CN118255717A - A dihydroacenaphthene derivative organic luminescent material, preparation method and electroluminescent device - Google Patents

Abstract

The present invention relates to the field of organic electroluminescent devices, and discloses a dihydroacenaphthene derivative organic luminescent material, a preparation method and an organic electroluminescent device. The dihydroacenaphthene derivative organic luminescent material has a dihydroacenaphthene skeleton and a "Y"-like structure, as shown in Formula 1. The organic electroluminescent compound provided by the present invention has high color purity, high lifespan and excellent luminous efficiency when used in an organic light-emitting device.

Description

A dihydroacenaphthene derivative organic luminescent material, preparation method and electroluminescent device

Technical Field

The 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 technique

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 (Alq ₃ ), and the second generation is phosphorescent materials of heavy metal complexes. Electroluminescent materials are composed of three primary colors: red, green and blue. 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 cannot meet the requirements in terms of purity, stability and efficiency, and usually require lamination processes 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, especially considering the requirements of current domestic OLED panel manufacturers. The development of an excellent blue light material should be put on the agenda.

Summary of the invention

The present invention aims to solve the 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 by the dihydroacenaphthene derivative of the present invention has high color purity and long service life.

In order to solve the above technical problems, the technical solutions provided by the present invention are as follows:

A dihydroacenaphthene derivative organic light-emitting material, the chemical structure of which is shown in Formula 1:

Wherein, R is independently selected from hydrogen, substituted or unsubstituted C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₃ -C ₃₀ heteroalkyl, substituted or unsubstituted C ₃ -C ₆ cycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, and substituted or unsubstituted heteroaryl.

Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ and Z ₈ are each independently selected from C or N.

_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;

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, phenanthryl, fluorenyl, spirobifluorenyl, thienyl, furanyl, pyrrolyl, imidazolyl, oxadiazolyl, pyridyl, bipyridyl, triazine, acridinyl, quinolyl, quinazolinyl, indolyl, dibenzofuranyl, phenoxazinyl, phenothiazinyl and phenanthridinyl groups are replaced by tritium.

More preferably, R is selected from one of the following compounds:

Preferably, the dihydroacenaphthene derivative is one of the following compounds:

The present invention also provides a method for preparing the above-mentioned dihydroacenaphthene derivative organic light-emitting material. The reaction process of the preparation method is as follows, and the specific steps are as follows:

(1) Preparation of intermediate I: 5-acenaphtheneboronic acid, toluene, compound a, anhydrous sodium carbonate, catalyst Pd(pph ₃ ) ₄ , ethanol and deionized water were added to a three-necked flask, stirred evenly, reacted at 60° C. for 12 h, and after the reaction was completed, cooled to room temperature, and the reactant was post-treated to obtain intermediate I;

(2) Preparation of Intermediate II: Add Intermediate I, toluene, compound b, anhydrous sodium carbonate, catalyst Pd(pph ₃ ) ₄ , ethanol and deionized water into a three-necked flask, stir evenly, react at 60° C. for 12 h, and after the reaction is completed, cool to room temperature, and post-treat the reactant 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, it 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.

Here, R, Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , Z ₈ , and Z ₉ have the same meanings as those in the above formula 1.

The present invention also provides the use of the above-mentioned dihydroacenaphthene 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.

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 comprises the above-mentioned dihydroacenaphthene derivative organic light-emitting material.

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.

Preferably, the light-emitting layer comprises a host material and a guest material. When the guest material is an organic light-emitting material of a dihydroacenaphthene derivative, the molar percentage of the guest material is 1-30%.

In another aspect, the present invention provides an electronic device, wherein the electronic device comprises the organic electroluminescent device as described above.

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

The present invention provides a dihydroacenaphthene-based material with a skeleton, which can effectively regulate the formation of conjugated groups to obtain higher luminous efficiency. When used as a light-emitting layer material, the driving voltage of the device can be reduced and the photoelectric efficiency and life of the device can be improved. In addition, when the dihydroacenaphthene-based derivative of the present invention is used as a light-emitting layer material of an OLED device, the OLED device exhibits the characteristics of high color purity.

Detailed ways

The technical solution of the present invention is further described below by specific implementation methods. 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.

Example 1: This example involves the preparation of the above-mentioned compound 1, and the specific reaction process is as follows:

(1) Preparation of intermediate 1-3: 5-acenaphtheneboronic acid (12 g, compound 1-1) and toluene (200 ml), compound 1-2 (15 g), anhydrous sodium carbonate (11.1 g), catalyst Pd(pph ₃ ) 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 1-3 (14.6 g) with a yield of 83%.

(2) Preparation of intermediate 1-5: Similar to the preparation of intermediate 1-3, only the corresponding amount of intermediate 1-3 and compound 1-4 were used to replace compound 1-1 and compound 1-2 to obtain intermediate 1-5 (11.5 g) with a yield of 73%.

(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-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 1 (14.4 g) with a yield of 68%.

Mass spectrum m/z: theoretical value: 652.29; measured value: 649.38;

Theoretical element content C ₄₉ H ₃₆ N ₂ : C, 90.15; H, 5.56; N, 4.29;

Measured element contents of C ₄₉ H ₃₆ N ₂ : C, 89.10; H, 5.22; N, 3.98.

Example 2: This example involves the preparation of the above-mentioned compound 4, and the specific reaction process is as follows:

(1) Preparation of Intermediate 2-3: The preparation of Intermediate 1-3 in Example 1 was the same as that of Intermediate 1-3 to obtain Intermediate 2-3.

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

(3) Preparation of Compound 2: Similar to 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 with a yield of 65%.

Mass spectrum m/z: theoretical value: 662.27; measured value: 665.82;

Theoretical element content C ₅₀ H ₃₄ N ₂ : C, 90.60; H, 5.17; N, 4.23;

Measured element contents of C ₅₀ H ₃₄ N ₂ : C, 90.05; H, 4.96; N, 4.02.

Example 3: This example involves the preparation of the above-mentioned compound 13, and the specific reaction process is as follows:

(1) Preparation of Intermediate 3-3: The preparation of Intermediate 1-3 in Example 1 was the same as that of Intermediate 1-3 to obtain Intermediate 3-3.

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

(3) Preparation of Compound 13: The preparation was similar to that of Compound 1, except that Intermediate 3-5 was used instead of Intermediate 1-5 to finally obtain Compound 13 (8.54 g) with a yield of 68%.

Mass spectrum m/z: theoretical value: 650.27; measured value: 648.64;

Theoretical element content C ₄₉ H ₃₄ N ₂ : C, 90.43; H, 5.27; N, 4.30;

Measured element contents of C ₄₉ H ₃₄ N ₂ : C, 89.91; H, 5.01; N, 4.15.

Example 4: This example involves the preparation of the above-mentioned compound 54, and the specific reaction process is as follows:

(1) Preparation of intermediate 4-3: The preparation of intermediate 1-3 in Example 1 was the same as that of intermediate 1-3 to obtain intermediate 4-3.

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

Preparation of compound 54: Similar to the preparation 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 obtaining compound 54 (9.55 g) with a yield of 73%.

Mass spectrum m/z: theoretical value: 652.26; measured value: 650.37;

Theoretical element content C ₄₇ H ₃₂ N ₄ : C, 86.48; H, 4.94; N, 8.58;

Measured element contents of C ₄₇ H ₃₂ N ₄ : C, 84.92; H, 4.76; N, 7.86.

Device Examples 1-4 and Comparative Example 1:

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).

The 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;

Second electrode (negative electrode): Al;

The main material of the light-emitting layer is TCTA, and the guest material is the dihydroacenaphthene derivative in the above-mentioned embodiment 1-4.

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.

In the above device embodiment and comparative example 1, the structural formula corresponding to the abbreviation of the material is as follows:

Performance test: The luminous efficiency of the device embodiments and comparative examples was tested, and the items and results are shown in Table 1.

The device performance data is measured at a brightness of 1000 nits, and the lifespan (LT95) data is calculated at a current density of 20 mA/ ^cm2 .

Table 1 Performance test results of device embodiments 1-4 and comparative examples

project color LE(cd/A) V(V) LT95(hr) CIEx CIE Device Example 1 blue 4.76 3.43 223 0.16 0.83 Device Example 2 blue 4.61 3.76 256 0.16 0.086 Device Example 3 blue 4.56 3.46 199 0.16 0.092 Device Example 4 blue 4.88 3.65 156 0.16 0.090 Comparative Example 1 blue 3.85 4.8 122 0.13 0.101

From the results in Table 1, it can be seen that when the dihydroacenaphthene derivative is used as the guest material of the light-emitting layer, the organic electroluminescent device shows high color purity. Most importantly, the organic electroluminescent devices of device examples 1-4 have a long service life.

The present invention uses the above-mentioned embodiments to illustrate the dihydroacenaphthene derivative organic light-emitting material, preparation method and application thereof, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments 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 (10)

1. A dihydroacenaphthene 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 C ₁ -C ₃₀ alkyl, substituted or unsubstituted C ₃ -C ₃₀ heteroalkyl, substituted or unsubstituted C ₃ -C ₆ cycloalkyl, substituted or unsubstituted C ₆ -C ₃₀ aryl, substituted or unsubstituted heteroaryl; wherein Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₆ , Z ₇ , and Z ₈ are each independently selected from C or N; _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, triazine, acridinyl, quinolyl, quinazolinyl, indolyl, dibenzofuranyl, phenoxazinyl, phenothiazinyl, phenanthridinyl. 2. An organic light-emitting material of dihydroacenaphthene derivative as claimed in 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, phenanthryl, fluorenyl, spirobifluorenyl, thienyl, furanyl, pyrrolyl, imidazolyl, oxadiazolyl, pyridyl, bipyridyl, triazine, 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 the dihydroacenaphthene 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 comprises the following steps: (1) Preparation of intermediate I: 5-acenaphtheneboric acid, toluene, compound a, anhydrous sodium carbonate, catalyst Pd(pph ₃ ) ₄ , ethanol, and deionized water were added to a three-necked flask, stirred evenly, and reacted at 60° C. for 12 h. After the reaction was completed, the reactant was post-treated to obtain intermediate I; (2) Preparation of Intermediate II: Add Intermediate I, toluene, compound b, anhydrous sodium carbonate, catalyst Pd(pph ₃ ) ₄ , ethanol and deionized water into a three-necked flask, stir evenly, react at 60° C. for 12 h, and after the reaction is completed, cool to room temperature, and post-treat the reactant 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, it 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. Use of the dihydroacenaphthene derivative organic light-emitting material according to any one of claims 1 to 3, characterized in that the dihydroacenaphthene derivative organic light-emitting material can be used in the preparation of a light-emitting device. 6. The application according to claim 5 is 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, and 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, and when the guest material is the dihydroacenaphthene derivative organic light-emitting material as described in any one of claims 1 to 3, the molar percentage 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.