Dihydroacenaphthenyl derivative organic luminescent material, preparation method and electroluminescent device
By using dihydrogenase-based derivatives as organic luminescent materials, the problems of insufficient purity, stability and efficiency of blue light materials are solved, and organic electroluminescent devices with high color purity and long life are realized, reducing the driving voltage and improving the photoelectric efficiency.
Patent Information
- Application Number
- CN202510368241.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2024-03-26
- Filing Date
- 2025-03-26
- Publication Date
- 2025-08-12
AI Technical Summary
Existing blue light organic electroluminescent materials have shortcomings in terms of purity, stability and efficiency, and are difficult to meet the requirements of high-end display and lighting fields.
Using dihydrogenase-based derivatives as organic luminescent materials, high color purity organic electroluminescent devices are prepared by specific synthetic methods, including stacked structures to improve luminescence efficiency and lifetime.
A deep blue luminescent material with high color purity and long life is achieved, reducing the driving voltage of the device and improving the photoelectric efficiency.
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Figure CN120463646A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of organic electroluminescent devices, and in particular to an acenaphthene derivative organic luminescent material, a preparation method and an electroluminescent device. Background Art
[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 luminescent materials is represented by tris(8-hydroxyquinoline)aluminum (Alq3), and the second generation is phosphorescent materials of heavy metal complexes. Electroluminescent materials are composed of three primary colors: red, green and blue. Among them, except for blue light materials, the performance of red and green light materials can meet the requirements of the lighting field and high-end display. This is mainly because the blue light materials are not as pure, stable and efficient as the requirements, and usually require a lamination process to make up for it. Recently, the development of a high-efficiency and long-life blue light organic electroluminescent device has become an urgent issue for R&D personnel. In particular, considering the current requirements of domestic OLED panel manufacturers, the development of an excellent blue light material should be put on the agenda. Summary of the Invention
[0003] The present invention aims to solve existing technical problems and provides a deep blue light-emitting material with high luminous efficiency and long life, a preparation method thereof, and an organic electroluminescent device. The organic electroluminescent device formed from the dihydroacenaphthene derivative of the present invention has high color purity and a long service life.
[0004] In order to solve the above technical problems, the technical solutions provided by the present invention are as follows:
[0005] A dihydroacenaphthenyl derivative organic light-emitting material, whose chemical structure is shown in Formula 1:
[0006]
[0007] wherein R is independently selected from hydrogen, substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C3-C 30 heteroalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted heteroaryl.
[0008] Z1, Z2, Z3, Z4, Z5, Z6, Z7, and Z8 are each independently selected from C or N.
[0009] Z 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, anthracenyl, naphthyl, phenanthrenyl, fluorenyl, spirobifluorenyl, thienyl, furanyl, pyrrolyl, imidazolyl, oxadiazolyl, pyridyl, bipyridyl, triazinyl, acridinyl, quinolyl, quinazolinyl, indolyl, dibenzofuranyl, phenoxazinyl, phenothiazinyl, phenanthridinyl;
[0010] One or more hydrogen atoms in 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, anthracenyl, naphthyl, phenanthrenyl, fluorenyl, spirobifluorenyl, thienyl, furanyl, pyrrolyl, imidazolyl, oxadiazolyl, pyridyl, bipyridyl, triazinyl, acridinyl, quinolyl, quinazolinyl, indolyl, dibenzofuranyl, phenoxazinyl, phenothiazinyl, and phenanthridinyl groups are replaced by tritium.
[0011] More preferably, R is selected from one of the following compounds:
[0012]
[0013] Preferably, the dihydroacenaphthenyl derivative is one of the following compounds:
[0014]
[0015]
[0016]
[0017]
[0018]
[0019]
[0020]
[0021]
[0022]
[0023]
[0024]
[0025]
[0026] The present invention also provides a method for preparing the above-mentioned dihydroacenaphthenyl derivative organic light-emitting material. The reaction process of the preparation method is as follows, and the specific steps are as follows:
[0027]
[0028] (1) Preparation of Intermediate I: 5-acenaphtheneboronic acid, toluene, compound a, anhydrous sodium carbonate, catalyst Pd(pph3)4, ethanol, and deionized water were added to a three-necked flask, stirred evenly, and reacted at 60°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and the reactants were post-treated to obtain Intermediate I.
[0029] (2) Preparation of Intermediate II: Add Intermediate I, toluene, compound b, anhydrous sodium carbonate, catalyst Pd(pph3)4, ethanol, and deionized water into a three-necked flask, stir evenly, and react at 60°C for 12 hours. After the reaction is complete, cool to room temperature and post-treat the reactants to obtain Intermediate II.
[0030] (3) Preparation of dihydroacenaphthene derivative organic light-emitting material: Compound C, intermediate II, cesium carbonate, palladium acetate, tri-tert-butyl phosphine, and xylene were added to a three-necked flask in sequence and reacted at 100°C for 24 hours. After the reaction was completed, the mixture was extracted with dichloromethane and dried over anhydrous magnesium sulfate. The solid was then separated and purified by silica gel column chromatography to obtain a dihydroacenaphthene derivative organic light-emitting material.
[0031] Among them, the meanings of R, Z1, Z2, Z3, Z4, Z5, Z6, Z7, Z8, and Z9 are the same as those in the above formula 1.
[0032] The present invention also provides the use of the above-mentioned dihydroacenaphthenyl derivative organic light-emitting material in the preparation of a light-emitting device. The optical device is 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.
[0033] On the other hand, the present invention provides an organic electroluminescent device, which consists of three parts: a first electrode (positive electrode), a second electrode (negative electrode) and an organic layer therebetween, wherein the organic layer includes the above-mentioned dihydroacenaphthene derivative organic light-emitting material.
[0034] Preferably, the organic layer is a stacked layer, 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.
[0035] Preferably, the light-emitting layer comprises a host material and a guest material. When the guest material is an organic light-emitting material selected from a dihydroacenaphthene derivative, the molar ratio of the guest material is 1-30%.
[0036] In another aspect, the present invention provides an electronic device comprising the organic electroluminescent device as described above.
[0037] Compared with the prior art, the present invention has the following beneficial effects:
[0038] The present invention provides a dihydroacenaphthenyl derivative with a backbone that effectively regulates the formation of conjugated groups, achieving high luminous efficiency. When used as a light-emitting layer material, it can reduce the device's driving voltage and improve the device's photoelectric efficiency and lifespan. Furthermore, when the dihydroacenaphthenyl derivative is used as a light-emitting layer material in an OLED device, the OLED device exhibits high color purity. DETAILED DESCRIPTION
[0039] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.
[0040] Example 1: This example involves the preparation of the above-mentioned compound 13. The specific reaction process is as follows:
[0041]
[0042] (1) Preparation of intermediate 13-3: 5-acenaphtheneboronic acid (12 g, compound 13-1), toluene (200 ml), compound 13-2 (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-necked flask, stirred evenly, and reacted at 60°C for 12 h. After the reaction was completed, the mixture was cooled to room temperature, extracted with ethyl acetate, dried with magnesium sulfate, filtered, concentrated, and finally separated and purified by silica gel column to obtain intermediate 13-3 (11.3 g) with a yield of 52.8%.
[0043] (2) Preparation of intermediate 13-5: Similar to the preparation of intermediate 13-3, only the corresponding amounts of intermediate 13-3 and compound 13-4 were used to replace compound 13-1 and compound 13-2 to obtain intermediate 13-5 (10.2 g) with a yield of 57.8%.
[0044] (3) Preparation of compound 13: Compound 13-6 (4.2 g), intermediate 13-5 (10.2 g), cesium carbonate (Cs2CO3, 11.5 g), palladium acetate (Pd(OAc)2, 0.2 g), tri-tert-butyl phosphine (0.6 g), and xylene (100 ml) were added in sequence into a 250 ml three-necked flask and reacted at 100°C for 24 h. After the reaction was completed, the mixture was extracted with dichloromethane and dried over anhydrous magnesium sulfate. The solid was then separated and purified by silica gel column chromatography to obtain compound 13 (6.2 g) with a yield of 51.4%.
[0045] Mass spectrum m / z: theoretical value: 650.27; measured value: 650.26;
[0046] Theoretical element content C 49 H 34 N2:C,90.43;H,5.27;N,4.30;
[0047] Measured element content C 49 H 34 N2:C,90.40;H,5.25;N,4.28.
[0048] Example 2: This example involves the preparation of the above-mentioned compound 27. The specific reaction process is as follows:
[0049]
[0050] (1) Preparation of Intermediate 27-3: The preparation of Intermediate 13-3 in Example 1 was the same as that of Intermediate 27-3 to obtain Intermediate 27-3.
[0051] (2) The preparation of intermediate 27-5 was similar to that of intermediate 13-5 in Example 1, except that compound 27-4 was used instead of compound 13-4 to obtain intermediate 27-5.
[0052] (3) Preparation of compound 27: The preparation was similar to that of compound 13, except that intermediate 27-5 was used instead of intermediate 13-5, and compound 27 (10.8 g) was finally obtained with a yield of 48.1%.
[0053] Mass spectrum m / z: theoretical value: 651.26; measured value: 651.25;
[0054] Theoretical element content C 49 H 33 ON:C,90.29;H,5.10;O,2.45;N,2.15;
[0055] Measured element content C 49 H 33ON:C,90.28;H,5.09;O,2.44;N,2.14.
[0056] Example 3: This example involves the preparation of the above-mentioned compound 41. The specific reaction process is as follows:
[0057]
[0058] (1) Preparation of Intermediate 41-3: The preparation of Intermediate 13-3 in Example 1 was the same as that of Intermediate 13-3 to obtain Intermediate 41-3.
[0059] (2) The preparation of intermediate 41-5 was similar to that of intermediate 13-5 in Example 1, except that compound 41-4 was used instead of compound 13-4 to obtain intermediate 41-5.
[0060] (3) Preparation of compound 41: The preparation was similar to that of compound 13, except that intermediate 41-5 was used instead of intermediate 13-5, and compound 41 (7.98 g) was finally obtained with a yield of 46.0%.
[0061] Mass spectrum m / z: theoretical value: 742.30; measured value: 742.31;
[0062] Theoretical element content C 55 H 38 ON2:C,88.92;H,5.16;O,2.15;N,3.77;
[0063] Measured element content C 55 H 38 ON2:C,88.91;H,5.17;O,2.14;N,3.76.
[0064] Example 4: This example involves the preparation of the above-mentioned compound 65. The specific reaction process is as follows:
[0065]
[0066] (1) Preparation of Intermediate 65-3: The preparation of Intermediate 13-3 in Example 1 was the same as that of Intermediate 65-3 to obtain Intermediate 65-3.
[0067] (2) The preparation of intermediate 65-5 was similar to the preparation of intermediate 13-5 in Example 1, except that compound 65-4 was used instead of compound 13-4 to obtain intermediate 65-5.
[0068] Preparation of compound 65: Similar to the preparation of compound 13, except that intermediate 65-5 was used instead of intermediate 13-5, and compound 65-6 was used instead of compound 13-6, to finally obtain compound 65 (8.43 g) with a yield of 45.8%.
[0069] Mass spectrum m / z: theoretical value: 700.29; measured value: 700.28;
[0070] Theoretical element content C 53 H 36 N2:C,90.83;H,5.18;N,4.00;
[0071] Measured element content C 53 H 36 N2:C,90.82;H,5.17;N,4.01.
[0072] Device Examples 1-4 and Comparative Example 1:
[0073] Device Examples 1-4 provide an OLED device, which comprises, from bottom to top, a first electrode (positive electrode), a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a second electrode (negative electrode).
[0074] The materials of each layer are as follows:
[0075] First electrode (positive electrode): ITO (indium tin oxide);
[0076] Hole injection layer: HAT-CN;
[0077] Hole transport layer: TAPC;
[0078] Electron transport layer: TmPyPB;
[0079] Electron injection layer: Liq;
[0080] Second electrode (negative electrode): Al;
[0081] The host material of the light-emitting layer is TCTA, and the guest material is the dihydroacenaphthene derivative in the above-mentioned embodiment 1-4.
[0082] The only difference between Comparative Example 1 and Device Examples 1-4 is that the guest material of the light-emitting layer is the compound mCP.
[0083] In the above device examples and comparative example 1, the structural formulas corresponding to the abbreviations of the materials are as follows:
[0084]
[0085] Table 1 Performance test results of device examples 1-4 and comparative examples
[0086] project color LE(cd / A) V(V) LT95(hr) CIEx CIE Device Example 1 blue 4.73 3.47 219 0.16 0.085 Device Example 2 blue 4.58 3.53 262 0.16 0.087 Device Example 3 blue 4.64 3.72 173 0.16 0.090 Device Example 4 blue 4.84 3.56 198 0.16 0.088 Comparative Example 1 blue 3.85 4.8 122 0.13 0.101
[0087] Performance test: The luminous efficiency of the device embodiment and the comparative example was tested. The items and results are shown in Table 1.
[0088] The device performance data is measured at a brightness of 1000 nits, and the lifespan (LT95) data is measured at a current density of 20 mA / cm 2 Calculated under the conditions.
[0089] From the results in Table 1, it can be seen that when the dihydroacenaphthenyl derivative is used as the guest material of the light-emitting layer, the organic electroluminescent device exhibits high color purity. Most importantly, the organic electroluminescent devices of device examples 1-4 have a long service life.
[0090] The present invention uses the above-described embodiments to illustrate the dihydroacenaphthenyl derivative organic light-emitting material, preparation method, and application thereof. However, the present invention is not limited to the above-described embodiments, and it does not mean that the present invention must rely on the above-described embodiments in order to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements of various raw materials in the products of the present invention, addition of auxiliary components, and selection of specific methods, etc., are all within the scope of protection and disclosure of the present invention.
Claims
1. A dihydroacenaphthenyl derivative organic light-emitting material, characterized in that: The dihydroacenaphthene derivative organic light-emitting material has a structure shown in Formula 1: wherein R is independently selected from hydrogen, substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C3-C 30 heteroalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted heteroaryl; wherein Z1, Z2, Z3, Z4, Z5, Z6, Z7, and Z8 are each independently selected from C or N; 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, anthracenyl, naphthyl, phenanthrenyl, fluorenyl, spirobifluorenyl, thienyl, furanyl, pyrrolyl, imidazolyl, oxadiazolyl, pyridyl, bipyridyl, triazinyl, acridinyl, quinolinyl, quinazolinyl, indolyl, dibenzofuranyl, phenoxazinyl, phenothiazinyl, and phenanthridinyl.
2. An organic light-emitting material of dihydroacenaphthene derivative according to claim 1, wherein said R is selected from one of the following compounds of the structural formula: One or more hydrogen atoms in 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, anthracenyl, naphthyl, phenanthrenyl, fluorenyl, spirobifluorenyl, thienyl, furanyl, pyrrolyl, imidazolyl, oxadiazolyl, pyridyl, bipyridyl, triazinyl, acridinyl, quinolyl, quinazolinyl, indolyl, dibenzofuranyl, phenoxazinyl, phenothiazinyl, and phenanthridinyl groups are replaced by tritium.
3. The dihydroacenaphthene derivative organic light-emitting material according to claim 1 or 2, characterized in that: The dihydroacenaphthene derivative organic light-emitting material is any one of the following compounds:
4. A method for preparing an organic light-emitting material of a dihydroacenaphthene derivative according to any one of claims 1 to 3, characterized in that: The reaction process of the preparation method is as follows, and comprises the following steps: (1) Preparation of intermediate I: 5-acenaphtheneboronic acid, toluene, compound a, anhydrous sodium carbonate, catalyst Pd(pph3)4, ethanol, and deionized water were added to a three-necked flask, stirred evenly, and reacted at 60°C for 12 hours. After the reaction was completed, the reactants were post-treated to obtain intermediate I; (2) Preparation of Intermediate II: Add Intermediate I, toluene, compound b, anhydrous sodium carbonate, catalyst Pd(pph3)4, ethanol, and deionized water into a three-necked flask, stir evenly, and react at 60°C for 12 hours. After the reaction is complete, cool to room temperature and post-treat the reactants to obtain Intermediate II. (3) Preparation of dihydroacenaphthene derivative organic light-emitting material: Compound C, intermediate II, cesium carbonate, palladium acetate, tri-tert-butyl phosphine, and xylene were added to a three-necked flask in sequence and reacted at 100°C for 24 hours. After the reaction was completed, the mixture was extracted with dichloromethane and dried over anhydrous magnesium sulfate. The solid was then separated and purified by silica gel column chromatography to obtain a dihydroacenaphthene derivative organic light-emitting material.
5. A use of the dihydroacenaphthenyl derivative organic light-emitting material according to any one of claims 1 to 3, characterized in that: The dihydroacenaphthenyl derivative organic light-emitting material can be used in preparing light-emitting devices.
6. The use according to claim 5, characterized in that The light-emitting device is 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.
7. An organic electroluminescent device, characterized in that: The organic electroluminescent device consists of three parts: a first electrode, a second electrode, and an organic layer therebetween. The organic layer comprises the dihydroacenaphthene derivative organic light-emitting material according to any one of claims 1 to 3.
8. The electroluminescent device according to claim 7, characterized in that: The organic layer is a stacked layer, 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.
9. The electroluminescent device according to claim 8, characterized in that The light-emitting layer comprises a host material and a guest material. When the guest material is the dihydroacenaphthene derivative organic light-emitting material according to any one of claims 1 to 3, the molar ratio of the guest material is 1-30%.
10. An electronic device, characterized in that: The electronic device comprises the organic electroluminescent device according to any one of claims 7 to 9.