Compound containing carbazole and triazine and application thereof

Abstract

The invention provides a compound containing carbazole and triazine and application thereof, and the compound containing carbazole and triazine has a structure as shown in a formula I. The structure of the compound is designed, so that the obtained compound containing carbazole has excellent performance; the organic light-emitting device prepared by using the compound as a light-emitting layer material has relatively low driving voltage and relatively high current efficiency.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic optoelectronic display, and particularly relates to a compound containing carbazole and triazine and its application. Background Art

[0002] An organic light emitting diode (OLED) is a display component that utilizes the phenomenon of self-luminescence. It has a large viewing angle. Compared with liquid crystal display components, OLED components are thinner, lighter, have a faster response speed, and can achieve flexible display. Therefore, its application as a full-color display component or lighting device is highly anticipated.

[0003] Generally, the organic light emitting phenomenon refers to the phenomenon of converting electrical energy into light energy using organic substances. An organic light emitting diode that utilizes the organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic layer sandwiched between the anode and the cathode.

[0004] Among them, in order to improve the efficiency and stability of the organic light emitting diode, the organic layer is in most cases composed of a multi-layer structure formed by different substances respectively. 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 diode, holes in the anode will be injected into the organic layer, and 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, thus generating light. Such an organic light emitting diode is widely recognized as having characteristics such as self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed responsiveness.

[0005] Currently, the research on organic electroluminescent materials has been widely carried out in the academic and industrial fields. Among them, the transport performance and light emitting efficiency of the materials restrict the industrialization of light emitting devices. Therefore, designing and finding a compound as a new type of OLED material to overcome the deficiencies that occur in the actual application process is the focus and future research trend of OLED material research work. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a compound containing carbazole and triazine and its application. Through the structural design of the compound containing carbazole and triazine, the obtained compound containing carbazole and triazine has excellent properties and is suitable for use as a light emitting layer material in organic electroluminescent devices.

[0007] To achieve this purpose, the present invention adopts the following technical solutions:

[0008] On the one hand, the present invention provides a compound containing carbazole and triazine, and the compound containing carbazole and triazine has a structure shown in Formula I:

[0009]

[0010] Wherein, X is selected from an oxygen atom, a sulfur atom or N-R1;

[0011] Ar1, Ar2, Ar3, Ar4 and Ar5 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0012] R1 is selected from substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0013] When the substituted or unsubstituted group contains a substituent, the substituent is selected from deuterium, F, CN, C1-C 12 alkyl, C6-C 30 aryl or C3-C 30 heteroaryl;

[0014] And all hydrogen atoms in Formula I can each independently be substituted by deuterium, F, CN, C1-C 12 alkyl, C6-C 30 aryl or C3-C 30 heteroaryl;

[0015] Preferably, the C1-C 12 alkyl is selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, pivalyl, n-hexyl or cyclohexyl.

[0016] More preferably, the C1-C 12 alkyl is selected from methyl, ethyl, isopropyl or tert-butyl.

[0017] Preferably, the C6-C 30 aryl refers to the general term of the monovalent group remaining after removing one hydrogen atom from the aromatic nucleus carbon of the aromatic hydrocarbon molecule; the C6-C 30 aryl includes monocyclic aryl or polycyclic aryl.

[0018] Preferably, the C6-C 30 aryl is selected from phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, indenyl, fluorenyl, perylenyl, phenanthryl, pyrenyl, fluoranthenyl, fluorenyl, spirobifluorenyl or benzophenanthryl.

[0019] More preferably, the C6-C 30 aryl is selected from phenyl, biphenyl, naphthyl.

[0020] Preferably, the C3-C 30 heteroaryl refers to the general term of the group obtained by replacing one or more aryl nucleus carbons in the aryl with heteroatoms; the heteroatoms of the C3-C 30 heteroaryl are selected from oxygen, sulfur, nitrogen or silicon; the C3-C 30 heteroaryl includes monocyclic heteroaryl or polycyclic heteroaryl.

[0021] Preferably, the C3-C 30 heteroaryl is selected from pyridyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, diarylamino, benzofurocarbazolyl, benzofurothiophenyl or triazinyl.

[0022] More preferably, the C3-C 30 heteroaryl is selected from pyridyl, dibenzofuranyl, dibenzothiophenyl or carbazolyl.

[0023] Preferably, the R1 is selected from phenyl, biphenyl, terphenyl, naphthyl, pyridyl, methyl, ethyl or tert-butyl;

[0024] Preferably, Ar1, Ar2, Ar3, Ar4 and Ar5 are each independently selected from hydrogen, tert-butyl, phenyl, naphthyl, biphenyl, terphenyl, diphenylamino, dibenzothiophenyl, dibenzofuranyl or where the wavy line represents the connection site of the group.

[0025] Preferably, the compound containing carbazole and triazine is selected from any one of Compounds 1-46:

[0026]

[0027]

[0028] Some specific structural forms of the compound containing carbazole and triazine are listed in the present invention, but the compound containing carbazole and triazine in the present invention is not limited to the listed chemical structures. Any structure based on the structure shown in Formula I and satisfying the above-defined conditions for X, Ar1, Ar2, Ar3, Ar4, Ar5 should be included.

[0029] In a second aspect, the present invention provides an organic electroluminescent device, and the organic electroluminescent device includes the compound containing carbazole and triazine as described in the first aspect.

[0030] Preferably, 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 compound containing carbazole and triazine as described in the first aspect.

[0031] Preferably, the organic layer includes a light-emitting layer, and the material of the light-emitting layer includes the compound containing carbazole and triazine as described in the first aspect.

[0032] Furthermore, the light-emitting layer is prepared by a vapor deposition method.

[0033] In a third aspect, the present invention provides a display device, which includes the organic electroluminescent device as described in the second aspect.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] By designing the structure of the compound containing carbazole and triazine, the obtained compound containing carbazole and triazine has good light-emitting performance, can be used for preparing an organic electroluminescent device, especially as the light-emitting layer material in 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. Specific Embodiments

[0036] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0037] Preparation Example 1

[0038]

[0039] (1) Synthesis of Intermediate 1-1

[0040] Under nitrogen protection, add 500 mL of dry tetrahydrofuran, 200 mL of water, 0.1 mol of triazine dicationic bromide, 0.12 mol of 3-bromo-5-chlorophenylboronic acid, 0.005 mol of tetrakis(triphenylphosphine)palladium, and 0.15 mol of potassium carbonate to a 1000 mL three-necked flask, heat to 65 °C and react for 6 h, then cool to room temperature, separate the liquid, dry the organic phase with sodium sulfate, perform column chromatography, concentrate the chromatography solution to dryness, and recrystallize with toluene and ethanol to obtain Intermediate 1-1;

[0041] Perform mass spectrometry detection on Intermediate 1-1, and the measured mass-to-charge ratio (m / z) is 599.1.

[0042] (2) Synthesis of Intermediate 1

[0043] Take 0.05 mol of intermediate 1-1, dissolve it in 300 ml of tetrahydrofuran, and cool it to a temperature between -80 °C and -75 °C. Then, dropwise add 0.06 mol of n-butyllithium (2.5 M). During the dropping process, maintain the temperature between -80 °C and -70 °C. After the dropping is complete, continue to stir for 1 h while maintaining the temperature between -80 °C and -70 °C. Then, dropwise add 0.07 mol of trimethylchlorosilane. During the dropping process, maintain the temperature between -80 °C and -70 °C. After the dropping is complete, react for 1 h while maintaining the temperature between -80 °C and -70 °C. Then, stop maintaining the temperature and slowly warm it up to room temperature. Then, slowly pour the reaction solution into 2 L of an ice-water mixture to precipitate the product. The crude product obtained after suction filtration is recrystallized with toluene and acetone to obtain intermediate 1.

[0044] Perform mass spectrometry detection on intermediate 1, and the measured mass-to-charge ratio (m / z) is 779.2.

[0045] Preparation Example 2

[0046] This example provides a method for synthesizing intermediate 2, which is as follows:

[0047]

[0048] Referring to the synthesis method of Preparation Example 1, replace 3-bromo-5-chlorophenylboronic acid in Preparation Example 1 with an equimolar amount of 2-chloro-5-bromophenylboronic acid, and other conditions remain unchanged to obtain intermediate 2.

[0049] Perform mass spectrometry detection on intermediate 2: The measured mass spectrum (m / z): 779.2.

[0050] Referring to Preparation Example 1 and Preparation Example 2, the following intermediates can be obtained. The specific results are shown in Table 1.

[0051] Table 1

[0052]

[0053]

[0054] Synthesis Example 1

[0055] This example provides a method for synthesizing compound 1, which is as follows:

[0056]

[0057] Under nitrogen protection, 400 mL of dry toluene, 200 mL of ethanol, 200 mL of water, 0.1 mol of intermediate 1, 0.11 mol of dibenzofuran-4-boronic acid, 0.005 mol of 0.001 mol of Pd2(dba)3 (tris(dibenzylideneacetone)dipalladium), 0.005 mol of xphos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl), and 0.15 mol of potassium carbonate were added to a 2000 mL three-necked flask. After heating to 78 °C and refluxing for 12 h, the temperature was lowered to room temperature. The layers were separated, and the organic phase was dried over sodium sulfate and subjected to column chromatography. The eluent was concentrated to dryness and recrystallized with toluene and ethanol to obtain Compound 1;

[0058] Compound 1 was subjected to mass spectrometry, and the measured mass-to-charge ratio (m / z) was 911.3.

[0059] Synthesis Example 2

[0060] This example provides a method for synthesizing Compound 2, which is as follows:

[0061]

[0062] Referring to the synthesis method of Synthesis Example 1, equimolar amount of dibenzofuran-2-boronic acid was used to replace dibenzofuran-4-boronic acid in Synthesis Example 1, and Compound 2 could be obtained under the same other conditions.

[0063] Compound 2 was subjected to mass spectrometry: The measured mass spectrum (m / z): 911.3.

[0064] Synthesis Example 3

[0065] This example provides a method for synthesizing Compound 3, which is as follows:

[0066]

[0067] Referring to the synthesis method of Synthesis Example 1, equimolar amount of dibenzofuran-1-boronic acid was used to replace dibenzofuran-4-boronic acid in Synthesis Example 1, and Compound 3 could be obtained under the same other conditions.

[0068] Compound 3 was subjected to mass spectrometry: The measured mass spectrum (m / z): 911.3.

[0069] Synthesis Example 4

[0070] This example provides a method for synthesizing Compound 4, which is as follows:

[0071]

[0072] Referring to the synthesis method of Synthesis Example 1, replacing intermediate 1 in Synthesis Example 1 with an equimolar amount of intermediate 2, and keeping other conditions unchanged, compound 4 can be obtained.

[0073] Compound 4 was subjected to mass spectrometry, and the measured mass-to-charge ratio (m / z): 911.3.

[0074] Synthesis Example 5

[0075] This example provides a method for synthesizing compound 7, which is as follows:

[0076]

[0077] Referring to the synthesis method of Synthesis Example 1, replacing dibenzofuran-4-boronic acid in Synthesis Example 1 with an equimolar amount of dibenzothiophene-4-boronic acid, and keeping other conditions unchanged, compound 7 can be obtained.

[0078] Compound 7 was subjected to mass spectrometry, and the measured mass-to-charge ratio (m / z): 927.3.

[0079] Synthesis Example 6

[0080] This example provides a method for synthesizing compound 14, which is as follows:

[0081]

[0082] Referring to the synthesis method of Synthesis Example 1, replacing dibenzofuran-4-boronic acid in Synthesis Example 1 with an equimolar amount of 9-phenylcarbazole-3-boronic acid, and keeping other conditions unchanged, compound 14 can be obtained.

[0083] Compound 14 was subjected to mass spectrometry, and the measured mass-to-charge ratio (m / z): 986.4.

[0084] Synthesis Example 7

[0085] This example provides a method for synthesizing compound 15, which is as follows:

[0086]

[0087] Referring to the synthesis method of Synthesis Example 1, replacing dibenzofuran-4-boronic acid in Synthesis Example 1 with an equimolar amount of 4-phenyldibenzofuran-2-boronic acid, and keeping other conditions unchanged, compound 15 can be obtained.

[0088] Compound 15 was subjected to mass spectrometry, and the measured mass-to-charge ratio (m / z): 987.3.

[0089] Referring to the synthesis methods of the above compounds and combining with common organic synthesis means, compounds 21, 22, 25, 29 and 34 were prepared and subjected to mass spectrometry detection. The test results are shown in Table 2 below.

[0090] Table 2

[0091]

[0092]

[0093] For compounds without specific synthesis steps listed, they can be prepared by combining the common general knowledge in the art with the above examples.

[0094] The specific structures of the compounds used in the following device examples and device comparative examples are as follows:

[0095]

[0096]

[0097] In the following device examples, the compounds containing carbazole and triazine provided by the present invention are selected as the host materials for the light-emitting layer in the organic electroluminescent device, and in the device comparative examples, the above ETH-1, ETH-2, and ETH-3 are selected as the host materials for the light-emitting layer in the organic electroluminescent device.

[0098] Device Example 1

[0099] This device example provides an organic electroluminescent device, using compound 1 provided by the synthesis example 1 of the present invention as the host material for the light-emitting layer; and in this example, the light-emitting layer is prepared by evaporation.

[0100] The structure of the organic electroluminescent device is:

[0101] ITO / HT(40nm) / Compound 1:D-1 5% / TPBI(30nm) / LiF(0.5nm) / Al(150nm).

[0102] The preparation method of the above organic electroluminescent device is as follows:

[0103] 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, then ultrasonically degreased in a mixed solvent of acetone and ethanol, and then baked in a clean environment until completely dehydrated, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam on the surface to improve the surface properties and enhance the binding ability with the hole injection layer;

[0104] Place the above glass substrate in a vacuum chamber, evacuate to 1×10 -5 ~9×10-6 Pa, HT was vacuum-evaporated on the anode as the hole transport layer at a deposition rate of 0.1 nm / s, and the deposited film thickness was 40 nm;

[0105] The light-emitting layer was vacuum-evaporated on the hole transport layer at a deposition rate of 0.1 nm / s, and the total deposited film thickness was 30 nm. The host material of the light-emitting layer was Compound 1 provided by this patent, and the doping material was Compound D-1. 5% refers to the doping ratio of the doping material, that is, the volume ratio of the host material to the doping material in the light-emitting layer is 95:5.

[0106] TPBI was vacuum-evaporated on the light-emitting layer as the electron transport layer of the device at a deposition rate of 0.1 nm / s, and the total deposited film thickness was 30 nm;

[0107] 0.5 nm of LiF and 150 nm of Al were vacuum-evaporated on the electron transport layer as the electron injection layer and the cathode.

[0108] The brightness, driving voltage, current efficiency, and lifetime of the fabricated organic light-emitting device were measured, as shown in Table 3.

[0109] Device Examples 2 - 12

[0110] Device Examples 2 - 12 respectively provide an organic light-emitting device, which is only different from Device Example 1 in that the host material of the light-emitting layer is different (see Table 3 for details), and other conditions are the same as those in Device Example 1.

[0111] Device Comparative Examples 1 - 3

[0112] Device Comparative Examples 1 - 3 respectively provide an organic light-emitting device, which is only different from Device Example 1 in that the host material of the light-emitting layer is different (see Table 3 for details), and other conditions are the same as those in Device Example 1.

[0113] Performance Test

[0114] The driving voltage, current efficiency, and lifetime LT90 of the above-provided OLED devices were tested; among them, LT90 refers to the time required for the brightness to drop to 90% of the original brightness while keeping the current density unchanged when the initial brightness is 1000 nit. The test items include the brightness, driving voltage, and current efficiency of the organic light-emitting device. The data of the driving voltage, current efficiency, and LT90 are all relative values at a brightness of 1000 cd / m 2 (based on the test data of ETH-1). The performance test results of the organic light-emitting device are shown in Table 3 below.

[0115] Table 3

[0116]

[0117]

[0118] As can be seen from the above, through structural design, the present invention obtains a compound suitable as a host material for a light-emitting layer, and the organic electroluminescent device prepared therefrom has a lower driving voltage, a higher current efficiency, and a longer service life.

[0119] The applicant declares that the present invention uses the above embodiments to illustrate the carbazole- and triazine-containing compounds of the present invention and their applications, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A compound containing carbazole and triazine, characterized in that, The compound containing carbazole and triazine has a structure shown in Formula I: Wherein, X is selected from an oxygen atom, a sulfur atom or N-R1; Ar1, Ar2, Ar3, Ar4 and Ar5 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl; R1 is selected from substituted or unsubstituted C1-C 12 alkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl; When the substituted or unsubstituted group contains a substituent, the substituent is selected from deuterium, F, CN, C1-C 12 alkyl, C6-C 30 aryl or C3-C 30 heteroaryl; and all hydrogen atoms in Formula I may each independently be replaced by deuterium, F, CN, C1-C 12 alkyl, C6-C 30 aryl or C3-C 30 heteroaryl.

2. The compound containing carbazole and triazine according to claim 1, characterized in that, The C1 to C 12 alkyl group is selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, pivalyl, n-hexyl or cyclohexyl; More preferably, the C1-C 12 alkyl group is selected from methyl, ethyl, isopropyl or tert-butyl.

3. The compound containing carbazole and triazine according to claim 1, characterized in that, The aryl group of C6-C 30 is selected from phenyl, biphenyl, terphenyl, naphthyl, anthryl, indenyl, fluorenyl, perylenyl, phenanthryl, pyrenyl, fluoranthenyl, spirobifluorenyl or benzophenanthryl; More preferably, the C6-C 30 aryl is selected from phenyl, biphenyl, and naphthyl.

4. The compound containing carbazole and triazine according to claim 1, characterized in that, The C3-C 30 heteroatom of the heteroaryl is selected from oxygen, sulfur, nitrogen or silicon; Preferably, the C3-C 30 heteroaryl is selected from pyridyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, diarylamino, benzofurocarbazolyl, benzofurothienyl or triazinyl; More preferably, the C3-C 30 heteroaryl is selected from pyridyl, dibenzofuranyl, dibenzothiophenyl or carbazolyl.

5. The compound containing carbazole and triazine according to claim 1, characterized in that, The R1 is selected from a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a pyridyl group, a methyl group, an ethyl group or a tert-butyl group; Preferably, Ar1, Ar2, Ar3, Ar4 and Ar5 are each independently selected from hydrogen, tert-butyl, phenyl, naphthyl, biphenyl, terphenyl, diphenylamino, dibenzothienyl, dibenzofuranyl or wherein the wavy line represents the connection site of the group.

6. The compound containing carbazole and triazine according to any one of claims 1-5, characterized in that, The compound containing carbazole and triazine is selected from any one of Compounds 1 to 46:

7. An organic electroluminescent device, characterized in that, The organic electroluminescent device comprises the compound containing carbazole and triazine according to any one of claims 1 to 6.

8. The organic electroluminescent device according to claim 7, wherein, 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 organic layer includes a light-emitting layer; the light-emitting layer includes the compound containing carbazole and triazine according to any one of claims 1 to 6.

9. The organic electroluminescent device according to claim 8, wherein The light-emitting layer is prepared by a vapor deposition method.

10. A display device, characterized in that, The display device includes the organic electroluminescent device according to any one of claims 7 to 9.

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