6, 6-dimethyl-6H-benzo [cd] pyrene compound and application thereof

Abstract

The invention provides a 6, 6-dimethyl-6H-benzo [cd] pyrene compound and an application of the 6, 6-dimethyl-6H-benzo [cd] pyrene compound. The 6, 6-dimethyl-6H-benzo [cd] pyrene compound has a structure as shown in a formula I in the specification. According to the present invention, the 6, 6-dimethyl-6H-benzo [cd] pyrene compound is designed through the structure of the 6, 6-dimethyl-6H-benzo [cd] pyrene compound, and the obtained 6, 6-dimethyl-6H-benzo [cd] pyrene compound has excellent performance, and is suitable for being used as the luminescent layer material in the organic electroluminescent device.

Description

Technical Field

[0001] The invention belongs to the field of organic photoelectric technology, and specifically relates to a 6,6-dimethyl-6H-benzo[cd]pyrene compound and application thereof. 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, and high-speed responsiveness.

[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] In view of the shortcomings of the prior art, the object of the present invention is to provide a 6,6-dimethyl-6H-benzo[cd]pyrene compound and its application. The present invention is designed through the structure of 6,6-dimethyl-6H-benzo[cd]pyrene compound, and the obtained 6,6-dimethyl-6H-benzo[cd]pyrene compound has excellent performance and is suitable for use as a light-emitting layer material in an organic electroluminescent device.

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

[0008] In a first aspect, the present invention provides a 6,6-dimethyl-6H-benzo[cd]pyrene compound, wherein the 6,6-dimethyl-6H-benzo[cd]pyrene compound has a structure as shown in the following formula I:

[0009]

[0010] Wherein, Ar is selected from substituted or unsubstituted C6-C30 aryl groups;

[0011] The substituted substituent is selected from at least one of a C6-C20 aryl group and a C1-C6 alkyl group;

[0012] The hydrogen atoms in the compound of formula I may each independently be substituted by any one of a deuterium atom (—D), —F, —CN, a C1-C12 alkyl group, a C6-C30 aryl group or a C3-C30 heteroaryl group.

[0013] The present invention is designed through the structure of 6,6-dimethyl-6H-benzo[cd]pyrene compounds, and the obtained 6,6-dimethyl-6H-benzo[cd]pyrene compounds have excellent performance. The organic electroluminescent device prepared by using the 6,6-dimethyl-6H-benzo[cd]pyrene compounds provided by the present invention as the light-emitting layer material has a lower driving voltage, a higher current efficiency and a longer life.

[0014] It should be noted that, in the present invention, "D" represents a deuterium atom, and the same applies hereinafter.

[0015] In the present invention, the C6-C30 aromatic group refers to the general term for a monovalent group remaining after removing a hydrogen atom from the aromatic core carbon of the aromatic hydrocarbon molecule, which can be a monocyclic aromatic group or a condensed-ring aromatic group, and illustratively includes but is not limited to: any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, indenyl, fluorenyl, perylenyl, phenanthrenyl, pyrenyl, fluoranthenyl, and triphenylenyl, or a combination of at least two of them.

[0016] The C3-C30 heteroaryl group refers to a general term for a monovalent group remaining after removing a hydrogen atom from the aromatic carbon of the heteroaromatic hydrocarbon molecule, which can be a monocyclic heteroaryl group or a condensed-ring heteroaryl group, and illustratively includes but is not limited to: any one of triazine, pyrazinyl, pyrimidinyl, pyridyl, isoquinolyl, quinolyl, quinoxalinyl, quinazolinyl, imidazolyl, benzimidazolyl, dibenzofuranyl, dibenzothiophenyl, benzodibenzofuranyl, benzodibenzothiophenyl, dinaphthofuranyl, and dinaphthothiophenyl, or a combination of at least two of them.

[0017] The C1-C12 alkyl group refers to a general term for a monovalent group remaining after removing a hydrogen atom from the carbon of an alkyl molecule, which may be chain-shaped or cyclic, and illustratively includes but is not limited to any one of methyl, ethyl, propyl, butyl, n-pentyl, n-hexyl, cyclohexyl, cyclopentyl, heptyl, octyl, nonyl, and adamantyl, or a combination of at least two of them.

[0018] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0019] As a preferred technical solution of the present invention, the 6,6-dimethyl-6H-benzo[cd]pyrene compound has a structure shown in the following formula I-1 or formula I-2:

[0020]

[0021] Wherein, Ar in the compound of formula I-1 or formula I-2 has the same definition as above;

[0022] The hydrogen atoms in the compound of formula I-1 or formula I-2 may each independently be substituted by any one of a deuterium atom (—D), —F, —CN, a C1-C12 alkyl group, a C6-C30 aryl group or a C3-C30 heteroaryl group.

[0023] As a preferred technical solution of the present invention, the C6-C30 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, indenyl, fluorenyl, perylenyl, phenanthrenyl, pyrenyl, fluoranthenyl or triphenylenyl.

[0024] Preferably, the C3-C30 heteroaryl group is selected from any one of triazine, pyrazinyl, pyrimidinyl, pyridyl, isoquinolyl, quinolyl, quinoxalinyl, quinazolinyl, imidazolyl, benzimidazolyl, dibenzofuranyl, dibenzothiophenyl, benzodibenzofuranyl, benzodibenzothiophenyl, dinaphthofuranyl or dinaphthothiophenyl.

[0025] Preferably, the C6-C20 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl or phenanthryl.

[0026] Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl or cyclohexyl.

[0027] Preferably, the C1-C6 alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl or cyclohexyl.

[0028] As a preferred technical solution of the present invention, Ar is selected from the following substituted or unsubstituted groups: at least one of naphthyl, phenyl, biphenyl, and anthracenyl;

[0029] The substituted substituent is selected from at least one of phenyl, naphthyl, phenanthrenyl and biphenyl.

[0030] As a preferred technical solution of the present invention, the hydrogen atoms in the compound of formula I can be independently replaced by any one of a deuterium atom (-D), -F, -CN, phenyl, naphthyl, biphenyl, methyl, ethyl, isopropyl, tert-butyl or cyclohexyl, preferably a deuterium atom.

[0031] As a preferred technical solution of the present invention, the 6,6-dimethyl-6H-benzo[cd]pyrene compound is selected from any one of the following compounds:

[0032]

[0033]

[0034] As a preferred technical solution of the present invention, the compound of formula I is selected from any one of the following compounds:

[0035]

[0036] In a second aspect, the present invention provides an intermediate, wherein the intermediate comprises a compound having a structure shown in the following formula MA:

[0037]

[0038] Wherein, X is selected from any one of F, Cl, Br or I;

[0039] The intermediate is used to prepare the 6,6-dimethyl-6H-benzo[cd]pyrene compounds as described in the first aspect.

[0040] As a preferred technical solution of the present invention, the intermediate includes the following compounds:

[0041]

[0042] Wherein, X is selected from any one of F, Cl, Br or I.

[0043] Preferably, the intermediate includes the following compounds:

[0044]

[0045] In a third aspect, the present invention provides an organic electroluminescent device, wherein the organic electroluminescent device comprises the 6,6-dimethyl-6H-benzo[cd]pyrene compound as described in the first aspect.

[0046] As a preferred technical solution of the present invention, the organic electroluminescent device comprises a first electrode, a second electrode and an organic layer disposed between the first electrode and the second electrode;

[0047] The material of the organic layer includes the 6,6-dimethyl-6H-benzo[cd]pyrene compound as described in the first aspect.

[0048] Preferably, the organic layer comprises a light-emitting layer;

[0049] The main material of the light-emitting layer includes the 6,6-dimethyl-6H-benzo[cd]pyrene compound as described in the first aspect.

[0050] In a fourth aspect, the present invention provides a display device, comprising the organic electroluminescent device as described in the third aspect.

[0051] Compared with the prior art, the present invention has the following beneficial effects:

[0052] The present invention is designed through the structure of 6,6-dimethyl-6H-benzo[cd]pyrene compounds, and the obtained 6,6-dimethyl-6H-benzo[cd]pyrene compounds have excellent performance. The organic electroluminescent device prepared by using the 6,6-dimethyl-6H-benzo[cd]pyrene compounds provided by the present invention as the light-emitting layer material has a lower driving voltage, a higher current efficiency and a longer life. DETAILED DESCRIPTION

[0053] 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.

[0054] Preparation Example 1

[0055] This preparation example provides a method for synthesizing intermediate A, and the method for synthesizing intermediate A is as follows:

[0056]

[0057] (1) Synthesis of intermediate A-2

[0058] Under a nitrogen atmosphere, add 3.4 g of compound A-1 and 60 mL of tetrahydrofuran to a three-necked flask, then cool to -75 ° C, slowly add 0.01 mol of butyl lithium in n-hexane solution (concentration of 1.6M, 6.3 mL), then maintain at -78 ° C to -60 ° C for 30 min, slowly add 1.5 g of trimethyl borate, slowly warm to room temperature and stir for 2 h, add dilute hydrochloric acid and ethyl acetate, separate the liquids, wash the organic layer with saturated sodium chloride solution, and concentrate to dryness. The obtained viscous solid is the intermediate product A-2, which is directly subjected to the following reaction without separation.

[0059] (2) Synthesis of intermediate A

[0060] Under nitrogen protection, 60 mL of toluene, 30 mL of ethanol, and 20 mL of water were added to the three-necked flask in sequence, and then the intermediate product A-2 prepared in the previous step and 3.6 g of 2.12g (0.02mol) of sodium carbonate and 0.23g (0.0002mol) of tetrakistriphenylphosphine palladium were slowly heated to reflux for reaction for 8h, cooled to room temperature, separated by adding water, the organic layer was washed with water, dried with magnesium sulfate, the desiccant was removed, concentrated to dryness, and separated by silica gel column chromatography, eluted with petroleum ether: dichloromethane = 10:2 (volume ratio), to obtain 2.1g of intermediate A;

[0061] The obtained intermediate A was subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) was measured to be 574.13.

[0062] Preparation Example 2

[0063] This preparation example provides a method for synthesizing intermediate B, as described below:

[0064]

[0065] Referring to the preparation method of intermediate A provided in Preparation Example 1, intermediate B was prepared.

[0066] The obtained intermediate B was subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) was measured to be 574.13.

[0067] Synthesis Example 1

[0068] This embodiment provides a method for synthesizing compound 1, and the method for synthesizing compound 1 is as follows:

[0069]

[0070] 0.1 mol of intermediate A, 0.1 mol of phenylboronic acid, 0.15 mol of potassium carbonate, and 0.021 g of Pd-132 (di-tert-butyldichloro-(4-dimethylaminophenyl)phosphine palladium (II)) were added to a reaction bottle, and 200 mL of toluene, 100 mL of ethanol and 100 mL of water were added. The reaction was carried out at 80°C for 12 h under nitrogen insulation and monitored by TLC. After the reaction of the raw materials was completed, the liquids were separated, and the mixture was washed with water and extracted twice with 100 mL*2 of toluene. The organic phases were combined and washed twice with 300 mL*2 of water. After the organic phase was dried, it was passed through a silica gel column. The column liquid was concentrated to dryness and recrystallized with a mixed solvent of toluene and ethanol to obtain compound 1. The mass-to-charge ratio (m / z) was measured to be 572.25.

[0071] Synthesis Example 2-Synthesis Example 7

[0072] Synthesis Example 2 to Synthesis Example 7 provide a compound respectively. Referring to the synthesis method of Compound 1, different raw materials are used to prepare the corresponding compounds, and the mass spectrum is measured, and the mass-to-charge ratio (m / z) is recorded as shown in Table 1 below.

[0073] Table 1

[0074]

[0075]

[0076] Other compounds whose specific synthesis steps are not listed can be prepared by common knowledge in the art in combination with the above embodiments.

[0077] In the present invention, the specific structure of the materials used in the following application examples is as follows:

[0078]

[0079] Device Example 1

[0080] This device embodiment 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; the structure of the organic electroluminescent device is:

[0081] ITO / HT (40nm) / light-emitting layer main material: BD-2 3% (30nm) / TPBI (30nm) / LiF (0.5nm) / Al (150nm).

[0082] The preparation method of the organic electroluminescent device is as follows:

[0083] The glass substrate coated with an ITO transparent conductive layer (as an anode) is ultrasonically treated in a cleaning agent, then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol, baked in a clean environment until the water is completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam to improve the properties of the surface and enhance the binding ability with the hole layer;

[0084] The material was placed in a vacuum chamber and evacuated to 1×10 -5 ~1×10 -6 Pa, and are vacuum evaporated onto a cleaned ITO substrate in sequence, wherein the main material of the light-emitting layer: BD-2 3% (30 nm) 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 30 nm.

[0085] Device Examples 2-7

[0086] Device Examples 2-7 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 2 below for details), and other conditions are the same as those of Device Example 1.

[0087] Device Comparison Example 1-2

[0088] Device Comparative Examples 1-2 respectively provide an organic electroluminescent device, which differs from Device Example 1 only in that the main body of the light-emitting layer is different (see Table 2 below for details), and other conditions are the same as those of Device Example 1.

[0089] Performance Testing

[0090] Test the driving voltage, current efficiency and life LT90 of the OLED devices provided above; LT 90 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 of the organic electroluminescent device performance test results are shown in Table 2 below:

[0091] Table 2

[0092]

[0093]

[0094] The present invention is designed through the structure of 6,6-dimethyl-6H-benzo[cd]pyrene compounds, and the obtained 6,6-dimethyl-6H-benzo[cd]pyrene compounds have excellent performance. The organic electroluminescent device prepared by using the 6,6-dimethyl-6H-benzo[cd]pyrene compounds provided by the present invention as the light-emitting layer material has a lower driving voltage, a higher current efficiency and a longer life.

[0095] 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 6,6-dimethyl-6H-benzo[cd]pyrene compound, characterized in that: The 6,6-dimethyl-6H-benzo[cd]pyrene compound has a structure as shown in the following formula I: Wherein, Ar is selected from substituted or unsubstituted C6-C30 aryl groups; The substituted substituent is selected from at least one of a C6-C20 aryl group and a C1-C6 alkyl group; The hydrogen atoms in the compound of formula I may each independently be substituted by any one of a deuterium atom, -F, -CN, a C1-C12 alkyl group, a C6-C30 aryl group or a C3-C30 heteroaryl group.

2. The 6,6-dimethyl-6H-benzo[cd]pyrene compound according to claim 1, characterized in that: The 6,6-dimethyl-6H-benzo[cd]pyrene compound has a structure shown in the following formula I-1 or formula I-2: Wherein, Ar in the compound of formula I-1 or formula I-2 has the same definition as in claim 1; The hydrogen atoms in the compound of formula I-1 or formula I-2 may each independently be substituted by any one of a deuterium atom, -F, -CN, a C1-C12 alkyl group, a C6-C30 aryl group or a C3-C30 heteroaryl group.

3. The 6,6-dimethyl-6H-benzo[cd]pyrene compound according to claim 1 or 2, characterized in that: The C6-C30 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, indenyl, fluorenyl, perylenyl, phenanthrenyl, pyrenyl, fluoranthenyl or triphenylenyl; Preferably, the C3-C30 heteroaryl group is selected from any one of triazine, pyrazinyl, pyrimidinyl, pyridyl, isoquinolyl, quinolyl, quinoxalinyl, quinazolinyl, imidazolyl, benzimidazolyl, dibenzofuranyl, dibenzothiophenyl, benzodibenzofuranyl, benzodibenzothiophenyl, dinaphthofuranyl or dinaphthothiophenyl; Preferably, the C6-C20 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl or phenanthrenyl; Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl or cyclohexyl; Preferably, the C1-C6 alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl or cyclohexyl.

4. The 6,6-dimethyl-6H-benzo[cd]pyrene compound according to any one of claims 1 to 3, characterized in that: Ar is selected from the following substituted or unsubstituted groups: at least one of naphthyl, phenyl, biphenyl, and anthracenyl; The substituted substituent is selected from at least one of phenyl, naphthyl, phenanthrenyl, and biphenyl; Preferably, the hydrogen atoms in the compound of formula I can be replaced by any one of deuterium atoms (-D), -F, -CN, phenyl, naphthyl, biphenyl, methyl, ethyl, isopropyl, tert-butyl or cyclohexyl, more preferably deuterium atoms.

5. The 6,6-dimethyl-6H-benzo[cd]pyrene compound according to any one of claims 1 to 4, characterized in that: The 6,6-dimethyl-6H-benzo[cd]pyrene compound is selected from any one of the following compounds: Preferably, the compound of formula I is selected from any one of the following compounds:

6. An intermediate, characterized in that The intermediate includes a compound having a structure shown in the following formula MA: Wherein, X is selected from any one of F, Cl, Br or I; The intermediate is used to prepare the 6,6-dimethyl-6H-benzo[cd]pyrene compound as described in any one of claims 1 to 5.

7. The intermediate according to claim 6, characterized in that The intermediates include the following compounds: Wherein, X is selected from any one of F, Cl, Br or I; Preferably, the intermediate includes the following compounds:

8. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises the 6,6-dimethyl-6H-benzo[cd]pyrene compound according to any one of claims 1 to 5.

9. The organic electroluminescent device according to claim 8, characterized in that: 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 includes the 6,6-dimethyl-6H-benzo[cd]pyrene compound according to any one of claims 1 to 5; Preferably, the organic layer comprises a light-emitting layer; The host material of the light-emitting layer includes the 6,6-dimethyl-6H-benzo[cd]pyrene compound according to any one of claims 1 to 5.

10. A display device, characterized in that: The display device comprises the organic electroluminescent device according to claim 8 or 9.

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