 only in that the main material of the light-emitting layer is different (see Table 1 for details), and the other preparation steps and conditions are the same as those of Device Example 1.

[0103] Device Comparison Examples 1-3

[0104] The device comparative examples 1-3 provide an organic electroluminescent device, which is different from the device embodiment 1 only in that the main material of the light-emitting layer is different (see Table 1 for details), and the other preparation steps and conditions are the same as those of the device embodiment 1.

[0105] Performance Testing

[0106] Test method: The OLED-1000 multi-channel accelerated aging life and light color performance analysis system produced by Hangzhou Yuanfang was used to 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 device comparative example 1).

[0107] The performance test results are shown in Table 1 below.

[0108] Table 1

[0109]

[0110]

[0111] From the above content, it can be seen that in the present invention, by designing and searching for the structure of anthracene-heterocyclic compounds, anthracene-heterocyclic compounds that can be used as the main material of the light-emitting layer are obtained. Using this anthracene-heterocyclic compound as the main material of the light-emitting layer, an organic electroluminescent device with lower driving voltage, higher luminous efficiency and longer service life is prepared.

[0112] From the comparison of the relevant data of device embodiments 1-25 and device comparative examples 1-3, it can be seen that in the present invention, by designing the structure of the anthracene heterocyclic compound and further by specially selecting the R1, R2, and R3 groups in the anthracene heterocyclic compound (compound of Formula I), an anthracene heterocyclic compound suitable for use as the main material of the light-emitting layer of an organic electroluminescent device is obtained. By using this compound as the main material of the light-emitting layer, the current efficiency and service life of the organic electroluminescent device are further improved.

[0113] In summary, compared with the prior art, the present invention has the following beneficial effects:

[0114] The present invention designs and searches for the structure of anthracene-heterocyclic compounds to obtain anthracene-heterocyclic compounds with good luminescence properties, which can be used to prepare organic electroluminescent devices, especially as light-emitting layer materials in organic electroluminescent devices, and can effectively reduce the driving voltage of organic electroluminescent devices and improve the current efficiency of organic electroluminescent devices.

[0115] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0116] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An anthracene heterocyclic compound, characterized in that: It has the structure shown in the following formula I: Wherein, R1, R2 and R3 are each independently selected from substituted or unsubstituted C6 to C 40 Aryl, substituted or unsubstituted C6~C 40 Any of the heteroaryl groups; The hydrogen atoms in the compound of formula I are each independently replaced by a deuterium atom, F, CN, C6-C 30 Aryl or C6~C 40 The aromatic heterocyclic group is substituted with at least one of the following.

2. The anthraquinone heterocyclic compound according to claim 1, characterized in that C6~C 30 The aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, indenyl, fluorenyl, perylenyl, phenanthrenyl, pyrenyl, fluoranthenyl and triphenylenyl.

3. The anthraquinone heterocyclic compound according to claim 1, characterized in that: C6~C 40 The heteroatom in the aromatic heterocyclic group is selected from at least one of oxygen, sulfur, silicon, boron or nitrogen atoms.

4. The anthraquinone heterocyclic compound according to claim 1, characterized in that: C6~C 40 The aromatic heterocyclic group is selected from any one of benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, carbazole, diarylideneamine, benzofuranocarbazole, benzofuranothiophene and triazine.

5. The anthraquinone heterocyclic compound according to any one of claims 1 to 4, characterized in that: The anthracene-heterocyclic compound is selected from any one of the following compounds:

6. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises the anthraquinone heterocyclic compound according to any one of claims 1 to 4.

7. The organic electroluminescent device according to claim 6, characterized in that: The organic electroluminescent device comprises a first electrode, a second electrode and an organic layer arranged between the first electrode and the second electrode; the material of the organic layer comprises anthracene heterocyclic compounds.

8. The organic electroluminescent device according to claim 7, characterized in that: The organic layer includes a light-emitting layer; the light-emitting layer material includes anthracene-heterocyclic compounds.

9. A display device, characterized in that: The display device comprises the organic electroluminescent device according to claim 6.

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