An organic compound containing an azabenzene skeleton structure and use thereof

Abstract

The application belongs to the technical field of semiconductors, and particularly relates to an organic compound containing an azabenzene skeleton structure and application thereof. The organic compound containing an azabenzene skeleton structure shown in general formula (1) provided by the application contains two rigid groups of azabenzene and benzo nitrogen-containing five-membered heterocycle in the partial structure shown in general formula (1), and the material structural stability is improved; the material has high density, and high refractive index is obtained. The organic compound containing an azabenzene skeleton structure provided by the application can meet the requirements of the material on thermal stability, film crystallinity and light transmission of the light extraction layer of an OLED device, the azabenzene and benzo nitrogen-containing five-membered heterocycle structure are rigid groups, the thermal stability of the material is improved, and the material can be applied to mass production. After being applied to the light extraction layer of an OLED device, the light extraction efficiency of the OLED device can be effectively improved. In summary, the compound has good application effect and industrialization prospect in an OLED light-emitting device.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor technology, specifically relating to an organic compound containing a azirbenzene framework structure and its applications. Background Technology

[0002] Currently, Organic Light Emitting Diode (OLED) display technology has been applied in smartphones, tablets, and other fields, and will further expand to large-size applications such as televisions. However, the significant gap between the external and internal quantum efficiencies of OLEDs greatly restricts their development. Therefore, improving the light extraction efficiency of OLEDs has become a research hotspot. Due to total internal reflection at the interfaces between the ITO film and the glass substrate, and between the glass substrate and air, only about 20% of the light emitted into the forward external space of the OLED device is emitted from the organic material film's light output (EL). The remaining approximately 80% of the light is mainly confined within the organic material film, ITO film, and glass substrate in the form of waveguides. It is evident that the light extraction efficiency of conventional OLED devices is relatively low (approximately 20%), which severely restricts the development and application of OLEDs. Therefore, reducing the total internal reflection effect in OLED devices and increasing the proportion of light coupled into the forward external space (light extraction efficiency) has attracted widespread attention.

[0003] Currently, an important method to improve the external quantum efficiency of OLEDs is to form structures such as wrinkles, photonic crystals, microlens arrays (MLAs), and surface capping layers on the light-emitting surface of the substrate. The first two structures affect the angular distribution of the OLED's radiation spectrum, while the third structure has a complex fabrication process. However, using surface capping layers is simple and improves luminous efficiency by more than 30%, making it particularly noteworthy. According to optical principles, when light passes through a material with a refractive index of n1 to a material with a refractive index of n2 (n1 > n2), it can only enter the material with a refractive index of n2 within an angle of arcsin(n2 / n1). The absorptivity B can be calculated using the following formula:

[0004]

[0005] Let n1 = n 一般OLED有机材料 =1.70, n2=n 玻璃 =1.46, then 2B = 0.49. Assuming all outward-propagating light is reflected by the metal electrodes, only 51% of the light energy is waveguided by the high-refractive-index organic film and ITO layer. Similarly, the transmittance of light emitted from the glass substrate into the air can be calculated. Therefore, when light emitted from the organic layer exits the device, only about 17% of the light energy is visible to humans. Therefore, to address the current low light extraction efficiency of OLED devices, a light extraction layer material needs to be added to the device structure.

[0006] The main problems with current optical extraction layers are as follows:

[0007] The material has a low refractive index in the visible light field, resulting in low light extraction efficiency. When applied to OLED devices, the improvement in device luminous efficiency is limited. Summary of the Invention

[0008] The purpose of this invention is to provide an organic compound containing a azirbenzene framework structure and its application. The organic compound containing a azirbenzene framework structure provided by this invention has a high refractive index in the visible light field. When applied to the light extraction layer of OLED devices, it can effectively improve the luminous efficiency of OLED devices.

[0009] The organic compound containing a azirbenzene framework structure, as shown in general formula (1), provided by this invention contains both azirbenzene and nitrogen-containing multi-membered heterocyclic rigid groups in a portion of the structure shown in general formula (1), thereby improving the structural stability of the material. The material of this invention has a high density and achieves a high refractive index. The organic compound containing a azirbenzene framework structure provided by this invention can meet the requirements of OLED device light extraction layer for material thermal stability, film crystallinity, and light transmission. The azirbenzene and benzo[nitrogen-containing] five-membered heterocyclic structures are rigid groups, which improve the thermal stability of the material and make it suitable for mass production. After being applied to the light extraction layer of OLED devices, this invention can effectively improve the light extraction efficiency of OLED devices. In summary, the compound described in this invention has good application effects and industrialization prospects in OLED light-emitting devices. Attached Figure Description

[0010] Figure 1 This is a schematic diagram of the structure of an OLED device provided in an embodiment of the present invention;

[0011] Figure 1 In the diagram, 1-substrate layer, 2-anode layer, 3-hole injection layer, 4-hole transport layer, 5-electron blocking layer, 6-light emitting layer, 7-electron transport layer, 8-electron injection layer, 9-cathode layer, and 10-light extraction layer. Detailed Implementation

[0012] This invention provides an organic compound containing an azabenzene skeleton structure, having the structure shown in general formula (1):

[0013]

[0014] In general formula (1), at least one of X1-X6 is an N atom, three are carbon atoms, and the rest are C(R);

[0015] L1, L2, and L3 are independently single-bonded, substituted, or unsubstituted C6-C bonds, respectively. 30 One of the following: arylene, substituted or unsubstituted 5- to 30-membered heteroarylene containing one or more heteroatoms;

[0016] R1-R3 are each independently one of the structures shown in general formulas (2)-(5):

[0017]

[0018] At least one of R1-R3 has the structure shown in general formula (4), and at least two of Y1-Y4 in general formula (4) are N;

[0019] In general formula (2), R 14 Hydrogen atom, C1-C 20 Alkyl, substituted or unsubstituted C6-C 30 One of the following: aryl, substituted or unsubstituted 5- to 30-membered heteroaryl groups containing one or more heteroatoms;

[0020] Z in general formulas (2) and (3) and Y1-Y8 in general formula (4) are independently carbon atoms, nitrogen atoms or C(R), and Z or Y1-Y8 bonded to groups R4-R7 are carbon atoms;

[0021] The X in general formulas (2) and (3) is independently -O-, -S-, -N(R) 10 )-;

[0022] In general formula (5), X1 is -O-, -S-, -C(R) 11 (R) 12 - or -N(R) 13 X2 is -O-, -S-, -C(R) 11 (R) 12 )-、-N(R 13 - or single bond;

[0023] In general formulas (1)-(4), R in C(R) and in general formulas (2)-(5), R4-R9 are independently hydrogen atoms, halogens, cyano groups, and C1-C groups, respectively. 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C6-C 30 One of the following: aryl, substituted or unsubstituted 5- to 30-membered heteroaryl groups containing one or more heteroatoms;

[0024] The R 10 -R 13 C1-C respectively 20 Alkyl, substituted or unsubstituted C6-C 30 One of the following: aryl, substituted or unsubstituted 5- to 30-membered heteroaryl groups containing one or more heteroatoms;

[0025] The substituents of the substituent group can be independently deuterium, cyano, halogen, C1-C. 20 Alkyl group, protium atom, deuterium atom, tritium atom, substituted or unsubstituted C1-C 20 One or more of alkoxy, substituted or unsubstituted C6-30 aryl, or substituted or unsubstituted 5- to 30-membered heteroaryl containing heteroatoms;

[0026] The heteroatoms in the heteroaryl and heteroalkylene groups are independently one or more of nitrogen, oxygen, or sulfur.

[0027] In this invention, the organic compound containing the azabenzene skeleton structure preferably has any one of the structures of general formula (1-1) to general formula (1-3):

[0028]

[0029] In this invention, the organic compound containing the azabenzene skeleton structure preferably has any one of the structures of general formulas (1-4) to (1-12):

[0030]

[0031]

[0032] In this invention, the organic compound containing the azabenzene skeleton structure preferably has any one of the structures of general formulas (I-1) to (I-5):

[0033]

[0034]

[0035] In this invention, in general formulas (Ⅰ-1) to (Ⅰ-5), X1-X5 are each independently C(R) or nitrogen atoms.

[0036] In this invention, the general formula (4) preferably has the structure shown in general formula (4-1) or general formula (4-2):

[0037]

[0038] In general formulas (4-1)-(4-2), Y3, Y4, Y5, Y6, Y7, Y8, and Y8 are each independently C(R) or nitrogen atoms.

[0039] In this invention, L1, L2, and L3 are independently preferably single bonds, substituted or unsubstituted phenylene, substituted or unsubstituted diphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted naphthidylene, substituted or unsubstituted anthraceneylene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyridylene, or substituted or unsubstituted furanylene; R and R4-R9 are each independently one of hydrogen atom, methoxy, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthidylene, substituted or unsubstituted pyridylene, or substituted or unsubstituted furanylene; R 10 -R 13 Each of the following is independently one of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthidyl, substituted or unsubstituted pyridyl, or substituted or unsubstituted furanyl; said R 14 It is one of hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted diphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthidyl, substituted or unsubstituted pyridyl or substituted or unsubstituted furanyl; the substituent replacing the above groups is independently one or more of cyano, fluorine atom, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, phenyl, naphthyl, diphenyl, terphenyl, naphthidyl, pyridyl or furanyl.

[0040] In this invention, the organic compound containing the azabenzene skeleton structure preferably has any of the following structures:

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050] This invention provides the application of the organic compounds containing the azabenzene framework structure described in the above-described technical solution in the preparation of functional layers of organic electroluminescent devices.

[0051] The present invention provides an organic electroluminescent device, wherein the organic electroluminescent device comprises at least one functional layer containing an organic compound with a azirbenzene framework structure as described in the above technical solution.

[0052] In this invention, the functional layer preferably includes a light extraction layer, and the light extraction layer preferably contains an organic compound with a azirbenzene skeleton structure as described in the above technical solution.

[0053] This invention does not impose any special requirements on the structure of the organic electroluminescent device; a structure well-known to those skilled in the art can be used, for example, Figure 1 The structure shown. (As illustrated) Figure 1 As shown, the structure of the organic electroluminescent device includes a substrate layer 1, an anode layer 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light-emitting layer 6, an electron transport layer 7, an electron injection layer 8, a cathode layer 9, and a light extraction layer 10, which are stacked sequentially.

[0054] In this invention, the substrate layer 1 is made of transparent glass. The anode layer 2 is made of Ag and has a thickness of 100 nm. The hole injection layer 3 is made of HAT-CN and has a thickness of 10 nm. The hole transport layer 4 is made of HT-1 and has a thickness of 140 nm. The electron blocking layer 5 is made of EB-1 and has a thickness of 30 nm. The light-emitting layer is preferably made of GH-2 and GH-1 as the main materials and GD-1 as the dopant material, with a mass ratio of GH-2, GH-1, and GD-1 of 45:45:10 and a thickness of 40 nm. The electron transport layer 7 is made of ET-1 and Liq, with a mass ratio of ET-1 to Liq of 1:1 and a thickness of 40 nm. The electron injection layer 8 is preferably made of LiF and has a thickness of 1 nm. The cathode layer 9 is made of Mg and Ag, with a mass ratio of Mg to Ag of 1:9 and a thickness of 15 nm. The material of the light extraction layer 10 is preferably an organic compound containing a azirbenzene framework structure as described in the above technical solution, and the thickness is 70 nm.

[0055] In this invention, the electron transport layer 7 can also serve as a hole blocking layer.

[0056] In this invention, the chemical structures of HAT-CN, HT-1, EB-1, GD-1, ET-1, GH-1, GH-2, and Liq are as follows:

[0057]

[0058] In this invention, the preferred method for preparing the organic electroluminescent device is vacuum evaporation.

[0059] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the accompanying drawings and embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0060] Preparation of intermediate A: The synthetic route is as follows:

[0061]

[0062] Under a nitrogen atmosphere, weigh raw material I and dissolve it in tetrahydrofuran (THF), then add bis(pinacolyl)diboron, (1,1) ’ - Bis(diphenylphosphine)ferrocene)palladium(II) chloride and potassium acetate were added, and the mixture was stirred. The mixture of the above reactants was heated under reflux at a reaction temperature of 70-90℃ for 5-10 hours. After the reaction was completed, water was added for cooling, and the mixture was filtered and the filter cake was dried in a vacuum oven. The obtained residue was purified by silica gel column chromatography to obtain intermediate D. The molar ratio of raw material I to bis(pinacolyl)diboron was 1:1.0-3, the molar ratio of Pd(dppf)2Cl2 to raw material I was 0.001-0.04:1, the molar ratio of potassium acetate to raw material I was 1.0-4.0:1, and the ratio of raw material I to THF was 1g:10-30mL.

[0063]

[0064] Under a nitrogen atmosphere, raw material III was weighed and dissolved in N,N-dimethylformamide (DMF). Then, intermediate D and palladium acetate were added, and the mixture was stirred. Potassium phosphate aqueous solution was then added, and the mixture was heated under reflux at a reaction temperature of 120-150°C for 5-15 hours. After the reaction was completed, water was added after cooling, the mixture was filtered, and the filter cake was dried in a vacuum drying oven. The residue was purified by silica gel column chromatography to obtain intermediate A.

[0065] The molar ratio of raw material III to intermediate D is 1:1.0-3, the molar ratio of Pd(OAc)2 to raw material III is 0.001-0.04:1, the molar ratio of K3PO4 to raw material III is 1.0-4.0:1, and the ratio of DMF dosage to raw material III dosage is 1g:10-30mL.

[0066] Taking the synthesis of intermediate A-1 as an example: the synthetic route is as follows:

[0067]

[0068] (1) In a three-necked flask, nitrogen gas is introduced, and 0.02 mol of raw material I-1 is added and dissolved in 100 mL of tetrahydrofuran (THF). Then, 0.024 mol of bis(pinacolyl)diboron and 0.0002 mol of (1,1) ’ 1-Bis(diphenylphosphine)ferrocene)dichloropalladium(II) and 0.05 mol potassium acetate were added, and the mixture was stirred. The mixture of the above reactants was heated under reflux at 80 °C for 5 hours. After the reaction was completed, the mixture was cooled and 100 mL of water was added. The mixture was then filtered and dried in a vacuum oven. The residue obtained was purified by silica gel column chromatography to obtain intermediate D-1. Elemental analysis showed that the structure (molecular formula C) was... 20 H 21 BN2O2): Theoretical values: C, 72.31; H, 6.37; B, 3.25; N, 8.43; Measured values: C, 72.28; H, 6.38; B, 3.27; N, 8.41. LC-MS: Theoretical value: 332.17; Measured value: 333.34.

[0069] (2) Nitrogen gas was introduced into a three-necked flask, followed by the addition of 0.02 mol of starting material III-1 (2,4,6-trichloropyridine), 150 mL of LDM, 0.024 mol of intermediate D-1, and 0.0002 mol of palladium acetate. The mixture was stirred, and then 3 mL of 0.01 mol / mL K3PO4 aqueous solution was added. The mixture was heated to 150 °C and refluxed for 10 hours. A sample was taken and spotted onto a TLC plate, indicating that the reaction was complete. After natural cooling, water was added, the mixture was filtered, and dried in a vacuum drying oven. The residue was purified by silica gel column chromatography to obtain intermediate A-1. Elemental analysis revealed the structure (molecular formula C). 19 H 11 Cl2N3): Theoretical values: C, 64.79; H, 3.15; N, 11.93; Measured values: C, 64.82; H, 3.21; N, 11.89. LC-MS: Theoretical value: 351.03; Measured value: 352.12.

[0070] Taking the synthesis of intermediate A-7 as an example: the synthetic route is as follows:

[0071]

[0072] (1) In a three-necked flask, nitrogen gas is introduced, and 0.02 mol of raw material I-1 is added and dissolved in 100 mL of tetrahydrofuran (THF). Then, 0.024 mol of bis(pinacolyl)diboron and 0.0002 mol of (1,1) ’-Bis(diphenylphosphine)ferrocene)dichloropalladium(II) and 0.05 mol potassium acetate were added, and the mixture was stirred. The mixture of the above reactants was heated under reflux at 80 °C for 5 hours. After the reaction was completed, the mixture was cooled and 100 mL of water was added. The mixture was filtered and dried in a vacuum oven. The residue obtained was purified by silica gel column chromatography to obtain intermediate D-1.

[0073] (2) Nitrogen gas was introduced into a three-necked flask, followed by the addition of 0.02 mol of starting material III-2 (2,4,6-trichloropyridine), 150 mL of LDM, 0.048 mol of intermediate D-1, and 0.0002 mol of palladium acetate. The mixture was stirred, and then 3 mL of 0.01 mol / mL K3PO4 aqueous solution was added. The mixture was heated to 150 °C and refluxed for 10 hours. A sample was taken and spotted onto a TLC plate, indicating that the reaction was complete. After natural cooling, water was added, the mixture was filtered, and dried in a vacuum drying oven. The residue was purified by silica gel column chromatography to obtain intermediate A-7. Elemental analysis revealed the structure (molecular formula C). 33 H 20 ClN5): Theoretical values: C, 75.93; H, 3.86; N, 13.42; Measured values: C, 75.89; H, 3.91; N, 13.37. LC-MS: Theoretical value: 521.14; Measured value: 522.09.

[0074] Intermediate A was prepared using the same synthesis methods as intermediates A-1 and A-7. The specific structures of raw material I and raw material III are shown in Table 1.

[0075] Table 1. Specific Structures of Raw Material I and Raw Material III

[0076]

[0077]

[0078] Preparation of intermediate E: The synthetic route is as follows:

[0079]

[0080] Under a nitrogen atmosphere, raw material IV was weighed and dissolved in tetrahydrofuran (THF), and then bis(pinacolyl)diboron and (1,1) ’- Bis(diphenylphosphine)ferrocene)palladium(II) chloride and potassium acetate were added, and the mixture was stirred. The mixture of the above reactants was heated under reflux at a reaction temperature of 70-90℃ for 5-10 hours. After the reaction was completed, water was added for cooling, and the mixture was filtered and the filter cake was dried in a vacuum oven. The obtained residue was purified by silica gel column chromatography to obtain intermediate E. The molar ratio of raw material IV to bis(pinacolyl)diboron was 1:1.0-3, the molar ratio of Pd(dppf)2Cl2 to raw material IV was 0.001-0.04:1, the molar ratio of potassium acetate to raw material IV was 1.0-4.0:1, and the ratio of raw material IV to THF was 1g:10-30mL.

[0081] Taking the synthesis of intermediate E-1 as an example: the synthetic route is as follows:

[0082]

[0083] Nitrogen gas was introduced into a three-necked flask, and 0.02 mol of raw material IV-1 was added and dissolved in 100 mL of tetrahydrofuran (THF). Then, 0.024 mol of bis(pinacolyl)diboron and 0.0002 mol of (1,1) ’ 1-Bis(diphenylphosphine)ferrocene)dichloropalladium(II) and 0.05 mol potassium acetate were added, and the mixture was stirred. The mixture was then heated under reflux at 80 °C for 5 hours. After the reaction was completed, the mixture was cooled, 100 mL of water was added, and the mixture was filtered and dried in a vacuum oven. The residue was purified by silica gel column chromatography to obtain intermediate E-1; elemental analysis showed its structure (molecular formula C). 19 H 20 BNO3): Theoretical values: C, 71.05; H, 6.28; B, 3.37; N, 4.36; Measured values: C, 71.02; H, 6.31; B, 3.35; N, 4.37. LC-MS: Theoretical value: 321.15; Measured value: 322.27.

[0084] Other intermediates E are prepared according to the preparation method of intermediate E-1. The structural formulas of intermediates E and their corresponding raw materials used in this invention are shown in Table 2:

[0085] Table 2 Structural formulas of intermediate E and its corresponding raw materials

[0086]

[0087]

[0088] Example 1: Synthesis of Compound 1, the synthetic route is as follows:

[0089]

[0090] Nitrogen gas was introduced into a three-necked flask, followed by the addition of 0.01 mol of intermediate A-1, 150 mL of DMF, 0.03 mol of intermediate E-1, and 0.0002 mol of palladium acetate. The mixture was stirred, and then 2 mL of 0.01 mol / mL K3PO4 aqueous solution was added. The mixture was heated to 150 °C and refluxed for 24 hours. A sample was spotted onto a TLC plate, indicating complete reaction. After natural cooling, the mixture was extracted with 200 mL of dichloromethane, and the layers were separated. The extract was dried over anhydrous sodium sulfate, filtered, and the filtrate was rotary evaporated and purified by silica gel column chromatography to obtain compound 1. Elemental analysis revealed the structure (molecular formula C). 45 H 27 N5O2): Theoretical values: C, 80.70; H, 4.06; N, 10.46; Measured values: C, 80.72; H, 4.14; N, 10.49. LC-MS: Theoretical value: 669.22; Measured value: 670.24.

[0091] Example 2: Synthesis of compound 12, the synthetic route is as follows:

[0092]

[0093] Nitrogen gas was introduced into a three-necked flask, followed by the addition of 0.02 mol of intermediate A-2, 300 mL of DMF, 0.03 mol of intermediate E-2, and 0.0004 mol of palladium acetate. The mixture was stirred, and then 4 mL of 0.01 mol / mL K3PO4 aqueous solution was added. The mixture was heated to 150 °C and refluxed for 24 hours. A sample was spotted onto a TLC plate, indicating complete reaction. After natural cooling, the mixture was extracted with 200 mL of dichloromethane, and the layers were separated. The extract was dried over anhydrous sodium sulfate, filtered, and the filtrate was purified by rotary evaporation and silica gel column chromatography to obtain intermediate F-1. Elemental analysis revealed the structure (molecular formula C). 34 H 21 ClN4): Theoretical values: C, 78.38; H, 4.06; N, 10.75; Measured values: C, 78.40; H, 4.05; N, 10.77. LC-MS: Theoretical value: 520.15; Measured value: 521.28.

[0094] Nitrogen gas was introduced into a three-necked flask, followed by the addition of 0.01 mol of intermediate F-1, 150 mL of DMF, 0.015 mol of intermediate E-3, and 0.0002 mol of palladium acetate. The mixture was stirred, and then 2 mL of 0.01 mol / mL K3PO4 aqueous solution was added. The mixture was heated to 150 °C and refluxed for 24 hours. A sample was spotted onto a TLC plate, indicating complete reaction. After natural cooling, the mixture was extracted with 200 mL of dichloromethane, and the layers were separated. The extract was dried over anhydrous sodium sulfate, filtered, and the filtrate was rotary evaporated and purified by silica gel column chromatography to obtain the target compound 12. Elemental analysis revealed its structure (molecular formula C). 47 H 29N5O): Theoretical values: C, 83.04; H, 4.30; N, 10.30; Measured values: C, 83.01; H, 4.31; N, 10.34. LC-MS: Theoretical value: 679.24; Measured value: 680.38.

[0095] Example 3: Synthesis of compound 17, the synthetic route is as follows:

[0096]

[0097] The preparation method of compound 17 is the same as in Example 1, except that intermediate A-1 is replaced by intermediate A-3 and intermediate E-1 is replaced by intermediate E-4. The resulting target product, compound 17, has the following structure (molecular formula C10). 51 H 33 N7): Theoretical values ​​C, 82.35; H, 4.47; N, 13.18; Measured values ​​C, 82.41; H, 4.49; N, 13.22. LC-MS: Theoretical value 743.28, measured value 744.11.

[0098] Example 4: Synthesis of compound 28, the synthetic route is as follows:

[0099]

[0100] The preparation method of intermediate F-2 is the same as that of intermediate F-1 in Example 2, except that intermediate A-2 is replaced by intermediate A-3 and intermediate E-2 is replaced by intermediate E-4 to obtain intermediate F-2. Elemental analysis of the structure (molecular formula C) is performed. 32 H 20 ClN5): Theoretical values: C, 75.36; H, 3.95; N, 13.73; Measured values: C, 75.42; H, 3.97; N, 13.76. LC-MS: Theoretical value: 509.14; Measured value: 510.09.

[0101] Compound 28 was prepared using the same method as Compound 12 in Example 2, except that intermediate E-5 replaced intermediate E-3 and intermediate F-2 replaced intermediate F-1, yielding the target compound 28. Elemental analysis revealed its structure (molecular formula C). 53 H 37 N5): Theoretical values ​​C, 85.57; H, 5.01; N, 9.41; Measured values ​​C, 85.63; H, 5.04; N, 9.38. LC-MS: Theoretical value 743.30, measured value 744.38.

[0102] Example 5: Synthesis of compound 41, the synthetic route is as follows:

[0103]

[0104] The preparation method of compound 41 is the same as that of compound 1 in Example 1, except that intermediate A-1 is replaced by intermediate A-5. The resulting target product, compound 41, has the following structure (molecular formula C10). 44 H 26 N6O2): Theoretical values: C, 78.79; H, 3.91; N, 12.53; Measured values: C, 78.81; H, 3.90; N, 12.51. LC-MS: Theoretical value: 670.21; Measured value: 671.18.

[0105] Example 6: Synthesis of compound 49, the synthetic route is as follows:

[0106]

[0107] The preparation method of compound 49 is the same as in Example 2, except that intermediate A-2 is replaced by intermediate A-4, intermediate E-2 is replaced by intermediate E-1, and intermediate E-3 is replaced by intermediate E-7.

[0108] The target product compound 49 was obtained, and its elemental structure (molecular formula C) was analyzed. 43 H 25 N₅O₃): Theoretical values: C, 78.29; H, 3.82; N, 10.62; O, 7.28; Measured values: C, 78.30; H, 3.83; N, 10.60; O, 7.27. LC-MS: Theoretical value: 659.20; Measured value: 660.31.

[0109] Example 7: Synthesis of compound 59, the synthetic route is as follows:

[0110]

[0111] The preparation method of intermediate F-4 is the same as that of intermediate F-1 in Example 2, except that intermediate A-2 is replaced by intermediate A-5 and intermediate E-2 is replaced by intermediate E-8 to obtain intermediate F-4;

[0112] Compound 59 was prepared using the same method as Compound 12 in Example 2, except that intermediate F-4 replaced intermediate F-1 and intermediate E-9 replaced intermediate E-3, yielding the target compound 59. Elemental analysis revealed its structure (molecular formula C). 49 H 31 N7): Theoretical values ​​C, 81.99; H, 4.35; N, 13.66; Measured values ​​C, 82.01; H, 4.37; N, 13.72. LC-MS: Theoretical value 717.26, measured value 718.31.

[0113] Example 8: Synthesis of Compound 71

[0114]

[0115] The preparation method of compound 71 is the same as in Example 1, except that intermediate A-1 is replaced by intermediate A-13 and intermediate E-1 is replaced by intermediate E-10. The target product compound 71 is obtained. Elemental analysis of its structure (molecular formula C...) 48 H 36 N4): Theoretical values ​​C, 86.20; H, 5.43; N, 8.38; Measured values ​​C, 86.24; H, 5.41; N, 8.44. LC-MS: Theoretical value 668.29, measured value 669.40.

[0116] Example 9: Synthesis of compound 109, the synthetic route is as follows:

[0117]

[0118] Nitrogen gas was introduced into a three-necked flask, followed by the addition of 0.01 mol of intermediate A-7, 150 mL of DMF, 0.015 mol of intermediate E-11, and 0.0001 mol of palladium acetate. The mixture was stirred, and then 1 mL of 0.01 mol / mL K3PO4 aqueous solution was added. The mixture was heated to 150 °C and refluxed for 24 hours. A sample was spotted onto a TLC plate, indicating complete reaction. After natural cooling, the mixture was extracted with 200 mL of dichloromethane, and the layers were separated. The extract was dried over anhydrous sodium sulfate, filtered, and the filtrate was rotary evaporated and purified by silica gel column chromatography to obtain the target product compound 109. Elemental analysis revealed its structure (molecular formula C). 46 H 28 N6S): Theoretical values: C, 79.29; H, 4.05; N, 12.06; S, 4.60; Measured values: C, 79.31; H, 4.07; N, 12.03; S, 4.59. LC-MS: Theoretical value: 696.21; Measured value: 697.24.

[0119] Example 10: Synthesis of compound 112, the synthetic route is as follows:

[0120]

[0121] The preparation method of compound 112 is the same as in Example 9, except that intermediate E-11 is replaced by intermediate E-12. The resulting target product, compound 112, has the following structure according to elemental analysis (molecular formula C10). 49 H 31 N5): Theoretical values ​​C, 85.32; H, 4.53; N, 10.15; Measured values ​​C, 85.34; H, 4.49; N, 10.17. LC-MS: Theoretical value 689.26, measured value 690.32.

[0122] Example 11: Synthesis of compound 118, the synthetic route is as follows:

[0123]

[0124] The preparation method of compound 118 is the same as in Example 9, except that intermediate E-11 is replaced by intermediate E-13. The resulting target product, compound 118, has the following structure (molecular formula C10). 45 H 27 N5O): Theoretical values: C, 82.68; H, 4.16; N, 10.71; Measured values: C, 82.71; H, 4.18; N, 10.69. LC-MS: Theoretical value: 653.22; Measured value: 654.19.

[0125] Example 12: Synthesis of compound 143, the synthetic route is as follows:

[0126]

[0127] The preparation method of compound 143 is the same as in Example 1, except that intermediate A-1 is replaced by intermediate A-8, and intermediate E-1 is replaced by intermediate E-14. The resulting target product, compound 143, has the following structure according to elemental analysis (molecular formula C143). 50 H 31 N7): Theoretical values ​​C, 82.28; H, 4.28; N, 13.43; Measured values ​​C, 82.32; H, 4.31; N, 13.39. LC-MS: Theoretical value 729.26, measured value 730.31.

[0128] Example 13: Synthesis of compound 213, the synthetic route is as follows:

[0129]

[0130] The preparation method of compound 213 is the same as in Example 9, except that intermediate A-7 is replaced by intermediate A-11, and intermediate E-11 is replaced by intermediate E-15. The resulting target compound 213 has the following structure (molecular formula C10). 46 H 28 N6O): Theoretical values: C, 81.16; H, 4.15; N, 12.35; Measured values: C, 81.19; H, 4.18; N, 12.37. LC-MS: Theoretical value: 680.23; Measured value: 681.15.

[0131] Example 14: Synthesis of compound 225, the synthetic route is as follows:

[0132]

[0133] The preparation method of compound 225 is the same as in Example 1, except that intermediate A-1 is replaced by intermediate A-12 and intermediate E-1 is replaced by intermediate E-16. The resulting target product, compound 225, has the following elemental analysis structure (molecular formula C10). 48 H 30 N6): Theoretical values ​​C, 83.46; H, 4.38; N, 12.17; Measured values ​​C, 83.37; H, 4.41; N, 12.23. LC-MS: Theoretical value 690.25, measured value 691.34.

[0134] Application Example 1

[0135] according to Figure 1 The schematic diagram of the OLED light-emitting device shown is fabricated as follows:

[0136] a) The substrate layer 1 is transparent glass, and an anode layer 2 (Ag, with a thickness of 100nm) is deposited on the surface of the substrate layer 1 by vacuum evaporation.

[0137] b) HAT-CN with a thickness of 10 nm is deposited on the surface of the anode layer 2 by vacuum evaporation to serve as the hole injection layer 3;

[0138] c) HT-1 with a thickness of 140 nm is deposited on the surface of hole injection layer 3 by vacuum evaporation to serve as hole transport layer 4.

[0139] d) EB-1 with a thickness of 30 nm is deposited on the surface of hole transport layer 4 by vacuum evaporation to serve as electron blocking layer 5.

[0140] e) A light-emitting layer 6 is deposited on the surface of electron blocking layer 5, with GH-2 and GH-1 as the host materials and GD-1 as the dopant material. The mass ratio of GH-2, GH-1 and GD-1 is 45:45:10 and the thickness is 40nm.

[0141] f) On the surface of the light-emitting layer 6, ET-1 and Liq with a mass ratio of 1:1 are vapor-deposited by vacuum evaporation, with a thickness of 40 nm, to serve as the electron transport layer 7.

[0142] g) On the surface of electron transport layer 7, LiF with a thickness of 1 nm is vacuum-deposited as electron injection layer 8;

[0143] h) On the surface of electron injection layer 8, a Mg:Ag layer with a mass ratio of 1:9 and a thickness of 15 nm is vacuum-deposited as cathode layer 9.

[0144] i) On the surface of the cathode layer 9, the organic materials prepared in Examples 1 to 14 are deposited by vacuum evaporation, with a thickness of 70 nm, to obtain the organic materials prepared in Examples 1 to 14 as OLED light-emitting devices for the light extraction layer 10.

[0145] Comparative Example 1

[0146] The preparation method is basically the same as that in Application Example 1, except that Alq3 is used to replace the organic material prepared in Examples 1 to 14, with a thickness of 70 nm, to obtain an OLED light-emitting device with Alq3 as the light extraction layer.

[0147] In this comparative example, the chemical structure of Alq3 is as follows:

[0148] This invention details the application effect of the organic chemical with the structure shown in general formula (1) synthesized in this invention as a light extraction layer material for OLEDs using devices prepared in application examples and devices prepared in Comparative Example 1. The devices described in Examples 1-14 of this invention are fabricated using the same methods as those in Comparative Example 1, and the same substrate and electrode materials are used, with the electrode film thickness remaining consistent. The only difference is that the light extraction layer material in Examples 1-14 is changed. The performance test results of the devices obtained using each example as the light extraction layer material are shown in Table 3.

[0149] Table 3. Composition of OLED light-emitting devices prepared in application examples and comparative examples.

[0150]

[0151]

[0152] The test data of the obtained electroluminescent devices are shown in Table 4.

[0153] Table 4 shows the performance of OLED light-emitting devices prepared in application examples and comparative examples.

[0154]

[0155]

[0156] Note: Current efficiency was tested using an IVL (current-voltage-luminance) testing system at a current density of 10 mA / cm². 2 .

[0157] As can be seen from the results in Table 4, the light extraction efficiency of the organic compound of the present invention is significantly improved when applied to the fabrication of OLED light-emitting devices compared with that of Comparative Example 1.

[0158] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. An organic compound containing an azabenzene skeleton structure, characterized in that, It has any of the following structures: 。 2. The application of the organic compound containing the azabenzene framework structure as described in claim 1 in the preparation of the functional layer of an organic electroluminescent device.

3. An organic electroluminescent device, characterized in that, At least one functional layer of the organic electroluminescent device contains an organic compound with a azirbenzene framework structure as described in claim 1.

4. The organic electroluminescent device according to claim 3, characterized in that, The functional layer includes a light extraction layer containing an organic compound with a azirbenzene skeleton structure as described in claim 1.

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