A pyridazine and anthracene luminescent material and its application

Abstract

The present invention relates to the technical field of electronic luminescent materials, and more particularly to a pyridazine-anthracene luminescent material and its application. The structure of the pyridazine-anthracene luminescent material is shown in the following general formula [I]: #imgabs0# General formula [I]; wherein R is a substituted or unsubstituted C1-C30 alkane chain, a C1-C30 aryl group, or a C1-C30 heteroaryl group, the substituent of the substituted or unsubstituted group is selected from hydrogen, deuterium, a C1-C30 alkane chain, a C1-C30 aryl group, or a C1-C30 heteroaryl group, and the heteroatom of the heteroaryl group is selected from any one or more of N, O, and S. The compound of the present invention has good molecular stability when used in organic electroluminescent devices. The prepared OLED device has excellent optoelectronic properties, high thermal stability, low driving voltage, and high luminous efficiency, which can extend the service life of the device and has good luminous performance, and can well meet the requirements of device manufacturers.

Description

Technical Field

[0001] The present invention relates to a pyridazine and anthracene luminescent material and application thereof, belonging to the technical field of electronic luminescent materials. Background Art

[0002] Compared with liquid crystal displays, organic light emitting diodes (OLEDs) have the advantages of high brightness, thin size, fast response, stable performance, high contrast, wide viewing angle, full color, and relatively easy preparation of large-area flexible screens. They are very promising to replace existing LCD displays and fluorescent lighting, and their application prospects are very good.

[0003] The basic structure of an OLED device is similar to a "sandwich", including: indium tin oxide (ITO) connected to the positive electrode of electricity, a metal cathode, and a functional structural layer sandwiched between the positive and cathode electrodes. More fundamentally, the structural layer includes a hole transport layer (HTL), a light-emitting layer (EML), and an electron transport layer (ETL). When power is supplied to an appropriate voltage, the positive holes from the hole transport layer and the cathode charges from the electron transport layer will combine in the light-emitting layer. The carriers migrate within the corresponding organic layer and eventually reach the light-emitting layer and recombine to form excitons. When the excitons de-excite and return to the ground state, they emit photons through radiation decay. The color of the light mainly depends on the band gap width of the light-emitting material. Electroluminescent materials play a vital role in OLED display technology. Good electroluminescent materials are one of the key factors that determine the performance of light-emitting devices.

[0004] As far as the current OLED industry is concerned, luminescent materials still have problems such as short lifespan, low luminous efficiency, and poor thermal stability. Therefore, developing and designing a blue light luminescent material with good thermal stability, long luminous lifespan, and high color purity is still an important task for researchers. Summary of the Invention

[0005] In response to the deficiencies in the prior art, the present invention provides a pyridazine-anthracene luminescent material and its application. The pyridazine-anthracene luminescent material has good molecular stability. The prepared OLED device has excellent optoelectronic properties, high thermal stability, low driving voltage and high external quantum efficiency, which can extend the service life of the device and has excellent color purity, which can meet the requirements of device manufacturers.

[0006] The technical solution of the present invention to solve the above technical problems is as follows: a pyridazine-anthracene luminescent material, the structure of the pyridazine-anthracene luminescent material is shown in the following general formula [I]:

[0007] General formula [I];

[0008] The R is a substituted or unsubstituted C1~C30 alkane chain, a C1~C30 aryl group or a C1~C30 heteroaryl group, the substituent of the substituted or unsubstituted group is selected from hydrogen, deuterium, a C1~C30 alkane chain, a C1~C30 aryl group or a C1~C30 heteroaryl group, and the heteroatom of the heteroaryl group is selected from any one or more of N, O and S.

[0009] Furthermore, R is any one of biphenyl, deuterated biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, pyrenyl, chrysyl, benzochrysyl, fluorenyl, spirobifluorenyl, furanyl, carbazolyl, imidazolyl, thienyl, oxazolyl, thiazolyl, triazinyl, and triphenylene.

[0010] Furthermore, the R is any one of the following structural formulas:

[0011] ;

[0012] ;

[0013] ;

[0014] .

[0015] Furthermore, the structural formula of the pyridazine-anthracene luminescent material is any one of the following structural formulas:

[0016] ;

[0017] ;

[0018] ;

[0019] .

[0020] The invention also discloses an organic electroluminescent device, which contains the pyridazine and anthracene luminescent material of the invention.

[0021] Furthermore, the pyridazine anthracene luminescent material is applied to the luminescent layer of an organic electroluminescent device.

[0022] Furthermore, the pyridazine anthracene luminescent material is used as a luminescent host material in the luminescent layer of an organic electroluminescent device.

[0023] Furthermore, the pyridazine anthracene luminescent material is used as an electron transport material in an electron transport layer.

[0024] Furthermore, the pyridazine and anthracene luminescent material is applied to a light-emitting layer or an electron transport layer, and the organic electroluminescent device has a blue light characteristic.

[0025] The present invention also discloses an electronic device, which comprises the organic electroluminescent device of the present invention.

[0026] The beneficial effects of the present invention are:

[0027] (1) The pyridazine-anthracene luminescent material of the present invention exhibits advantages such as good thermal stability, high luminous efficiency, high external quantum efficiency, low driving voltage, and long life when applied to organic electroluminescent devices.

[0028] (2) The main structure of the pyridazine-anthracene luminescent material contains pyridazine, anthracene, and pyridine rigid fused ring materials, and has high thermal stability, making it a carrier transport material with hole transport, electron transport, and luminescence properties. Pyridazine also has a strong electron-withdrawing ability. Electron-withdrawing groups can be introduced at different sites to adjust the overlap of its HOMO / LUMO orbitals, thereby changing the size of its energy gap. Therefore, organic luminescent materials with different luminescent colors can be synthesized; the "heavy atom effect" in deuterated compounds can improve quantum efficiency and extend the life and stability of light-emitting device materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 is a schematic structural diagram of the organic electroluminescent device described in the embodiment;

[0030] In the figure, 1, transparent substrate layer; 2, transparent anode electrode layer; 3, hole injection layer; 4, hole transport layer; 5, electron blocking layer; 6, light-emitting layer; 7, hole blocking layer; 8, electron transport layer; 9, electron injection layer; 10, cathode reflective electrode layer. DETAILED DESCRIPTION

[0031] The present invention can be implemented in many other ways than those described herein, and those skilled in the art can make similar improvements without violating the scope of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used are only for describing specific embodiments and are not intended to limit the present invention.

[0033] 1. Preparation Example

[0034] Preparation of common intermediate compound F:

[0035] .

[0036] The preparation of compound F comprises the following steps:

[0037] (1) Under inert gas protection, 3,6-dichloropyridazine, o-nitrophenol, potassium carbonate, and DMF were added to a three-necked flask, and then the temperature was raised to 120.0℃ and kept warm. The molar ratio of 3,6-dichloropyridazine, o-nitrophenol, and potassium carbonate was 1.0:1.0:3.0eq. The reaction was kept at 120.0℃. After the reaction was complete, the product was hydrolyzed, extracted, washed with water, column chromatographed, and recrystallized to obtain a light yellow solid compound A with a total yield of 77.1% and a GC yield of 99.5%. GC-MS: theoretical value: 251.63, measured value: 251.01.

[0038] The NMR data of compound A are:

[0039] 1 H-NMR (Chloroform-d) δ 8.22 (dd, J = 7.5, 1.6 Hz, 2H), 7.74 (td, J =7.5, 1.5 Hz, 2H), 7.59 (d, J = 7.5 Hz, 2H), 7.54 (dd, J = 7.5, 1.5 Hz, 2H), 7.19 (td, J= 7.5, 1.5 Hz, 2H), 7.00 (d, J= 7.5 Hz, 2H).

[0040] 13 C NMR (Chloroform-d) δ 110.5, 114.8, 120.4, 125.7, 130.8, 133.4, 138.4, 151.1, 155.2, 163.3.

[0041] (2) Under inert gas protection, compound A, triphenylphosphine, and ODB were added to a three-necked flask, then heated to 160.0°C and maintained at this temperature. The molar ratio of compound A to triphenylphosphine was 1.0:2.5 eq. The reaction was allowed to proceed at 160.0°C. After the reaction was complete, the product was subjected to solvent removal, complexation, filtration, column chromatography, and recrystallization to obtain a yellow solid compound B. The total yield was 63.6%, and the GC yield was 99.5%. GC-MS: theoretical value: 219.63, measured value: 219.02.

[0042] The NMR data of compound B are:

[0043] 1 H-NMR (Chloroform-d) δ 8.02 (s, 1H), 7.29 (s, 1H), 7.15 (m, 3H), 7.04 (d, J = 2.6 Hz, 1H), 6.75 (m, 1H).

[0044] 13 C-NMR (Chloroform-d) δ 112.8, 114.5, 116.0, 120.0, 123.0, 131.8, 138.8, 142.7, 147.9, 159.6.

[0045] (3) Under inert gas protection, the temperature was controlled at 65.0-70.0°C. A tetrahydrofuran solution of 9-anthraceneboronic acid was slowly added to a solution containing 2-bromopyridine, potassium hydroxide, toluene, water, catalyst palladium acetate, and ligand 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl. The molar ratio of 9-anthraceneboronic acid, 2-bromopyridine, potassium hydroxide, catalyst, and ligand was 1:1:2.5:0.005:0.01 eq. The reaction was maintained for 10 h until complete reaction. After post-treatment, washing with water, column chromatography, and recrystallization, an off-white solid C was obtained. The total yield was 81.3%, and the GC yield was 99.5%. GC-MS: theoretical value: 334.22, measured value: 335.01.

[0046] The NMR data of compound C are:

[0047] 1 H-NMR(Chloroform-d) δ 8.68 (dd, J = 7.5, 1.4 Hz, 1H), 8.35 (dd, J =7.4, 1.6 Hz, 2H), 8.12 (dd, J = 7.4, 1.6 Hz, 2H), 7.81 (dd, J = 7.5, 1.5 Hz,1H), 7.70(td, J = 7.5, 1.5 Hz, 1H), 7.53 (td, J = 7.4, 1.7 Hz, 2H), 7.47 (td,J = 7.5, 1.6 Hz, 2H), 7.24 (td, J = 7.4, 1.6 Hz, 1H).

[0048] 13 C-NMR (Chloroform-d)δ 120.9, 123.3, 123.5, 125.3, 126.9, 127.4, 128.3, 129.9, 130.3, 131.0, 136.8, 149.1, 156.0.

[0049] (4) Under inert gas protection, the temperature was controlled at 0.0-5.0°C. The DMF solution of NBS was slowly added to the solution containing compound C and dichloroethane. The molar ratio of compound C to NBS was 1:1.2 eq. The reaction was maintained for 2 h until complete. After post-treatment, washing with water, column chromatography, and recrystallization, an off-white solid D was obtained. The total yield was 62.3%, and the GC yield was 99.3%. GC-MS: theoretical value: 255.32, measured value: 255.10.

[0050] The NMR data of compound D are:

[0051] 1 H-NMR(Chloroform-d) δ 8.66 (dd, J = 7.5, 1.4 Hz, 1H), 8.47 (m, 1H), 8.07 (dt, J = 7.1, 1.6 Hz, 4H), 7.79 (dd, J = 7.5, 1.6 Hz, 1H), 7.71 (td, J =7.5, 1.6Hz, 1H), 7.56 (m, 4H), 7.24 (td, J = 7.5, 1.6Hz, 1H).

[0052] 13 C-NMR (Chloroform-d)δ 120.9, 123.3, 125.0, 125.8, 126.2, 128.2, 128.6, 130.3, 132.4, 133.4, 136.8, 149.1, 156.0.

[0053] (5) Under inert gas protection, the temperature was controlled below -78.0°C. The n-butyl lithium solution was slowly added to a solution containing compound D, triisopropyl borate, and tetrahydrofuran. The molar ratio of compound D, n-butyl lithium, and triisopropyl borate was 1:1.3:1.5 eq. The reaction was maintained for 2 h until complete. After post-treatment, hydrolysis, water washing, solvent removal, and beating, an off-white solid E was obtained. The total yield was 87.8%, and the HPLC yield was 99.9%. LC-MS: theoretical value: 298.15, measured value: 298.12.

[0054] The NMR data of compound E are:

[0055] 1H-NMR(Chloroform-d) δ 8.66 (dd, J = 7.5, 1.5 Hz, 1H), 8.39 (m, 2H), 8.33 (m, 2H), 7.87 (dd, J = 7.5, 1.6 Hz, 1H), 7.72 (td, J = 7.5, 1.5 Hz, 1H),7.49 (m,6H), 7.23 (td, J = 7.5, 1.5 Hz, 1H).

[0056] 13 C-NMR (Chloroform-d) δ 120.9, 123.3, 124.1, 125.3, 126.7, 126.9, 127.5, 129.9, 130.3, 136.8, 139.2, 149.1, 156.0.

[0057] (6) Under inert gas protection, the temperature was controlled at 75.0-80.0°C. The tetrahydrofuran solution of compound E was slowly added to a solution containing compound B, potassium hydroxide, toluene, water, catalyst palladium acetate, and ligand 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl. The molar ratio of compound E, compound B, potassium carbonate, catalyst, and ligand was 1.2:1:2.5:0.005:0.01 eq. The reaction was maintained for 12 h until complete. After post-treatment, washing with water, column chromatography, and recrystallization, an off-white solid F was obtained. The total yield was 80.0%, and the HPLC yield was 99.8%. LC-MS: theoretical value: 438.49, measured value: 438.15.

[0058] The NMR data of compound F are:

[0059] 1 H-NMR(Chloroform-d) δ 8.67 (dd, J = 7.5, 1.5 Hz, 1H), 8.47 (m, 4H), 8.15 (s, 1H), 7.83 (dd, J = 7.5, 1.5 Hz, 1H), 7.74 (m, 2H), 7.52 (m, 4H), 7.23 (td, J =7.5, 1.5 Hz, 1H), 7.10 (dd, J = 7.1, 2.0 Hz, 1H), 7.07 (m, 2H), 6.75 (dd, J = 7.0, 2.0 Hz, 1H).

[0060] 13C-NMR (Chloroform-d) δ 112.8 , 114.5 , 116.0 , 120.0 , 120.9 ,123.0, 123.3 , 125.3 , 126.9 , 129.8 , 130.2 , 131.8 , 136.8 , 138.8, 142.7, 149.1, 155.9, 159.6.

[0061] Example 1

[0062] Synthesis of compound 12:

[0063] .

[0064] Under inert gas, 20.0 g (0.046 mol) of compound F, 10.89 g (0.046 mol) of intermediate 12, 6.6 g (0.068 mol) of sodium tert-butoxide, 400 mL of toluene, 0.42 g (0.46 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.43 g (0.91 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl were placed in a 1-L three-necked flask. The mixture was stirred and heated to 105°C. The reaction was maintained for 24 hours, with an HPLC yield of 95.8%. After extraction, washing with water, column chromatography, and recrystallization, 23.8 g of a light yellow-green solid compound 12 was obtained, with an overall yield of 81.5% and an HPLC yield of 99.95%. HPLC-MS: Calculated value: 640.75, measured value: 640.23.

[0065] The NMR data of compound 12 are:

[0066] 1H-NMR(Chloroform-d) δ 8.65 (dd, J = 7.5, 1.4 Hz, 1H), 8.45 (m, 4H), 7.83 (dd, J = 7.5, 1.4 Hz, 1H), 7.76 (m, 3H), 7.51 (dd, J = 7.5, 1.4 Hz, 1H),7.49 (m,4H), 7.29 (m, 3H), 7.17 (dd, J = 7.4, 1.7 Hz, 1H), 7.03 (dtd, J =22.2, 7.5, 1.7 Hz, 2H), 6.77 (dd, J = 7.4, 1.6 Hz, 1H), 6.51 (dp, J = 10.8,1.0 Hz, 1H), 6.08 (td, J = 6.2, 1.4 Hz, 1H), 5.89 (dt, J = 11.0, 6.2 Hz, 1H), 3.97 (dd, J = 6.2, 1.1 Hz, 2H), 3.86 (dd, J = 6.2, 0.9 Hz, 2H).

[0067] 13 C-NMR (Chloroform-d) δ 113.3 , 116.0 , 117.1 , 120.9 , 122.2 ,123.2, 124.5 , 124.7, 125.1 , 125.2 , 125.3 , 125.9 , 126.0 , 126.8, 127.5, 128.2, 129.8, 130.2, 130.9, 131.1, 134.5, 136.8, 141.5, 144.7, 149.1, 155.9, 159.6.

[0068] Example 2

[0069] Synthesis of compound 15:

[0070] .

[0071] Under inert gas, 20.0 g (0.046 mol) of compound F, 14.3 g (0.046 mol) of intermediate 15, 6.6 g (0.068 mol) of sodium tert-butoxide, 400 mL of toluene, 0.42 g (0.46 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.43 g (0.91 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl were placed in a 1-L three-necked flask. The mixture was stirred and heated to 105°C. The reaction was maintained for 18 hours, with an HPLC result of 93.8%. After extraction, washing with water, column chromatography, and recrystallization, 25.5 g of a light yellow-green solid compound 15 was obtained, with an overall yield of 78.1% and an HPLC result of 99.95%. LC-MS: Calculated value: 714.83, found: 714.24.

[0072] The NMR data of compound 15 are:

[0073] 1 H-NMR(Chloroform-d) δ 8.70 (d, J = 7.5 Hz, 1H), 8.67 (m, 2H), 8.45(m, 4H), 8.08 (dd, J = 7.5, 1.5 Hz, 1H), 7.95 (m, 1H), 7.92 (m, 2H), 7.81 (dd,J = 7.5, 1.5 Hz, 2H), 7.73 (s, 1H), 7.71 (m, 2H), 7.65 (m, 1H), 7.57 (m, 3H),7.50(m, 4H), 7.38 (dd,J = 7.5, 1.5 Hz, 1H), 7.23 (td, J = 7.4, 1.6 Hz, 1H), 7.11 (m, 2H), 7.02 (ddd, J = 7.5, 6.4, 2.7 Hz, 1H), 6.77 (dd, J = 7.4, 1.3Hz, 1H).

[0074] 13C-NMR (Chloroform-d) δ 113.3 , 116.0 , 117.7 , 120.8 , 120.9 ,122.2, 123.2 , 125.2 , 125.3 , 126.5 , 126.8 , 127.1 , 127.7 , 128.1 , 128.6, 129.8 , 130.1 , 130.5 , 130.7 , 132.1 , 132.4 , 132.8 , 134.5 , 136.8 ,137.2 , 141.6, 144.3 , 144.7 , 149.1, 155.9 , 159.6.

[0075] Example 3

[0076] Synthesis of compound 23:

[0077] .

[0078] Under inert gas, 20.0 g (0.046 mol) of compound F, 16.0 g (0.046 mol) of intermediate 23, 6.6 g (0.068 mol) of sodium tert-butoxide, 400 mL of toluene, 0.42 g (0.46 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.43 g (0.91 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl were placed in a 1-L three-necked flask. The mixture was stirred and heated to 105°C. The reaction was maintained at this temperature for 10 h. HPLC analysis revealed a 95.1% yield. After extraction, washing with water, column chromatography, and recrystallization, 28.7 g of compound 23, a light yellow-green solid, was obtained. The total yield was 83.5%, and the HPLC analysis revealed a 99.95% yield. LC-MS analysis revealed a theoretical value of 752.88 and a measured value of 752.26.

[0079] The NMR data of compound 23 are:

[0080] 1 H-NMR(Chloroform-d) δ 8.45 (m, 1H), 7.86 (m, 1H), 7.71 (m, 0H), 7.50(m, 1H), 7.41 (m, 2H), 7.09 (m, 1H), 6.83 (m, 1H).

[0081] 13C-NMR (Chloroform-d) δ 110.3 , 113.3 , 116.0 , 117.8 , 120.0 ,120.9, 121.2 , 122.2 , 123.2 , 123.8 , 125.3 , 126.9 , 128.5 , 128.9, 129.8, 130.2, 132.0, 134.5, 136.8, 139.8, 141.6, 144.3, 144.7, 149.1, 151.1, 155.9, 159.6.

[0082] Example 4

[0083] Synthesis of compound 32:

[0084] .

[0085] Under inert gas, 20.0 g (0.046 mol) of compound F, 12.7 g (0.046 mol) of intermediate 32, 6.6 g (0.068 mol) of sodium tert-butoxide, 400 mL of toluene, 0.42 g (0.46 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.43 g (0.91 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl were placed in a 1-L three-necked flask. The mixture was stirred and heated to 105°C for 8 h. HPLC analysis revealed a 95.1% yield. After extraction, washing with water, column chromatography, and recrystallization, 26.7 g of compound 32, a light yellow-green solid, was obtained. The total yield was 86.1%, and the HPLC analysis revealed a 99.95% yield. LC-MS analysis revealed a theoretical value of 680.77 and a measured value of 680.22.

[0086] The NMR data of compound 32 are:

[0087] 1H-NMR(Chloroform-d) δ 8.65 (dd, J = 7.5, 1.4 Hz, 1H), 8.41 (dt, J =5.7, 3.4 Hz, 4H), 7.83 (dd, J = 7.5, 1.4 Hz, 1H), 7.74 (s, 1H), 7.67 (td, J =7.5, 1.5Hz, 1H), 7.63 (m, 2H), 7.50 (m, 5H), 7.47 (m, 6H), 7.37 (m, 1H), 7.26(m, 2H), 7.13 (ddd, J = 15.4, 7.4, 1.6 Hz, 2H), 7.05 (dtd, J = 16.3, 7.4, 1.8Hz, 2H), 6.76 (dd, J = 7.2, 1.8 Hz, 1H).

[0088] 13 C-NMR (Chloroform-d) δ 111.3, 113.3, 116.0, 119.3, 120.9, 121.6, 122.2, 123.2, 125.2, 125.3, 126.7, 126.9, 127.9, 128.2, 128.8, 129.8, 130.2, 134.5, 136.8, 137.8, 138.4, 141.4, 144.7, 149.1, 154.6, 155.9, 159.6.

[0089] Example 5

[0090] Synthesis of compound 33:

[0091] .

[0092] Under inert gas, 20.0 g (0.046 mol) of compound F, 13.8 g (0.046 mol) of intermediate 33, 6.6 g (0.068 mol) of sodium tert-butoxide, 400 mL of toluene, 0.42 g (0.46 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.43 g (0.91 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl were placed in a 1-L three-necked flask. The mixture was stirred and heated to 105°C. The reaction was maintained at this temperature for 12 hours. HPLC analysis revealed a 95.1% yield. After extraction, washing with water, column chromatography, and recrystallization, 26.4 g of compound 33, a light yellow-green solid, was obtained. The total yield was 82.2%, and the HPLC analysis revealed a 99.95% yield. LC-MS analysis revealed a theoretical value of 704.79 and a measured value of 704.22.

[0093] The NMR data of compound 33 are:

[0094] 1 H-NMR(Chloroform-d) δ 9.33 (d, J = 0.8 Hz, 1H), 8.65 (dd, J = 7.5,1.4 Hz, 1H), 8.45 (m, 4H), 8.08 (d, J = 1.9 Hz, 1H), 8.05 (m, 2H), 7.85 (ddd,J = 7.6,4.3, 1.2 Hz, 2H), 7.81 (dd,J = 7.5, 1.5 Hz, 1H), 7.73 (s, 1H), 7.68(td,J = 7.4, 1.6 Hz, 1H), 7.60 (dd,J = 7.6, 1.5 Hz, 1H), 7.54 (dd, J = 7.4,1.6 Hz,1H), 7.51 (m, 5H), 7.42 (dd, J = 7.8, 1.5 Hz, 1H), 7.37 (td, J = 7.4,1.6 Hz, 1H), 7.23 (td, J = 7.4, 1.6 Hz, 1H), 7.12 (dd, J = 7.4, 1.7 Hz, 1H), 7.08 (td,J = 7.4, 1.6 Hz, 1H), 7.02 (td, J = 7.4, 1.7 Hz, 1H), 6.78 (dd, J =7.3, 1.5 Hz, 1H).

[0095] 13 C-NMR (Chloroform-d) δ 107.0 , 111.6 , 113.3 , 115.2 , 116.0 ,120.8, 120.9 , 122.2 , 122.4 , 123.2 , 124.2 , 124.8 , 125.3 , 126.9, 127.1, 127.3, 127.5, 128.2, 129.8, 130.2, 132.1, 133.9, 134.5, 136.8,141.5, 144.7, 149.1, 155.2, 155.8 , 155.9, 159.6.

[0096] Example 6

[0097] Synthesis of compound 46:

[0098] .

[0099] Under inert gas, 20.0 g (0.046 mol) of compound F, 16.4 g (0.046 mol) of intermediate 46, 6.6 g (0.068 mol) of sodium tert-butoxide, 400 mL of toluene, 0.42 g (0.46 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.43 g (0.91 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl were placed in a 1-L three-necked flask. The mixture was stirred and heated to 105°C. The reaction was maintained for 16 hours, with an HPLC yield of 95.1%. After extraction, washing with water, column chromatography, and recrystallization, 27.0 g of a light yellow-green solid, compound 46, was obtained. The total yield was 77.9%, and the HPLC yield was 99.95%. LC-MS: Calculated value: 760.91, found: 760.30.

[0100] The NMR data of compound 46 are:

[0101] 1 H-NMR(Chloroform-d) δ 8.65 (dd, J = 7.5, 1.4 Hz, 1H), 8.45 (m, 4H), 8.10 (dd, J = 7.3, 1.7 Hz, 1H), 8.00 (d, J = 7.5 Hz, 1H), 7.84 (m, 2H), 7.73(s, 1H),7.68 (td, J = 7.5, 1.5 Hz, 1H), 7.63 (m, 1H), 7.53 (m, 9H), 7.31 (m,4H), 7.13 (m, 1H), 7.09 (m, 2H), 6.78 (m, 1H).

[0102] 13 C-NMR (Chloroform-d) δ 109.7 , 110.3 , 113.3 , 116.0 , 117.8 ,120.2, 120.9 , 121.2 , 122.2 , 123.1 , 123.2 , 124.9 , 125.3 , 126.2 , 126.7, 126.9 , 129.4 , 129.8 , 130.2 , 134.5 , 136.8 , 138.1 , 138.5 , 139.9 ,140.6 , 141.3, 141.6 , 144.3 , 144.7 , 149.1 , 155.9, 159.6.

[0103] Example 7

[0104] Synthesis of compound 53:

[0105] .

[0106] Under inert gas, 20.0 g (0.046 mol) of compound F, 11.2 g (0.046 mol) of intermediate 53, 6.6 g (0.068 mol) of sodium tert-butoxide, 400 mL of toluene, 0.42 g (0.46 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.43 g (0.91 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl were placed in a 1-L three-necked flask. The mixture was stirred and heated to 105°C. The reaction was maintained at this temperature for 12 h. HPLC analysis revealed a 95.1% yield. After extraction, washing with water, column chromatography, and recrystallization, 21.0 g of a light yellow-green solid, compound 53, was obtained. The total yield was 71.2%, and the HPLC analysis revealed a 99.95% yield. LC-MS analysis revealed a theoretical value of 647.76, and a measured value of 647.18.

[0107] The NMR data of compound 53 are:

[0108] 1 H-NMR(Chloroform-d) δ 8.65 (dd, J = 7.5, 1.4 Hz, 1H), 8.45 (m, 4H), 7.94 (m, 2H), 7.83 (dd, J = 7.5, 1.4 Hz, 1H), 7.77 (s, 1H), 7.71 (dd, J =7.3, 1.7 Hz,1H), 7.67 (td, J = 7.5, 1.5 Hz, 1H), 7.52 (m, 8H), 7.44 (m, 1H),7.23 (td, J = 7.5, 1.5 Hz, 1H), 7.15 (dd, J = 7.1, 1.9 Hz, 1H), 7.02 (dtd, J= 14.5, 7.5, 1.8Hz, 2H), 6.77 (dd, J = 7.2, 1.9 Hz, 1H).

[0109] 13C-NMR (Chloroform-d) δ 113.3, 114.8, 116.0, 120.9, 122.2, 123.2, 125.2, 125.3, 126.7, 126.9, 127.2, 128.4, 129.2, 129.8, 130.2, 134.4, 136.8, 137.8, 138.1, 141.6, 144.7, 148.6, 149.1, 155.9, 159.6, 166.8.

[0110] Example 8

[0111] Synthesis of compound 58:

[0112] .

[0113] Under inert gas, 20.0 g (0.046 mol) of compound F, 16.3 g (0.046 mol) of intermediate 58, 6.6 g (0.068 mol) of sodium tert-butoxide, 400 mL of toluene, 0.42 g (0.46 mmol) of tris(dibenzylideneacetone)dipalladium, and 0.43 g (0.91 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl were placed in a 1-L three-necked flask. The mixture was stirred and heated to 105°C. The reaction was maintained at this temperature for 10 h. HPLC analysis revealed a 95.1% yield. After extraction, washing with water, column chromatography, and recrystallization, 28.6 g of compound 58, a light yellow-green solid, was obtained. The total yield was 82.5%, and the HPLC analysis revealed a 99.95% yield. LC-MS analysis revealed a theoretical value of 759.93 and a measured value of 759.35.

[0114] The NMR data of compound 58 are:

[0115] 1H-NMR(Chloroform-d) δ 8.65 (dd, J = 7.5, 1.4 Hz, 1H), 8.40 (ddd, J =5.7, 4.1, 3.1 Hz, 4H), 7.81 (dd, J = 7.4, 1.5 Hz, 1H), 7.68 (td, J = 7.5, 1.5Hz, 1H),7.50 (m, 4H), 7.40 (s, 1H), 7.23 (td, J = 7.4, 1.6 Hz, 1H), 7.16 (dd,J = 7.4, 1.6 Hz, 1H), 7.06 (td, J = 7.5, 1.7 Hz, 1H), 7.01 (td, J = 7.4, 1.7Hz, 1H), 6.76 (dd, J = 7.3, 1.7 Hz, 1H).

[0116] 13 C-NMR (Chloroform-d) δ113.3, 116.0, 120.9, 122.2, 123.2, 125.3,126.7, 126.9, 129.8, 130.2, 134.5, 136.8, 138.5, 141.6, 144.7, 149.1, 155.9, 159.6, 162.6, 167.0.

[0117] The synthesis methods of other compounds included in the present invention are the same or similar to those in the specific embodiments and are not listed one by one. The mass-to-nuclear ratios of the synthesized compounds are shown in Tables 1 and 2 below.

[0118] Table 1 Mass-to-nuclear ratios of compounds 1-30

[0119]

[0120] Table 2 Mass-to-nuclear ratios of compounds 31-60

[0121]

[0122] 2. Preparation and Evaluation of Organic Electroluminescent Devices

[0123] The application effects of the OLED materials synthesized by the present invention on devices are described in detail through the following application cases 1-24 and comparative examples 1-3. The specific structural formulas of the compounds involved are as follows:

[0124] .

[0125] Comparative Example 1

[0126] The structure of organic electroluminescent devices is as follows Figure 1 As shown, a transparent anode electrode layer 2 (209 nm thick, made of indium tin oxide) with a transparent substrate layer 1 was treated: the glass transparent substrate layer 1 was washed, i.e., sequentially subjected to alkaline washing, deionized water washing, acetone ultrasonic cleaning, ethanol ultrasonic cleaning, and ultrapure water cleaning. After drying, the transparent anode electrode layer 2 was then subjected to UV-ozone cleaning to ensure that organic residues on the surface of the transparent anode electrode layer 2 were removed. After the above treatments, a hole injection layer 3 was evaporated on the transparent anode electrode layer 2 using a vacuum evaporation device to deposit a material of structural formula 1 (evaporation conditions: using a molybdenum crucible, an evaporation rate of 0.1 nm / s, and a vacuum degree of 4.0*10 -5 Pa), with a film thickness of 57nm. This layer of organic material is used as the hole injection layer 3. The hole injection layer 3 is then evaporated with a thickness of 23nm to form the hole transport layer 4. The hole transport layer 4 is then followed by an evaporation of a material of the structural formula 3 with a thickness of 19nm to form the electron blocking layer 5.

[0127] After the electron blocking layer 5 is deposited, the structural formula 4 material and Ir(PPy)3 are mixed as doping materials at a doping weight ratio of 94:6 and then deposited onto the empty electron blocking layer 5 (deposition conditions are: using a molybdenum crucible, a deposition rate of 0.1 nm / s, and a vacuum degree of 4.0*10 -5 Pa) to obtain the light-emitting layer 6, the thickness of the light-emitting layer 6 was 32 nm.

[0128] The hole-blocking layer 7 is prepared by vacuum-evaporating the hole-blocking layer 7 material (the material shown in structural formula 5) onto the light-emitting layer 6 after the light-emitting layer 6 (evaporation conditions: using a molybdenum crucible, evaporation rate 0.1nm / s, vacuum degree 4.0*10-5Pa). The vacuum-evaporated film thickness of this material is 19nm. After the evaporation is completed, the material shown in structural formula 6 is immediately evaporated to obtain the electron transport layer 8. The evaporated film thickness is 79nm. The electron injection layer 9 is formed on the electron transport layer 8 by vacuum evaporation using a 0.8nm thick lithium fluoride (LiF) layer.

[0129] On the electron injection layer 9 , a cathode reflective electrode layer 10 is formed by vacuum deposition. The cathode reflective electrode layer 10 is an aluminum (Al) layer having a thickness of 146 nm.

[0130] After the organic electroluminescent device is completed as described above, the anode and cathode are connected using a known driving circuit, and the luminous efficiency, luminous spectrum, and current-voltage characteristics of the device are measured.

[0131] Comparative Example 2

[0132] An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the main light-emitting material (Structural Formula 4) used in the light-emitting layer 6 of the organic electroluminescent device was changed to a compound of Structural Formula 5.

[0133] Application Example 1

[0134] An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the main light-emitting material (Structural Formula 4) used in the light-emitting layer 6 of the organic electroluminescent device was changed to Compound 12.

[0135] Application Example 2

[0136] An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the main light-emitting material (Structural Formula 4) used in the light-emitting layer 6 of the organic electroluminescent device was changed to Compound 15.

[0137] Application Example 3

[0138] An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the main light-emitting material (Structural Formula 4) used in the light-emitting layer 6 of the organic electroluminescent device was changed to Compound 23.

[0139] Application Example 4

[0140] An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the main light-emitting material (Structural Formula 4) used in the light-emitting layer 6 of the organic electroluminescent device was changed to Compound 32.

[0141] Application Example 5

[0142] An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the main light-emitting material (Structural Formula 4) used in the light-emitting layer 6 of the organic electroluminescent device was changed to Compound 33.

[0143] Application Example 6

[0144] An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the main light-emitting material (Structural Formula 4) used in the light-emitting layer 6 of the organic electroluminescent device was changed to Compound 46.

[0145] Application Example 7

[0146] An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the main light-emitting material (Structural Formula 4) used in the light-emitting layer 6 of the organic electroluminescent device was changed to Compound 53.

[0147] Application Example 8

[0148] An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the main light-emitting material (Structural Formula 4) used in the light-emitting layer 6 of the organic electroluminescent device was changed to Compound 58.

[0149] Application Example 9

[0150] An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the compound of formula 6 used in the electron transport layer 8 of the organic electroluminescent device was changed to compound 12.

[0151] Application Example 10

[0152] An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the compound of formula 6 used in the electron transport layer 8 of the organic electroluminescent device was changed to compound 33.

[0153] Application Example 11

[0154] An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the compound of formula 6 used in the electron transport layer 8 of the organic electroluminescent device was changed to compound 58.

[0155] Application Example 1-11 and Comparative Example 1-2 have the same brightness (1000cd / m 2 ), the test results under the same external ambient temperature (25.0℃) and the same humidity (40.0%) are shown in Table 3.

[0156] Table 3 Test results

[0157]

[0158] Comparison of the data in Table 3 demonstrates that light-emitting devices fabricated using the organic compounds of the present invention as OLED luminescent materials exhibit significant advantages in current efficiency, driving voltage, lifetime, external quantum efficiency, and other performance. Therefore, the application of the compounds prepared using the present invention in organic electroluminescent devices has significant commercial value and broad market and industrial prospects.

[0159] The technical features of the above-described embodiments can be combined arbitrarily. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are exhaustively listed. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0160] For those skilled in the art, several variations and improvements may be made without departing from the scope of the present invention, which all fall within the scope of protection of the present invention. The scope of protection of the present invention shall be based on the appended claims.

Claims

1. A pyridazine-anthracene luminescent material, characterized in that: The structure of the pyridazine and anthracene luminescent material is shown in the following general formula [I]: General formula [I]; The R is any one of biphenyl, deuterated biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, pyrenyl, chrysyl, benzochrysyl, fluorenyl, spirobifluorenyl, furanyl, carbazolyl, imidazolyl, thienyl, oxazolyl, thiazolyl, triazinyl, and triphenylene.

2. A pyridazine-anthracene luminescent material, characterized in that: The structural formula of the pyridazine and anthracene luminescent material is any one of the following structural formulas: 。 3. An organic electroluminescent device, characterized in that: The organic electroluminescent device contains the pyridazine-anthracene luminescent material according to any one of claims 1 to 2.

4. The organic electroluminescent device according to claim 3, characterized in that: The pyridazine anthracene luminescent material is applied to the luminescent layer of an organic electroluminescent device.

5. The organic electroluminescent device according to claim 4, characterized in that: The pyridazine and anthracene luminescent material is used as a luminescent host material in the luminescent layer of an organic electroluminescent device.

6. The organic electroluminescent device according to claim 3, characterized in that: The pyridazine anthracene luminescent material is used as an electron transport material in an electron transport layer.

7. The organic electroluminescent device according to claim 3, characterized in that: The pyridazine and anthracene luminescent material is applied to a luminescent layer or an electron transport layer, and the organic electroluminescent device has a blue light characteristic.

8. An electronic device, characterized in that: The electronic device comprises the organic electroluminescent device according to any one of claims 3 to 7.

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