WO2019185060A1

WO2019185060A1 - Compound using arylamine-attached bi-dimethylfluorene as nucleus, and application thereof

Info

Publication number: WO2019185060A1
Application number: PCT/CN2019/080632
Authority: WO
Inventors: 陈海峰; 李崇; 张兆超; 徐浩杰
Original assignee: 江苏三月光电科技有限公司
Priority date: 2018-03-29
Filing date: 2019-03-29
Publication date: 2019-10-03

Abstract

The present invention relates to the technical field of semiconductors. Disclosed are a compound using arylamine-attached bi-dimethylfluorene as a nucleus, and an application thereof. The structure of the compound provided in the present invention is represented in general formula (1). Also disclosed is an application of the compound. The compound in the present invention is not easy to crystallize and aggregate due to intermolecular interaction, and has a good film forming property. The compound in the present invention can be used as a hole transport layer material in an organic electroluminescent device. The organic electroluminescent device in which the compound in the present invention is applied has good photoelectric properties, and can be adapted to and meet application requirements of panel manufacturing enterprises better.

Description

Compound with arylamine and didimethylhydrazine as core and its application

Technical field

The invention relates to a compound with arylamine and didimethyl hydrazine as its core and its application, and belongs to the technical field of semiconductors.

Background technique

Organic Light Emission Diodes (OLED) device technology can be used to manufacture new display products, as well as to create new lighting products. It is expected to replace existing liquid crystal displays and fluorescent lighting, and has a wide application prospect. The OLED light-emitting device is like a sandwich structure, including an electrode material film layer and an organic functional material sandwiched between different electrode film layers, and various functional materials are superposed on each other according to the purpose to form an OLED light-emitting device. The OLED light-emitting device functions as a current device. When a voltage is applied to the electrodes at both ends thereof and the positive and negative charges in the organic layer functional material film layer are applied by the electric field, the positive and negative charges are further recombined in the light-emitting layer, that is, the OLED electroluminescence is generated.

At present, OLED display technology has been applied in the fields of smart phones, tablet computers, etc., and will further expand to large-size applications such as television, but the luminous efficiency and service life of OLED devices are compared with actual product application requirements. Further improvement is needed. At present, research on improving the performance of OLED light-emitting devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and improving the service life of the device. In order to realize the continuous improvement of the performance of OLED devices, it is not only necessary to innovate from the structure and fabrication process of OLED devices, but also to continuously research and innovate OLED photoelectric functional materials, and to create higher performance OLED functional materials.

The OLED optoelectronic functional materials applied to OLED devices can be divided into two categories from the use of charge injection transport materials and luminescent materials. Further, the charge injection transport material may be further classified into an electron injection transport material, an electron blocking material, a hole injection transport material, and a hole blocking material, and the luminescent material may be further divided into a host luminescent material and a dopant material.

In order to produce high-performance OLED light-emitting devices, various organic functional materials are required to have good photoelectric properties. For example, as a charge transport material, it is required to have good carrier mobility, high glass transition temperature, etc., as a main body of the light-emitting layer. The material has good bipolarity, appropriate HOMO/LUMO energy levels, and the like.

The OLED photoelectric functional material film layer constituting the OLED device includes at least two layers or more, and the industrially applied OLED device structure includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron transport. Layers, electron injection layers and other film layers, that is to say, the photoelectric functional materials applied to the OLED device include at least hole injection materials, hole transport materials, luminescent materials, electron transport materials, etc., and the material types and combinations are rich. And the characteristics of diversity. In addition, for different configurations of OLED devices, the optoelectronic functional materials used have strong selectivity, and the performance of the same materials in different structural devices may be completely different.

Therefore, in view of the industrial application requirements of current OLED devices and the different functional film layers of OLED devices, the photoelectric characteristics of devices must be selected to be more suitable and higher performance OLED functional materials or material combinations in order to achieve high efficiency and long life of the device. And the comprehensive characteristics of low voltage. As far as the actual demand of the current OLED display lighting industry is concerned, the development of OLED materials is still far from enough. It is lagging behind the requirements of panel manufacturers, and it is especially important to develop higher performance organic functional materials as material enterprises.

Summary of the invention

One of the objects of the present invention is to provide a compound having an aromatic amine and didimethyl hydrazine as a core. The compound provided by the invention has arylamine and didimethyl hydrazine as the core, has high glass transition temperature and molecular thermal stability, suitable HOMO and LUMO energy levels, high Eg, and can be effectively improved by device structure optimization. The optoelectronic properties of OLED devices and the lifetime of OLED devices.

The technical solution of the present invention to solve the above technical problems is as follows: a compound having an aromatic amine and didimethyl fluorene as a core, and the structure of the compound is as shown in the general formula (1):

In the formula (1), Ar is represented by a single bond, a C ₆ -C ₆₀ aryl group or a C ₅ -C ₆₀ heteroaryl group, and any of the C ₆ -C ₆₀ aryl group or the C ₅ -C ₆₀ heteroaryl group A H atom may be substituted by a C ₁ -C ₁₀ alkyl group;

R is represented by the structure represented by the formula (2) or the formula (3);

In the general formula (2) and the general formula (3), when Z and Y are the same or different, they are represented by an N atom or CR ₁ , and when R _{1 is} present, the same or different is represented by a hydrogen atom, a cyano group or a C ₁ -C. _{a 20-} or branched-chain substituted alkyl group, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms;

L ₁ and L _{2 are} represented as a single bond, a C ₆ -C ₆₀ aryl group or a C ₅ -C ₆₀ heteroaryl group, and any H atom of the C ₆ -C ₆₀ aryl group or the C ₅ -C ₆₀ heteroaryl group Can be substituted by a C ₁ -C ₁₀ alkyl group;

X represents an oxygen atom, a sulfur atom, an alkyl-substituted alkylene group, an aryl-substituted alkylene group, an alkyl-substituted imido group or an aryl-substituted imido group.

The compound of the invention is an arylamine-bis-dimethyl hydrazine compound, and the arylamine is bonded to the bisdimethyl hydrazine structure, so that it has strong hole transporting ability, high hole mobility, and can be used as a hole transporting material. The high hole transport rate can improve the efficiency of the organic electroluminescent device; at the appropriate LUMO level, it acts as an electron blocking, enhances the recombination efficiency of the excitons in the light-emitting layer, and lowers the high current density. The efficiency roll-off reduces the device voltage and improves the current efficiency and lifetime of the device.

Based on the above technical solutions, the present invention can also be improved as follows.

Further, in the formula (1), Ar is represented by a phenylene group, a biphenylylene group, a triphenylene group, a naphthylene group or a pyridylene group, and the phenylene group, a biphenylylene group, and a triphenylene group. Any one of the H, naphthylene or pyridylene groups may be substituted by methyl, ethyl, propyl, isopropyl, butyl, t-butyl;

In the general formula (2) and the general formula (3), Z or Y is represented by the same or different N atom or CR ₁ , and the same or different R ₁ is represented by a hydrogen atom, a cyano group, a methyl group, and a B group. Base, propyl, butyl, isopropyl, tert-butyl, pentyl, hexyl, phenyl, biphenyl, triphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl or carbazolyl Wherein the methyl, ethyl, propyl, butyl, isopropyl, t-butyl, pentyl, hexyl, phenyl, biphenyl, triphenyl, naphthyl, dibenzofuranyl, two Any H atom of the benzothienyl or oxazolyl group may be substituted by methyl, ethyl, propyl, isopropyl, t-butyl, phenyl or biphenyl;

L ₁ and L _{2 are} represented by a single bond, a phenylene group, a biphenylylene group, a triphenylene group, a naphthylene group or a pyridylene group, and the phenylene group, a biphenylylene group, a triphenylene group, a naphthylene group. Any H atom in the group or pyridylene group may be substituted with a methyl group, an ethyl group, a propyl group, and an isomer thereof.

Further, the specific structural formula of the compound is:

Any of them.

Another object of the present invention is to provide an organic electroluminescent device. When the OLED device is applied, the compound of the invention can maintain high film stability by optimizing the structure of the device, can effectively improve the photoelectric performance of the OLED device and the lifetime of the OLED device, and the compound of the invention has good performance in the OLED light-emitting device. Application effects and industrialization prospects.

The technical solution of the present invention to solve the above technical problems is as follows: An organic electroluminescent device, wherein at least one functional layer contains the above-mentioned compound having an aromatic amine and didimethyl fluorene as a core.

Further, the functional layer is a light-emitting layer and/or an electron blocking layer and/or a hole transport layer.

A third object of the invention is to provide an illumination or display element. The organic electroluminescent device of the invention can be applied to illumination or display originals, so that the current efficiency, power efficiency and external quantum efficiency of the device are greatly improved; at the same time, the device lifetime is improved obviously, and the OLED light-emitting device has good performance. The application effect has a good industrialization prospect.

The technical solution of the present invention to solve the above technical problems is as follows: an illumination or display element comprising the organic electroluminescent device as described above.

The beneficial effects of the invention are:

1. The compound of the present invention is an arylamine-bis-dimethyl hydrazine compound, and the arylamine is bonded to a bisdimethyl hydrazine structure to have a strong hole transporting ability and a high hole mobility as a hole transporting material. The high hole transport rate can improve the efficiency of the organic electroluminescent device; at the appropriate LUMO level, it acts as an electron blocking, enhances the recombination efficiency of the excitons in the light-emitting layer, and lowers the high current density. The efficiency roll-off reduces the device voltage and improves the current efficiency and lifetime of the device.

2. The compound of the present invention is mainly composed of an aromatic amine and didimethyl fluorene, and the three branches connected are radial. After the material is formed into a film, the branches can cross each other to form a dense layer, thereby reducing the material in the film. Leakage current after application of OLED devices, thus increasing device lifetime.

3. When the OLED device is applied, the compound of the invention can maintain high film stability by optimizing the device structure, can effectively improve the photoelectric performance of the OLED device and the lifetime of the OLED device, and the compound of the invention is in the OLED light-emitting device. Has a good application effect and industrialization prospects.

4. The compound of the invention has high glass transition temperature and molecular thermal stability, suitable HOMO and LUMO energy levels, high Eg, and optimized by device structure, can effectively improve the photoelectric performance of the OLED device and the lifetime of the OLED device.

5. The organic electroluminescent device of the invention can be applied to illumination or display originals, so that the current efficiency, power efficiency and external quantum efficiency of the device are greatly improved; at the same time, the device lifetime is greatly improved, in the OLED light-emitting device. It has good application effect and has good industrialization prospects.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view showing the structure of a device to which the compound of the present invention is applied, wherein the components represented by the respective numerals are as follows:

1, transparent substrate layer, 2, ITO anode layer, 3, hole injection layer, 4, hole transport layer a, 5, hole transport layer b, 6, luminescent layer, 7, electron transport layer, 8, electron injection Layer, 9, cathode reflective electrode layer.

2 is a graph showing current efficiency versus temperature for an OLED device of the present invention.

3 is a graph showing a leakage current test of a reverse voltage of a device fabricated in Device Example 1 and Device Comparative Example 1 of the present invention.

detailed description

The principles and features of the present invention are described in the following with reference to the accompanying drawings.

The structures of the intermediates synthesized in the following Synthesis Examples 1 to 10 are as follows.

Synthesis Example 1 (Synthesis of Intermediate 1)

0.1 mol of the starting material 2-amino-9,9-dimethylhydrazine and 0.12 mol of the starting material 2-bromo-9,9-dimethylhydrazine were dissolved in 500 mL of anhydrous toluene, and after removing oxygen, 0.005 mol of Pd ₂ (dba) was added. ₃ and 0.15 mol of tri-tert-butylphosphine, reacted at 110 ° C for 24 hours under an inert atmosphere, and the reaction progress was continuously monitored by TLC during the reaction. After the reaction of the raw materials was completed, the mixture was cooled, filtered, and the filtrate was evaporated to remove the solvent. After a silica gel column, Intermediate 1 was obtained; Elemental structure (Molecular C ₃₀ H ₂₇ N): Theory C, 89.73; H, 6.78; N, 3.49; Test: C, 89.74; H, 6.78; N, 3.48; ESI-MS (m/z) (M+): Theory: 401.55, found 401.90.

Synthesis Example 2 (Synthesis of Intermediate 2)

0.01 mol of Intermediate 1 and 0.012 mol of 1,4-dibromobenzene were dissolved in 150 mL of anhydrous toluene, and after deoxidation, 0.0005 mol of Pd ₂ (dba) ₃ and 0.015 mol of tri-tert-butylphosphine were added, and 110 under an inert atmosphere. The reaction was carried out for 24 hours at °C. During the reaction, the progress of the reaction was continuously monitored by TLC. After the reaction of the starting material was completed, the mixture was cooled and filtered, and the filtrate was evaporated to remove the solvent. The crude product was passed through a silica gel column to obtain intermediate 2; Elemental analysis structure (Molecular Formula C ₃₆ H ₃₀ BrN): Theory C, 77.69; H, 5.43; Br, 14.36; N, 2.52; C, 77.68; H, 5.43; Br, 14.36; N, 2.53; ESI-MS (m/z) (M+): The theoretical value is 556.55 and the measured value is 556.84.

Synthesis Example 3 (Synthesis of Intermediate 3)

In Synthesis Example 2, except that 1,3-dibromobenzene was used instead of 1,4-dibromobenzene, the reaction was carried out in the same manner to obtain Intermediate 3; Elemental Analysis Structure (Molecular Formula C ₃₆ H ₃₀ BrN): Theory C, 77.69; H, 5.43; Br, 14.36; N, 2.52; Found: C, 77.69; H, 5.43; Br, 14.37; N, 2.53; ESI-MS (m/z) (M+): For 556.55, the measured value is 556.74.

Synthesis Example 4 (Synthesis of Intermediate 4)

Dissolving 0.01 mol of the raw material 3,5-dibromobiphenyl and 0.012 mol of the starting material 4-dibenzofuran boric acid in a mixed solution of 150 mL (V _toluene : V _ethanol = 5:1) of toluene and ethanol, and adding 0.0002 after deoxidation. Mol Pd(PPh ₃ ) ₄ and 0.02 mol K ₂ CO _{3 were} reacted in an inert atmosphere at 110 ° C for 24 hours. During the reaction, the progress of the reaction was continuously monitored by TLC. After the reaction of the starting materials was completed, the mixture was cooled, filtered, and the filtrate was evaporated. The solvent, the crude product by silica gel column chromatography to give intermediate 4; elemental analysis for structure (molecular formula C ₂₄ H ₁₅ BrO): theory C, 72.19; H, 3.79; Br, 20.01; test value: C, 72.19; H, 3.79 ; Br, 20.02; ESI-MS (m/z) (M+): calc. 399.29.

Synthesis Example 5 (Synthesis of Intermediate 5)

Under an inert atmosphere, weigh 0.01 mol of intermediate 4, 0.0075 mol of bis(pinacol) diboron, 0.0005 mol of Pd(dppf)Cl ₂ and 0.022 mol of potassium acetate in 150 ml of toluene, and react at 100-120 ° C. - 24 hours, sampling plate, complete reaction, natural cooling, filtration, rotary distillation of the filtrate to obtain a crude product, a neutral silica gel column to obtain intermediate 5; elemental analysis structure (molecular formula C ₂₄ H ₁₇ BO ₃ ): theoretical value C, 79.15; H, 4.71; B, 2.97; Found: C, 79.15; H, 4.71; B, 2.98; ESI-MS (m/z) (M+): Theory: 364.21.

Synthesis Example 6 (Synthesis of Intermediate 6)

In Synthesis Example 4, except that 2,5-dibromobiphenyl was used instead of 1,3,5-tribromobenzene, the reaction was carried out in the same manner to obtain Intermediate 6; Elemental Analysis Structure (Molecular Formula C ₂₄ H ₁₅ BrO) The theoretical value is C, 72.19; H, 3.79; Br, 20.0; Test value: C, 72.19; H, 3.79; Br, 20.00; ESI-MS (m/z) (M+): theoretical value: 399.29, measured value It is 399.53.

Synthesis Example 7 (Synthesis of Intermediate 7)

In the synthesis example 5, except that the intermediate 6 was used instead of the intermediate 4, the reaction was carried out in the same manner to obtain the intermediate 7; the elemental analysis structure (the molecular formula C ₂₄ H ₁₇ BO ₃ ): theoretical value C, 79.15; H, 4.71; B, 2.97; Test: C, 79.15; H, 4.71; B, 2.98; ESI-MS (m/z) (M+): Theory: 364.21.

Synthesis Example 8 (Synthesis of Intermediate 8)

In Synthesis Example 4, except that 2,5-dibromobiphenyl was used instead of 1,3,5-tribromobenzene, and dibenzofuran-2-boronic acid was used instead of 4-dibenzofuran boric acid. After the reaction, Intermediate 8 was obtained; Elemental Analytical structure (Molecular formula C ₂₄ H ₁₅ BrO): Theory C, 72.19; H, 3.79; Br, 20.01; Test value: C, 72.19; H, 3.79; Br, 20.02; ESI-MS (m/z) (M+): calc. 399.29.

Synthesis Example 9 (Synthesis of Intermediate 9)

In the synthesis example 5, except that the intermediate 8 was used instead of the intermediate 4, the reaction was carried out in the same manner to obtain the intermediate 9; the elemental analysis structure (Molecular Formula C ₂₄ H ₁₇ BO ₃ ): Theoretical value C, 79.15; H, 4.71; B, 2.97; Test value: C, 79.14; H, 4.71; B, 2.97; ESI-MS (m/z) (M+): Theory: 364.21.

Synthesis Example 10 (Synthesis of Intermediate 10)

In Synthesis Example 4, except that 3,5-dibromobiphenyl was used instead of 1,3,5-tribromobenzene, and 9,9-dimethylindole-2-boronic acid was used instead of 4-dibenzofuran boric acid. After the reaction was carried out in the same manner, Intermediate 10 was obtained. Elemental analysis structure (Molecular formula C ₂₇ H ₂₁ Br): Theory C, 76.24; H, 4.98; Br, 18.78; Test value: C, 76.25; H, 4.98; </ RTI></RTI></RTI></RTI></RTI></RTI></RTI><RTIgt;

Synthesis Example 11 (Synthesis of Intermediate 11)

In the synthesis example 5, except that the intermediate 10 was used instead of the intermediate 4, the reaction was carried out in the same manner to obtain the intermediate 11; the elemental analysis structure (Molecular Formula C ₂₇ H ₂₃ BO ₂ ): Theoretical value C, 83.09; H, 5.94; B, 2.77; Measured: C, 83.08; H, 5.94; B, 2.77; ESI-MS (m/z) (M+): 390.29.

Synthesis Example 12 (Synthesis of Intermediate 12)

In Synthesis Example 4, except that 2,4-dibromobiphenyl was used instead of 1,3,5-tribromobenzene, and 9,9-dimethylindole-2-boronic acid was used instead of 4-dibenzofuran boric acid. In addition, the reaction was carried out in the same manner, to give intermediate 12; elemental analysis for structure (formula C ₂₇ H ₂₁ Br): theory C, 76.24; H, 4.98; Br, 18.78; test value: C, 76.25; H, 4.98 ; </ RTI></RTI></RTI></RTI></RTI></RTI></RTI><RTIgt;

Synthesis Example 13 (Synthesis of Intermediate 13)

In the synthesis example 5, except that the intermediate 12 was used instead of the intermediate 4, the reaction was carried out in the same manner to obtain the intermediate 13; the elemental analysis structure (the molecular formula C ₂₇ H ₂₃ BO ₂ ): theoretical value C, 83.09; H, 5.94; B, 2.77; Measured: C, 83.09; H, 5.94; B, 2.78; ESI-MS (m/z) (M+): 390.29.

Synthesis Example 14 (Synthesis of Intermediate 14)

In Synthesis Example 4, except that 2,5-dibromobiphenyl was used instead of 1,3,5-tribromobenzene, and 9,9-dimethylindole-4-boronic acid was used instead of 4-dibenzofuran boric acid. After the reaction was carried out in the same manner, Intermediate 14 was obtained. Elemental analysis structure (Molecular formula C ₂₇ H ₂₁ Br): Theory C, 76.24; H, 4.98; Br, 18.78; Test value: C, 76.25; H, 4.98; </ RTI></RTI></RTI></RTI></RTI></RTI></RTI><RTIgt;

Synthesis Example 15 (Synthesis of Intermediate 15)

In Synthesis Example 5, except that Intermediate 14 was used instead of Intermediate 4, the reaction was carried out in the same manner to obtain Intermediate 15; Elemental analysis structure (Molecular Formula C ₂₇ H ₂₃ BO ₂ ): Theory C, 83.09; H, 5.94; B, 2.77; Test value: C, 83.08; H, 5.94; B, 2.77; ESI-MS (m/z) (M+): Theory 390.29, found 390.83.

Synthesis Example 16 (Synthesis of Intermediate 16)

In Synthesis Example 4, except that 3,5-dibromobiphenyl was used instead of 1,3,5-tribromobenzene, and N-phenyl-3-oxazole boronic acid was used instead of 4-dibenzofuran boric acid. after the reaction was carried out in the same manner, to give intermediate 16; elemental analysis for structure (molecular formula C ₃₀ H ₂₀ BrN): theory C, 75.95; H, 4.25; Br, 16.84; N, 2.95; test value: C, 75.95; H, 4.25; Br, 16.85; N, 2.95; ESI-MS (m/z) (M+): Theory: 474.40.

Synthesis Example 17 (Synthesis of Intermediate 17)

In Synthesis Example 4, except that 2,5-dibromobiphenyl was used instead of 1,3,5-tribromobenzene, and N-phenyl-2-oxazol boric acid was used instead of 4-dibenzofuran boric acid. After the reaction was carried out in the same manner, Intermediate 17 was obtained. Elemental structure (M. C ₃₀ H ₂₀ BrN): Theory C, 75.95; H, 4.25; Br, 16.84; N, 2.95; Test value: C, 75.95; 4.25; Br, 16.84; N, 2.96; ESI-MS (m/z) (M+): Theory: 474.40.

Synthesis Example 18 (Synthesis of Intermediate 18)

In the synthesis example 5, except that the intermediate 17 was used instead of the intermediate 4, the reaction was carried out in the same manner to obtain the intermediate 18; the elemental analysis structure (Molecular Formula C ₃₀ H ₂₂ BNO ₂ ): Theoretical value C, 82.02; H, 5.05; B, 2.46; N, 3.19; Test: C, 82.02; H, 5.05; B, 2.46; N, 3.18; ESI-MS (m/z) (M+): Theory: 439.32, found 439.93 .

Synthesis Example 19 (Synthesis of Intermediate 19)

In Synthesis Example 4, except that 2,4-dibromobiphenyl was used instead of 1,3,5-tribromobenzene, and N-phenyl-3-carbazole boronic acid was used instead of 4-dibenzofuran boric acid. After the reaction was carried out, the intermediate 19 was obtained. Elemental structure (M. C ₃₀ H ₂₀ BrN): C, 75.95; H, 4.25; Br, 16.84; N, 2.95; Test value: C, 75.96; 4.25; Br, 16.84; N, 2.95; ESI-MS (m/z) (M+): Theory: 474.40.

Synthesis Example 20 (Synthesis of Intermediate 20)

In the synthesis example 5, except that the intermediate 19 was used instead of the intermediate 4, the reaction was carried out in the same manner to obtain the intermediate 20; the elemental analysis structure (Molecular Formula C ₃₀ H ₂₂ BNO ₂ ): Theoretical value C, 82.02; H, </ RTI></RTI></RTI></RTI></RTI></RTI></RTI></RTI></RTI><RTIgt; .

Synthesis Example 21 (Synthesis of Intermediate 21)

In Synthesis Example 2, the reaction was carried out in the same manner except that 9H-pyridine [3,4-b]pyrene was used instead of the intermediate 1, and 3,5-dibromobiphenyl was used instead of 1,4-dibromobenzene. After that, intermediate 21 was obtained; Elemental analysis structure (Molecular formula C ₂₃ H ₁₅ BrN ₂ ): Theory C, 69.19; H, 3.79; Br, 20.01; N, 7.02; Test value: C, 69.19; H, 3.79; Br , 20.00; N, 7.02; ESI-MS (m/z) (M+): calc. 399.29.

Synthesis Example 22 (Synthesis of Intermediate 22)

In the synthesis example 5, except that the intermediate 21 was used instead of the intermediate 4, the reaction was carried out in the same manner to obtain the intermediate 22; the elemental analysis structure (the molecular formula C ₂₃ H ₁₇ BN ₂ O ₂ ): the theoretical value C, 75.85; H, 4.70; B, 2.97; N, 7.69; C, 75.84; H, 4.70; B, 2.97; N, 7.69; ESI-MS (m/z) (M+): 364.21. Is 364.64.

Synthesis Example 1 (Synthesis of Compound 1)

0.01 mol of the intermediate 2 and 0.012 mol of the intermediate 5 were dissolved in a mixed solution of 150 mL (V _toluene : V _ethanol = 5:1) of toluene and ethanol, and after adding oxygen, 0.0002 mol of Pd(PPh ₃ ) ₄ and 0.02 mol K were added. ₂ CO ₃ , reacted at 110 ° C for 24 hours under an inert atmosphere, and the reaction progress was continuously monitored by TLC during the reaction. After the reaction of the raw materials was completed, the mixture was cooled, filtered, and the filtrate was evaporated to remove the solvent. The crude product was passed through a silica gel column to obtain compound 1 ; Elemental analysis structure (Molecular Formula C ₆₀ H ₄₅ NO): Theory C, 90.53; H, 5.70; N, 1.76; Tests: C, 90.54; H, 5.70; N, 1.76; ESI-MS (m/z) (M+): The theoretical value is 796.03 and the measured value is 796.88.

Synthesis Example 2 (Synthesis of Compound 13)

In Synthesis Example 1, except that Intermediate 3 was used instead of Intermediate 2, and Intermediate 7 was used instead of Intermediate 5, the reaction was carried out in the same manner to obtain Compound 13; Elemental Analysis Structure (Molecular Formula C ₆₀ H ₄₅ NO) The theoretical value is C, 90.53; H, 5.70; N, 1.76; Test value: C, 90.53; H, 5.70; N, 1.75; ESI-MS (m/z) (M+): The theoretical value is 796.03. 796.68.

Synthesis Example 3 (Synthesis of Compound 30)

In Synthesis Example 1, except that Intermediate 3 was used instead of Intermediate 2, and Intermediate 9 was used instead of Intermediate 5, the reaction was carried out in the same manner to obtain Compound 30; Elemental Analysis Structure (Molecular Formula C ₆₀ H ₄₅ NO) The theoretical value is C, 90.53; H, 5.70; N, 1.76; Test value: C, 90.52; H, 5.70; N, 1.76; ESI-MS (m/z) (M+): The theoretical value is 796.03, measured value 796.41.

Synthesis Example 4 (Synthesis of Compound 41)

In the synthesis example 1, except that the intermediate 11 was used instead of the intermediate 5, the reaction was carried out in the same manner to give the compound 41; the elemental analysis structure (Molecular Formula C ₆₃ H ₅₁ N): Theoretical value C, 92.04; H, 6.25 ;N, 1.70; </ RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI></RTI></RTI><RTIgt;

Synthesis Example 5 (Synthesis of Compound 59)

In the synthesis example 1, except that the intermediate 13 was used instead of the intermediate 5, the reaction was carried out in the same manner to give the compound 59; the elemental analysis structure (Molecular Formula C ₆₃ H ₅₁ N): Theory C, 92.04; H, 6.25 ;N, 1.70; </ RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;

Synthesis Example 6 (Synthesis of Compound 73)

In Synthesis Example 1, except that the intermediate 15 was used instead of the intermediate 5, the reaction was carried out in the same manner to obtain the compound 73; the elemental analysis structure (Molecular Formula C ₆₃ H ₅₁ N): Theory C, 92.04; H, 6.25 ;N, 1.70; </ RTI><RTIgt;</RTI><RTIgt;</RTI><RTIgt;</RTI></RTI><RTIgt;

Synthesis Example 7 (Synthesis of Compound 87)

In Synthesis Example 1, except that Intermediate 3 was used instead of Intermediate 2, and Intermediate 16 was used instead of Intermediate 5, the reaction was carried out in the same manner to give Compound 87; Elemental Analysis Structure (Molecular Formula C ₆₆ H ₅₀ N _{2 )} The theoretical value is C, 91.00; H, 5.79; N, 3.22; Test value: C, 91.00; H, 5.78; N, 3.22; ESI-MS (m/z) (M+): theoretical value 871.14, measured value It is 871.67.

Synthesis Example 8 (Synthesis of Compound 98)

In the synthesis example 1, except that the intermediate 18 was used instead of the intermediate 5, the reaction was carried out in the same manner to obtain the compound 98; the elemental analysis structure (the molecular formula C ₆₆ H ₅₀ N ₂ ): the theoretical value C, 91.00; H, 5.79; N, 3.22; Found: C, 91.01; H, 5.79; N, 3.20; ESI-MS (m/z) (M+): Theory: 871.14.

Synthesis Example 9 (Synthesis of Compound 108)

In Synthesis Example 1, except that the intermediate 20 was used instead of the intermediate 5, the reaction was carried out in the same manner to obtain the compound 108; the elemental analysis structure (Molecular Formula C ₆₆ H ₅₀ N ₂ ): Theoretical value C, 91.00; H, 5.79; N, 3.22; Test: C, 91.00; H, 5.79; N, 3.21; ESI-MS (m/z) (M+): Theory: 871.14, found 871.

Synthesis Example 10 (Synthesis of Compound 126)

In the synthesis example 1, except that the intermediate 22 was used instead of the intermediate 5, the reaction was carried out in the same manner to give the compound 126; the elemental analysis structure (Molecular Formula C ₅₉ H ₄₅ N ₃ ): Theoretical value C, 89.02; H, 5.70; N, 5.28; Test value: C, 89.03; H, 5.70; N, 5.27; ESI-MS (m/z) (M+): Theory: 796.03, found 796.43.

The application effects of the compound synthesized by the present invention as a hole transport layer material in a device will be described in detail below by way of Examples 1-10 and Comparative Examples 1, 2, and 3. The structural composition of the device obtained in each example is shown in Table 1. The test results of the obtained device are shown in Table 2.

Device Embodiment 1

Transparent substrate layer / ITO anode layer / hole injection layer (molybdenum trioxide MoO ₃ , thickness 10 nm) / hole transport layer a (NPB, thickness 40 nm) / hole transport layer b (Compound 1 prepared in the above example, thickness 80 nm) / luminescent layer (CBP and GD19 are mixed in a weight ratio of 100:5, thickness 40 nm) / electron transport layer (TPBI, thickness 40 nm) / electron injection layer (LiF, thickness 1 nm) / cathode reflective electrode layer (Al) . The structure of the materials involved is as follows:

The specific preparation process is as follows:

As shown in FIG. 1, the transparent substrate layer 1 is a transparent substrate such as a transparent PI film, glass, or the like. The ITO anode layer 2 (having a film thickness of 150 nm) was washed, that is, washed with alkali, washed with pure water, dried, and subjected to ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, molybdenum trioxide MoO ₃ having a thickness of 10 nm was deposited as a hole injecting layer 3 by a vacuum vapor deposition apparatus. Next, NPB having a thickness of 40 nm was vapor-deposited as the hole transport layer a. Immediately thereafter, a compound 1 having a thickness of 80 nm was evaporated as the hole transport layer b. After the vapor deposition of the hole transporting material is completed, the light emitting layer 6 of the OLED light emitting device is fabricated, and the structure thereof includes CBP used as the host material of the OLED light emitting layer 6, and GD19 is used as a doping material, and the doping ratio of the doping material is 5% by weight. The thickness of the light-emitting layer was 40 nm. After the above-mentioned light-emitting layer 6, the vacuum evaporation of the electron transport layer material was continued to be TPBI. The vacuum evaporation film thickness of this material was 40 nm, and this layer was the electron transport layer 7. On the electron transport layer 7, a lithium fluoride (LiF) layer having a film thickness of 1 nm was formed by a vacuum evaporation apparatus, and this layer was an electron injection layer 8. On the electron injecting layer 8, an aluminum (Al) layer having a film thickness of 80 nm was formed by a vacuum deposition apparatus, and this layer was used as the cathode reflective electrode layer 9. After the OLED light-emitting device is completed as described above, the anode and the cathode are connected by a known driving circuit, and the current efficiency of the device and the life of the device are measured.

Table 1

Table 2

Description: The life test system is the OLED device life tester jointly researched by the owner of the invention and Shanghai University.

It can be seen from the results of Table 2 that the compound of the present invention can be applied to the fabrication of OLED light-emitting devices, and compared with Comparative Examples 1, 2, and 3, both the efficiency and the lifetime are greatly improved, particularly the driving of the device. The life expectancy has been greatly improved.

From the test data provided in the examples, the compound of the present invention has good application effects as a hole transport layer material in an OLED light-emitting device, and has a good industrialization prospect. Further, the OLED device prepared by the material of the present invention is relatively stable when operating at a low temperature, and the device examples 1, 6, and 10 and the device comparative example 1, the comparative example 2, and the comparative example 3 are in the range of -10 to 80 ° C. Test, the results are shown in Table 3 and Figure 2.

Table 3 Efficiency test results

As can be seen from the data in Table 3 and FIG. 2, device examples 1, 6, and 10 are device structures in which the materials of the present invention and known materials are matched, and compared with device comparative example 1, comparative example 2, and comparative example 3, not only low temperature efficiency High, and the efficiency rises steadily during the temperature rise.

In order to further test the beneficial effects produced by the compound of the present invention, the devices fabricated in Device Example 1 and Device Comparative Example 1 of the present invention were subjected to a reverse voltage leakage current test, and the test data is shown in FIG. As can be seen from FIG. 3, compared with the device fabricated in the device example 1 and the device comparative example 1 of the compound of the present invention, the leakage current is small and the current curve is stable. Therefore, the material of the present invention is applied to the device after fabrication. Long service life.

The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalents, improvements, etc., which are within the spirit and scope of the present invention, should be included in the protection of the present invention. Within the scope.

Claims

A compound having a arylamine-doped dimethyl hydrazine as a core, wherein the structure of the compound is as shown in the formula (1):

In the formula (1), Ar is represented by a single bond, a C 6 -C 60 aryl group or a C 5 -C 60 heteroaryl group, and any of the C 6 -C 60 aryl group or the C 5 -C 60 heteroaryl group A H atom may be substituted by a C 1 -C 10 alkyl group;

R is represented by the structure represented by the formula (2) or the formula (3);

In the general formula (2) and the general formula (3), when Z and Y are the same or different, they are represented by an N atom or CR 1 , and when R 1 is present, the same or different is represented by a hydrogen atom, a cyano group or a C 1 -C. a 20- or branched-chain substituted alkyl group, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms;

L 1 and L 2 are represented as a single bond, a C 6 -C 60 aryl group or a C 5 -C 60 heteroaryl group, and any H atom of the C 6 -C 60 aryl group or the C 5 -C 60 heteroaryl group Can be substituted by a C 1 -C 10 alkyl group;

X represents an oxygen atom, a sulfur atom, an alkyl-substituted alkylene group, an aryl-substituted alkylene group, an alkyl-substituted imido group or an aryl-substituted imido group.
The compound according to claim 1, wherein Ar in the formula (1) is represented by a phenylene group, a biphenylylene group or a sub-triene group. a phenyl group, a naphthylene group or a pyridylene group, and any one of the phenylene, biphenylene, triphenylene, naphthylene or pyridylene group may be methyl, ethyl or propyl. Isopropyl, butyl, tert-butyl substitution;

In the general formula (2) and the general formula (3), Z or Y is represented by the same or different N atom or CR 1 , and the same or different R 1 is represented by a hydrogen atom, a cyano group, a methyl group, and a B group. Base, propyl, butyl, isopropyl, tert-butyl, pentyl, hexyl, phenyl, biphenyl, triphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl or carbazolyl Wherein the methyl, ethyl, propyl, butyl, isopropyl, t-butyl, pentyl, hexyl, phenyl, biphenyl, triphenyl, naphthyl, dibenzofuranyl, two Any H atom of the benzothienyl or oxazolyl group may be substituted by methyl, ethyl, propyl, isopropyl, t-butyl, phenyl or biphenyl;

L 1 and L 2 are represented by a single bond, a phenylene group, a biphenylylene group, a triphenylene group, a naphthylene group or a pyridylene group, and the phenylene group, a biphenylylene group, a triphenylene group, a naphthylene group. Any H atom in the group or pyridylene group may be substituted with a methyl group, an ethyl group, a propyl group, and an isomer thereof.
The compound according to claim 1, wherein the specific structural formula of the compound is:

Any of them.
An organic electroluminescent device characterized in that at least one functional layer comprises a compound having an aromatic amine-dimethyl hydrazine as a core according to any one of claims 1 to 3.
The organic electroluminescent device according to claim 4, wherein the functional layer is a light-emitting layer and/or an electron blocking layer and/or a hole transport layer.
An illumination or display element comprising the organic electroluminescent device of claim 4 or 5.