Acenaphthene derivative organic light-emitting material, preparation method and electroluminescent device

Abstract

A deep blue light emitting material with high luminous efficiency and long life, a preparation method thereof, and an organic electroluminescent device are provided. The present invention relates to an acenaphthene derivative organic light-emitting material as shown in formula 1. The light-emitting material has an acenaphthene skeleton and has a "Y" shaped structure. JPEG0007639226000037.jpg63170

Description

[Technical field]

[0001] The present invention relates to the field of organic electroluminescent devices, in particular to acenaphthene derivative organic light-emitting materials, preparation methods and electroluminescent devices. [Background technology]

[0002] Compared with traditional light-emitting diodes (LEDs), organic light-emitting diodes (OLEDs) have the advantages of high brightness, fast response, low driving voltage, high luminous efficiency, and flexible design. The first generation of OLED emitting materials is represented by tris(8-hydroxyquinoline)aluminum (Alq3), and the second generation is a phosphorescent material of heavy metal complex. Electroluminescent materials are composed of three primary colors: red, green, and blue. In addition to blue light materials, the performance of red light materials and green light materials can meet the requirements of the lighting field and high-end displays. The main reason is that the purity, stability, and efficiency of blue light materials are low and cannot meet the requirements, and a lamination process is usually required to make up for it. In recent years, the development of high-efficiency and long-life blue light organic electroluminescent devices has become an urgent task for researchers. Especially considering the current requirements of domestic OLED panel manufacturers, the development of excellent blue light materials should be on the agenda. Summary of the Invention [Problem to be solved by the invention]

[0003] The present invention aims to solve the existing technical problems and provide a deep blue light emitting material with high luminous efficiency and long life, its preparation method, and organic electroluminescent device. The organic electroluminescent device formed by the acenaphthene derivative of the present invention has high color purity and long life. [Means for solving the problem]

[0004] The technical solutions provided by the present invention to solve the above technical problems are as follows: The acenaphthene derivative organic light-emitting material has the chemical structure shown in Formula 1. JPEG0007639226000001.jpg63170In the formula, R is independently hydrogen or a substituted or unsubstituted C1-C 30 Alkyl groups, substituted or unsubstituted C3-C 30 Heteroalkyl groups, substituted or unsubstituted C3-C6 cycloalkyl groups, substituted or unsubstituted C6-C 30 The aryl group is selected from a substituted or unsubstituted heteroaryl group.

[0005] Z1, Z2, Z3, Z4, Z5, Z6, Z7, and Z8 are each independently selected from C or N.

[0006] Z9 is selected from hydrogen, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, terphenyl, anthryl, naphthyl, phenanthryl, fluorenyl, spirobifluorenyl, thienyl, furyl, pyrrolyl, imidazolyl, diazolyl, pyridyl, bipyridyl, triazinyl, acridinyl, quinolyl, quinazolinyl, indolyl, dibenzofuryl, phenoxazinyl, phenothiazinyl, and phenanthridinyl. One or more hydrogen atoms of the methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, terphenyl, anthryl, naphthyl, phenanthryl, fluorenyl, spirobifluorenyl, thienyl, furyl, pyrrolyl, imidazolyl, diazolyl, pyridyl, bipyridyl, triazinyl, acridinyl, quinolyl, quinazolinyl, indolyl, dibenzofuryl, phenoxazinyl, phenothiazinyl, and phenanthridinyl are substituted with tritium.

[0007] More preferably, said R is selected from one of the compounds of the following structural formulas: JPEG0007639226000002.jpg55170

[0008] Preferably, the acenaphthene derivative is one of the following compounds: JPEG0007639226000003.jpg70170JPEG0007639226000004.jpg201170JPEG0007639226000005.jpg219170 JPEG0007639226000006.jpg213170JPEG0007639226000007.jpg223170JPEG0007639226000008.jpg219170 JPEG0007639226000009.jpg215170JPEG0007639226000010.jpg213170JPEG0007639226000011.jpg220170 JPEG0007639226000012.jpg218170JPEG0007639226000013.jpg231170JPEG0007639226000014.jpg223170

[0009] The present invention further provides a method for preparing the above-mentioned acenaphthene derivative organic light-emitting material, the reaction process of which is shown below, and the specific steps are as follows: JPEG0007639226000015.jpg66170

[0010] (1) Preparation of intermediate I: Put acenaphthene-5-boronic acid, toluene, compound a, anhydrous sodium carbonate, catalyst Pd(pph3)4, ethanol, and deionized water into a three-neck flask, stir evenly, and react at 60°C for 12 hours. After the reaction is completed, cool to room temperature, and then treat the reactant to obtain intermediate I.

[0011] (2) Preparation of intermediate II: intermediate I, toluene, compound b, anhydrous sodium carbonate, catalyst Pd(pph3)4, ethanol, and deionized water are added to a three-neck flask, and the mixture is stirred uniformly and reacted at 60°C for 12 hours. After the reaction is completed, the mixture is cooled to room temperature, and the reactant is post-treated to obtain intermediate II.

[0012] (3) Preparation of acenaphthene derivative organic luminescent material: Compound c, intermediate II, cesium carbonate, palladium acetate, tri-tert-butylphosphine, and xylene are placed in a three-neck flask in this order, and reacted at 100°C for 24 hours. After the reaction is completed, the mixture is extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solid is separated and purified by silica gel column chromatography to obtain an acenaphthene derivative organic luminescent material.

[0013] Here, the meanings of R, Z1, Z2, Z3, Z4, Z5, Z6, Z7, Z8, and Z9 are the same as those corresponding to formula 1 above.

[0014] The present invention further provides a use of the above-mentioned acenaphthene derivative organic light-emitting material in preparing a light-emitting device, the optical device being any one of a flexible flat panel display, a flexible blue lighting system, a white flat panel lighting system, an organic solar cell, a light-emitting chemical cell, an organic thin film diode, and an organic light-emitting diode.

[0015] In another aspect, the present invention provides an organic electroluminescent device, which is composed of three parts: a first electrode (positive electrode), a second electrode (negative electrode), and an organic layer therebetween, the organic layer comprising the acenaphthene derivative organic light-emitting material described above.

[0016] Preferably, the organic layer is a stack, including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

[0017] Preferably, the light-emitting layer includes a host material and a guest material, and when an acenaphthene derivative organic light-emitting material is selected as the guest material, the molar percentage of the guest material is 1-30%.

[0018] In another aspect, the present invention provides an electronic device, the electronic device comprising an organic electroluminescent device as described above.

[0019] Compared with the prior art, the present invention has the following beneficial effects: The present invention provides a compound having an acenaphthene group as a backbone, which effectively controls the formation of a conjugated group and can obtain higher luminous efficiency, and when used as an emitting layer material, can reduce the driving voltage of a device and improve the photoelectric efficiency and life of the device. In addition, when the acenaphthene derivative described in the present invention is used as an emitting layer material of an OLED device, the OLED device exhibits a characteristic of high color purity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The technical solutions of the present invention will be further described below with reference to specific embodiments. Those skilled in the art should understand that the above examples are only for helping the understanding of the present invention, and should not be regarded as specific limitations to the present invention.

[0021] Example 1: This example relates to the preparation of the above compound 1, and the specific reaction process is as follows: JPEG0007639226000016.jpg68170

[0022] (1) Preparation of intermediate 1-3: Acenaphthene-5-boronic acid (12 g, compound 1-1), toluene (200 ml), compound 1-2 (15 g), anhydrous sodium carbonate (11.1 g), catalyst Pd(pph3)4 (30.1 g), ethanol (40 g), and deionized water (40 g) were added to a three-neck flask, and the mixture was stirred uniformly and reacted at 60°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with ethyl acetate, dried over magnesium sulfate, filtered, concentrated, and finally separated and purified using a silica gel column to obtain intermediate 1-3 (14.6 g) in a yield of 83%.

[0023] (2) Preparation of intermediate 1-5: The same procedure as in the preparation of intermediate 1-3 was repeated, except that instead of compound 1-1 and compound 1-2, only the corresponding amounts of intermediate 1-3 and compound 1-4 were used to obtain intermediate 1-5 (11.5 g) in a yield of 73%.

[0024] (3) Preparation of compound 1: Compound 1-6 (6.5 g), intermediate 1-5 (19.8 g), cesium carbonate (Cs2CO3, 11.5 g), palladium acetate (Pd(OAc)2, 0.2 g), tri-tert-butylphosphine (0.6 g), and xylene (100 ml) were sequentially placed in a 250 ml three-neck flask and reacted at 100°C for 24 hours. After completion of the reaction, the mixture was extracted with dichloromethane and dried over anhydrous magnesium sulfate. The solid was separated and purified by silica gel column chromatography to obtain compound 1 (14.4 g) in a yield of 68%.

[0025] Mass spectrum m / z: theoretical: 652.29; observed: 649.38; Theoretical elemental content C49H36N2: C, 90.15; H, 5.56; N, 4.29; Measured elemental content C49H36N2: C, 89.10; H, 5.22; N, 3.98.

[0026] Example 2: This example relates to the preparation of the above compound 4, and the specific reaction process is as follows: JPEG0007639226000017.jpg73170(1) Preparation of intermediate 2-3: The preparation of intermediate 2-3 was the same as that of intermediate 1-3 in Example 1, and intermediate 2-3 was obtained.

[0027] (2) The preparation of intermediate 2-5 was similar to that of intermediate 1-5 in Example 1, except that compound 2-4 was used instead of compound 1-4, to obtain intermediate 2-5.

[0028] (3) Preparation of compound 2: The same as the preparation of compound 1, except that intermediate 2-5 was used instead of intermediate 1-5, and finally compound 4 (9.36 g) was obtained in 65% yield.

[0029] Mass spectrum m / z: theoretical: 662.27; observed: 665.82; Theoretical elemental content C50H34N2: C, 90.60; H, 5.17; N, 4.23; The measured elemental content of C50H34N2 was: C, 90.05; H, 4.96; N, 4.02.

[0030] Example 3: This example relates to the preparation of the above compound 13, and the specific reaction process is as follows: JPEG0007639226000018.jpg73170(1) Preparation of intermediate 3-3: The preparation of intermediate 3-3 was the same as that of intermediate 1-3 in Example 1, to obtain intermediate 3-3.

[0031] (2) The preparation of intermediate 3-5 was similar to that of intermediate 1-5 in Example 1, except that compound 3-4 was used instead of compound 1-4, to obtain intermediate 3-5.

[0032] (3) Preparation of compound 13: The same as the preparation of compound 1, except that intermediate 3-5 was used instead of intermediate 1-5, and finally compound 13 (8.54 g) was obtained in 68% yield.

[0033] Mass spectrum m / z: theoretical: 650.27; observed: 648.64; Theoretical elemental content C49H34N2: C, 90.43; H, 5.27; N, 4.30; Measured elemental content C49H34N2: C, 89.91; H, 5.01; N, 4.15.

[0034] Example 4: This example relates to the preparation of the above compound 54, and the specific reaction process is as follows: JPEG0007639226000019.jpg73170(1) Preparation of intermediate 4-3: The preparation of intermediate 4-3 was the same as that of intermediate 1-3 in Example 1, to obtain intermediate 4-3.

[0035] (2) The preparation of intermediate 4-5 was similar to the preparation of intermediate 1-5 in Example 1, except that compound 4-4 was used instead of compound 1-4, to obtain intermediate 4-5.

[0036] Preparation of compound 54: The procedure was the same as that of compound 1, except that intermediate 4-5 was used instead of intermediate 1-5, and compound 4-6 was used instead of compound 1-6. Finally, compound 54 (9.55 g) was obtained in a yield of 73%.

[0037] Mass spectrum m / z: theoretical: 652.26; observed: 650.37; Theoretical element content C 47 H 32 N4: C, 86.48; H, 4.94; N, 8.58; Measured element content C 47 H 32 N4: C, 84.92; H, 4.76; N, 7.86.

[0038] Device Examples 1-4 and Comparative Example 1: Device Examples 1-4 provide OLED devices that, from bottom to top, are a first electrode (anode), a hole injection layer, a hole transport layer, an electron blocking layer, an emissive layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a second electrode (anode).

[0039] The constituent materials of each layer are as follows: First electrode (positive electrode): ITO (indium tin oxide); Hole injection layer: HAT-CN; Hole transport layer: TAPC; Electron transport layer: TmPyPB; Electron injection layer: Liq; 2nd electrode (negative electrode): Al; TCTA was selected as the host material for the light-emitting layer, and the acenaphthene derivative of Example 1-4 described above was selected as the guest material.

[0040] The only difference between Comparative Example 1 and Device Examples 1-4 is that the guest material in the light-emitting layer is the compound mCP.

[0041] In the above device examples and comparative example 1, the structural formulas corresponding to the abbreviated names of the materials are as follows. JPEG0007639226000020.jpg85170Performance test: A luminous efficiency test was carried out for the device examples and comparative examples. The items and results are shown in Table 1.

[0042] Here, device performance data is measured at a brightness of 1000nits, and lifetime (LT95) data is measured at 20mA / cm 2 The calculation was performed at a current density of 1000 s.

[0043] JPEG0007639226000021.jpg38170From the results in Table 1, it can be seen that when an acenaphthene derivative is used as a guest material in the light-emitting layer, the organic electroluminescent device exhibits high color purity. Most importantly, the organic electroluminescent device of Device Example 1-4 has a long service life.

[0044] The present invention uses the above examples to illustrate the acenaphthene derivative organic light-emitting material of the present invention, the preparation method and its use, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must be carried out by relying on the above examples. Those skilled in the art should understand that any improvements to the present invention, equivalent replacement of each raw material of the product of the present invention, addition of auxiliary components, selection of specific methods, etc. are all included in the protection scope and disclosure scope of the present invention.

Claims

1. An acenaphthene derivative organic light-emitting material, the acenaphthene derivative organic light-emitting material having a structure shown in Formula 1: In the formula, R is independently hydrogen, substituted or unsubstituted C １ -C ３０ Alkyl group, substituted or unsubstituted C ３ -C ３０ Heteroalkyl groups, substituted or unsubstituted C ３ -C ６ Cycloalkyl groups, substituted or unsubstituted C ６ -C ３０ aryl groups, substituted or unsubstituted heteroaryl groups; Here, Z １ , Z ２ , Z ３ , Z ４ , Z ５ , Z ６ , Z ７ , Z ８ are each independently selected from C or N; Z ９ is selected from hydrogen, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, terphenyl, anthryl, naphthyl, phenanthryl, fluorenyl, spirobifluorenyl, thienyl, furyl, pyrrolyl, imidazolyl, diazolyl, pyridyl, bipyridyl, triazinyl, acridinyl, quinolyl, quinazolinyl, indolyl, dibenzofuryl, phenoxazinyl, phenothiazinyl, and phenanthridinyl.

2. R is selected from one of the compounds of the following structural formulas: The acenaphthene derivative organic light-emitting material according to claim 1, wherein one or more hydrogen atoms of the methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, terphenyl, anthryl, naphthyl, phenanthryl, fluorenyl, spirobifluorenyl, thienyl, furyl, pyrrolyl, imidazolyl, diazolyl, pyridyl, bipyridyl, triazinyl, acridinyl, quinolyl, quinazolinyl, indolyl, dibenzofuryl, phenoxazinyl, phenothiazinyl, and phenanthridinyl are substituted with tritium.

3. 2. The acenaphthene derivative organic light-emitting material according to claim 1, wherein the acenaphthene derivative organic light-emitting material is any one of the following compounds:

4. A method for preparing an acenaphthene derivative organic light-emitting material according to any one of claims 1 to 3, characterized in that the reaction process of the preparation method is as follows and includes the following steps: (1) Preparation of intermediate I: In a three-neck flask, acenaphthene-5-boronic acid, toluene, compound a, anhydrous sodium carbonate, catalyst Pd(pph ３ ) ４ ethanol and deionized water were added, and the mixture was stirred uniformly and reacted at 60° C. for 12 hours. After the reaction was completed, the reactant was post-treated to obtain intermediate I. (2) Preparation of intermediate II: In a three-neck flask, intermediate I, toluene, compound b, anhydrous sodium carbonate, catalyst Pd(pph ３ ) ４ , ethanol, and deionized water were added, and the mixture was stirred uniformly and reacted at 60° C. for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the reactant was post-treated to obtain intermediate II. (3) Preparation of acenaphthene derivative organic luminescent material: Compound c, intermediate II, cesium carbonate, palladium acetate, tri-tert-butylphosphine, and xylene are sequentially placed in a three-neck flask and reacted at 100° C. for 24 hours. After the reaction is completed, the mixture is extracted with dichloromethane and dried over anhydrous magnesium sulfate. The solid is separated and purified by silica gel column chromatography to obtain an acenaphthene derivative organic luminescent material.

5. Use of the acenaphthene derivative organic light-emitting material according to any one of claims 1 to 3, characterized in that the acenaphthene derivative organic light-emitting material can be used in the manufacture of a light-emitting device.

6. 6. The use according to claim 5, wherein the light emitting device is one of a flexible flat panel display, a flexible blue lighting system, a white flat panel lighting system, an organic solar cell, a light emitting chemical cell, an organic thin film diode, and an organic light emitting diode.

7. 13. An organic electroluminescent device, comprising three parts: a first electrode, a second electrode, and an organic layer therebetween, the organic layer comprising the acenaphthene derivative organic light-emitting material according to claim 1.

8. 8. The electroluminescent device of claim 7, wherein the organic layer is a stack, comprising a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

9. The electroluminescent device of claim 8, wherein the light-emitting layer comprises a host material and a guest material, and when the guest material is selected as the acenaphthene derivative organic light-emitting material of claim 1, the molar percentage of the guest material is 1-30%.

10. 10. An electronic device comprising the organic electroluminescent device according to claim 7.

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