Pyridazino anthracene luminescent material and application thereof

Abstract

The invention relates to the technical field of electronic luminescent materials, in particular to a pyridazino anthracene luminescent material and application thereof, the structure of the pyridazino anthracene luminescent material is as shown in the following general formula [I]: # imgabs0 # general formula [I], r is a substituted or unsubstituted C1-C30 alkane chain, a C1-C30 aryl group or a C1-C30 heteroaryl group, a substituent group of the substituted or unsubstituted alkane chain is selected from hydrogen, deuterium, the C1-C30 alkane chain, the C1-C30 aryl group or the C1-C30 heteroaryl group, and a heteroatom of the heteroaryl group is selected from any one or more of N, O and S. The compound has good molecular stability when applied to an organic light-emitting device, the prepared OLED device has excellent photoelectric performance, high thermal stability, low driving voltage and high light-emitting efficiency, the service life of the device can be prolonged, the light-emitting performance is good, and the organic light-emitting device can be widely applied to the field of organic light-emitting devices. And the requirements of device manufacturers can be well met.

Description

Technical Field

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

[0002] Organic electroluminescence (Organic Light Emitting Diode, abbreviated as OLED), compared with liquid crystal displays, has the advantages of high brightness, thin volume, rapid response, stable performance, high contrast, wide viewing angle, full color, and relatively easy preparation of large-area flexible screens. It is very promising to replace existing LCD displays and fluorescent lamp lighting, and has excellent application prospects.

[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 structure layer sandwiched between the positive and negative electrodes. More basically, the structure layer includes a hole transport layer (HTL), a light-emitting layer (EML), and an electron transport layer (ETL). When electricity 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 in the corresponding organic layers and finally reach the light-emitting layer and recombine to form excitons. When the excitons de-excite and return to the ground state, photons are emitted via radiative decay. The emission color mainly depends on the bandgap width of the luminescent material. Electroluminescent materials play a crucial role in OLED display technology. A good electroluminescent material is one of the key factors determining the performance of the light-emitting device.

[0004] In the current OLED industry, there are still problems such as short lifespan, low luminous efficiency, and poor thermal stability of luminescent materials. 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] Aiming at the deficiencies of the existing technology, the present invention provides a pyridazine-anthracene-based luminescent material and its application. The pyridazine-anthracene-based luminescent material has good molecular stability. The prepared OLED device has excellent optoelectronic properties, with high thermal stability, low driving voltage, and high external quantum efficiency. It can extend the service life of the device and has excellent color purity, meeting 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-based luminescent material, and the structure of the pyridazine-anthracene-based luminescent material is shown in the following general formula [I]: General formula [I]; R is a substituted or unsubstituted C1-C30 alkane chain, C1-C30 aryl group or C1-C30 heteroaryl group, and the substituents of the substituted or unsubstituted group are selected from hydrogen, deuterium, C1-C30 alkane chain, C1-C30 aryl group or C1-C30 heteroaryl group. The heteroatoms of the heteroaryl group are selected from any one or more of N, O, and S.

[0007] Further, R is any one of biphenyl, deuterated biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, pyrenyl, chrysenyl, benzochrysenyl, fluorenyl, spirobifluorenyl, furyl, carbazolyl, imidazolyl, thienyl, oxazolyl, thiazolyl, triazinyl, triphenylenyl.

[0008] Further, R is any one of the following structural formulas: ; ; ; .

[0009] Further, the structural formula of the pyridazine-anthracene-based light-emitting material is any one of the following structural formulas: ; ; ; .

[0010] The present invention also discloses an organic electroluminescent device containing the pyridazine-anthracene-based light-emitting material of the present invention.

[0011] Further, the pyridazine-anthracene-based light-emitting material is applied to the light-emitting layer of the organic electroluminescent device.

[0012] Further, the pyridazine-anthracene-based light-emitting material is used as a light-emitting host material and applied to the light-emitting layer of the organic electroluminescent device.

[0013] Further, the pyridazine-anthracene-based light-emitting material is used as an electron transport material and applied in the electron transport layer.

[0014] Further, the pyridazine-anthracene-based light-emitting material is applied to the light-emitting layer or the electron transport layer, and the organic electroluminescent device has blue light characteristics.

[0015] The present invention also discloses an electronic device containing the organic electroluminescent device of the present invention.

[0016] The beneficial effects of the present invention are: (1) The pyridazine-anthracene-based luminescent material of the present invention exhibits excellent thermal stability, high luminous efficiency, high external quantum efficiency, low driving voltage, and long lifespan when applied in organic electroluminescent devices.

[0017] (2) The main structure of the pyridazine-anthracene-based luminescent material contains rigid fused-ring materials of pyridazine, anthracene, and pyridine simultaneously, which has high thermal stability and enables it to serve as a charge carrier transport material with hole transport, electron transport, and luminescence properties. Pyridazine also has a strong electron-withdrawing ability, and electron-withdrawing groups can be introduced at different sites to adjust the overlap degree of its HOMO / LUMO orbitals, thereby changing the energy gap size. Therefore, organic luminescent materials with different emission colors can be synthesized; the "heavy atom effect" in deuterated compounds can improve the quantum efficiency, extend the lifespan, and enhance the stability of the luminescent device materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a schematic structural diagram of the organic electroluminescent device described in the embodiments; In the figure, 1 is a transparent substrate layer; 2 is a transparent anode electrode layer; 3 is a hole injection layer; 4 is a hole transport layer; 5 is an electron blocking layer; 6 is a light-emitting layer; 7 is a hole blocking layer; 8 is an electron transport layer; 9 is an electron injection layer; 10 is a cathode reflective electrode layer. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0019] The following provides a detailed description of the specific embodiments of the present invention. The present invention can be implemented in many other ways different from those described herein. Those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed.

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention belongs. The terms used are only for describing the specific embodiments and are not intended to limit the present invention.

[0021] I. Preparation Examples Preparation of the common intermediate compound F: .

[0022] The preparation of compound F includes the following steps: (1)Under the protection of inert gas, 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 °C for heat preservation. The molar ratio of 3,6-dichloropyridazine, o-nitrophenol, and potassium carbonate was 1.0:1.0:3.0 eq. The reaction was carried out at 120.0 °C for heat preservation. After the reaction was complete, hydrolysis, extraction with water washing, column chromatography, and recrystallization were carried out to obtain a light yellow solid compound A. The total yield was 77.1%, and the GC was 99.5%. GC-MS: Theoretical value: 251.63, Measured value: 251.01.

[0023] The NMR data of compound A are as follows: 1 1H-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).

[0024] 13 13C NMR (Chloroform-d) δ 110.5, 114.8, 120.4, 125.7, 130.8,133.4, 138.4, 151.1, 155.2, 163.3.

[0025] (2)Under the protection of inert gas, compound A, triphenylphosphine, and ODB were added to a three-necked flask, and then the temperature was raised to 160.0 °C for heat preservation. The molar ratio of compound A to triphenylphosphine was 1.0:2.5 eq. The reaction was carried out at 160.0 °C for heat preservation. After the reaction was complete, the solvent was removed, complexation, filtration, column chromatography, and recrystallization were carried out to obtain a yellow solid compound B. The total yield was 63.6%, and the GC was 99.5%. GC-MS: Theoretical value: 219.63, Measured value: 219.02.

[0026] The NMR data of compound B are as follows: 1 1H-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).

[0027] 1313C-NMR (Chloroform-d) δ 112.8, 114.5, 116.0, 120.0, 123.0, 131.8, 138.8, 142.7, 147.9, 159.6。

[0028] (3)Under the protection of inert gas, the temperature was controlled at 65.0 - 70.0 °C, and the tetrahydrofuran solution of 9-anthracene boronic acid was slowly added to the solution containing 2-bromopyridine, potassium hydroxide, toluene, water, the catalyst palladium acetate, and the ligand 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl. The molar ratio of 9-anthracene boronic acid, 2-bromopyridine, potassium hydroxide, the catalyst, and the ligand was 1:1:2.5:0.005:0.01 eq. The reaction was kept warm for 10 h until it was complete. After treatment by washing with water, column chromatography, and recrystallization, a white solid C was obtained. The total yield was 81.3%, and the GC purity was 99.5%. GC-MS: Theoretical value: 334.22, Measured value: 335.01.

[0029] The NMR data of compound C are as follows: 1 1H-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).

[0030] 13 13C-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。

[0031] (4) Under the protection of inert gas, the temperature was controlled at 0.0 - 5.0 °C, and 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, and the reaction was kept warm for 2 h until completion. After treatment by washing with water, column chromatography, and recrystallization, off-white solid D was obtained. The total yield was 62.3%, and the GC purity was 99.3%. GC-MS: theoretical value: 255.32, measured value: 255.10.

[0032] The NMR data of compound D are as follows: 1 1H-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, 1.6 Hz, 1H), 7.56 (m, 4H), 7.24 (td, J = 7.5, 1.6 Hz, 1H).

[0033] 13 13C-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.

[0034] (5) Under the protection of inert gas, the temperature was controlled below -78.0 °C, and the n-butyllithium solution was slowly added to the solution containing compound D, triisopropyl borate, and tetrahydrofuran. The molar ratio of compound D to n-butyllithium to triisopropyl borate was 1:1.3:1.5 eq, and the reaction was kept warm for 2 h until completion. After treatment by hydrolysis, washing with water, desolvation, and pulping, off-white solid E was obtained. The total yield was 87.8%, and the HPLC purity was 99.9%. LC-MS: theoretical value: 298.15, measured value: 298.12.

[0035] The NMR data of compound E are as follows: 11H-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). 13 13C-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. Under the protection of inert gas, while controlling the temperature at 75.0 - 80.0 °C, slowly add the tetrahydrofuran solution of compound E to the 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 is 1.2:1:2.5:0.005:0.01 eq. Keep the temperature for 12 h until the reaction is complete. The post - treatment includes washing with water, column chromatography, and recrystallization to obtain off - white solid F. The total yield is 80.0%, HPLC: 99.8%. LC - MS: theoretical value: 438.49, measured value: 438.15.

[0036] The NMR data of compound F are as follows: 1 1H-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).

[0037] 1313C-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.

[0038] Example 1 Synthesis of Compound 12: .

[0039] Under the protection of 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 weighed and placed in a 1 L three-necked flask. The mixture was stirred and heated to 105 °C and kept at this temperature for reaction for 24 h. HPLC: 95.8%. After extraction, washing with water, column chromatography, and recrystallization, 23.8 g of light yellowish-green solid Compound 12 was obtained, with an overall yield of 81.5% and HPLC: 99.95%. HPLC-MS: Theoretical value: 640.75, Measured value: 640.23.

[0040] The NMR data of Compound 12 are as follows: 11H-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).

[0041] 13 13C-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.

[0042] Example 2 Synthesis of Compound 15: .

[0043] Under the protection of 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 weighed and placed in a 1 L three-necked flask. The mixture was stirred and heated to 105 °C, and the reaction was carried out at this temperature for 18 h. HPLC: 93.8%. After extraction, washing with water, column chromatography, and recrystallization, 25.5 g of a light yellowish green solid compound 15 was obtained, with an overall yield of 78.1% and HPLC: 99.95%. LC-MS: theoretical value: 714.83, measured value: 714.24.

[0044] The NMR data of compound 15 are as follows: 1 1H-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, 1.3 Hz, 1H).

[0045] 1313C-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。

[0046] Example 3 Synthesis of Compound 23: 。

[0047] Under the protection of 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 weighed and placed in a 1 L three-necked flask. The mixture was stirred and heated to 105 °C and kept at this temperature for reaction for 10 h. HPLC: 95.1%. After extraction, washing with water, column chromatography, and recrystallization, 28.7 g of light yellowish green solid Compound 23 was obtained with an overall yield of 83.5% and HPLC: 99.95%. LC-MS: Theoretical value: 752.88, Measured value: 752.26.

[0048] The NMR data of Compound 23 are as follows: 1 1H-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)。

[0049] 1313C-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。

[0050] Example 4 Synthesis of Compound 32: 。

[0051] Under the protection of 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 weighed and placed in a 1 L three-necked flask. The mixture was stirred and heated to 105 °C and kept at this temperature for reaction for 8 h. HPLC: 95.1%. After extraction, washing with water, column chromatography, and recrystallization, 26.7 g of light yellowish green solid Compound 32 was obtained, with an overall yield of 86.1% and HPLC: 99.95%. LC-MS: Theoretical value: 680.77, Measured value: 680.22.

[0052] The NMR data of Compound 32 are as follows: 1 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).

[0053] 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.

[0054] Example 5 Synthesis of Compound 33: .

[0055] Under the protection of 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 weighed and placed in a 1 L three-necked flask. The mixture was stirred and heated to 105 °C, and the reaction was carried out at this temperature for 12 h. HPLC: 95.1%. After extraction, washing with water, column chromatography, and recrystallization, 26.4 g of a light yellowish green solid Compound 33 was obtained, with an overall yield of 82.2% and HPLC: 99.95%. LC-MS: Theoretical value: 704.79, Measured value: 704.22.

[0056] The NMR data of Compound 33 are as follows: 1H-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).

[0057] 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.

[0058] Example 6 Synthesis of Compound 46: .

[0059] Under the protection of 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 weighed and placed in a 1 L three-necked flask. The mixture was stirred and heated to 105 °C, and the reaction was carried out at this temperature for 16 h. HPLC: 95.1%. After extraction, washing with water, column chromatography, and recrystallization, 27.0 g of light yellowish-green solid compound 46 was obtained, with an overall yield of 77.9% and HPLC: 99.95%. LC-MS: theoretical value: 760.91, measured value: 760.30.

[0060] The NMR data of compound 46 are as follows: 1 1H-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).

[0061] 13 13C-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.

[0062] Example 7 Synthesis of compound 53: .

[0063] Under the protection of 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 weighed and placed in a 1 L three-necked flask. The mixture was stirred and heated to 105 °C and kept at this temperature for reaction for 12 h. HPLC: 95.1%. After extraction, washing with water, column chromatography, and recrystallization, 21.0 g of light yellowish green solid compound 53 was obtained, with an overall yield of 71.2% and HPLC: 99.95%. LC-MS: theoretical value: 647.76, measured value: 647.18.

[0064] The NMR data of compound 53 are as follows: 1 1H-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, 1.8 Hz, 2H), 6.77 (dd, J = 7.2, 1.9 Hz, 1H).

[0065] 13 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.

[0066] Example 8 Synthesis of compound 58: 。

[0067] Under inert gas protection, 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 weighed and placed in a 1 L three-necked flask. The mixture was stirred and heated to 105 °C and kept at this temperature for reaction for 10 h. HPLC: 95.1%. After extraction, washing with water, column chromatography, and recrystallization, 28.6 g of a light yellowish green solid compound 58 was obtained, with an overall yield of 82.5% and HPLC: 99.95%. LC-MS: theoretical value: 759.93, measured value: 759.35.

[0068] The NMR data of compound 58 are as follows: 1 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, 1.5 Hz, 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, 1.7 Hz, 1H), 6.76 (dd, J = 7.3, 1.7 Hz, 1H).

[0069] 13 13C-NMR (Chloroform-d) δ 113.3, 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.

[0070] The synthesis methods of other compounds included in the present invention are the same as or similar to the specific implementation cases, and will not be listed one by one. The mass-to-charge ratios of the synthesized compounds are shown in Table 1 and Table 2 below.

[0071] Table 1 Mass-to-charge ratios of Compounds 1 - 30

[0072] Table 2 Mass-to-charge ratios of Compounds 31 - 60

[0073] II. Preparation and Evaluation of Organic Electroluminescent Devices Through the following Application Examples 1 - 24 and Comparative Examples 1 - 3, the application effects of the OLED materials synthesized by the present invention on devices are described in detail. The specific compound structural formulas involved are as follows: 。

[0074] Comparative Example 1 The structure of the organic electroluminescent device is as Figure 1 shown. The transparent anode electrode layer 2 (with a film thickness of 209 nm, indium tin oxide) on the transparent substrate layer 1 is processed: The glass transparent substrate layer 1 is washed, that is, alkali washing, deionized water washing, acetone ultrasonic cleaning, ethanol ultrasonic cleaning, ultrapure water cleaning, and drying are carried out in sequence, and then the transparent anode electrode layer 2 is subjected to UV-ozone washing to ensure the removal of organic residues on the surface of the transparent anode electrode layer 2. After the above treatment, a hole injection layer 3 is evaporated on the transparent anode electrode layer 2. Using a vacuum evaporation device, a material with Structural Formula I is evaporated (evaporation conditions: using a molybdenum crucible, evaporation rate 0.1 nm / s, vacuum degree 4.0*10 -5 Pa), and its film thickness is 57 nm. This organic material is used as the hole injection layer 3. Immediately after the hole injection layer 3, a material with Structural Formula II with a thickness of 23 nm is evaporated as the hole transport layer 4. Immediately after the hole transport layer 4, a material with Structural Formula III with a thickness of 19 nm is evaporated as the electron blocking layer 5.

[0075] After the evaporation of the electron blocking layer 5, a material with Structural Formula IV and Ir(PPy)3 are used as doping materials. After mixing them according to a doping weight ratio of 94:6, they are evaporated onto the electron blocking layer 5 (evaporation conditions: using a molybdenum crucible, evaporation rate 0.1 nm / s, vacuum degree 4.0*10 -5 Pa) to obtain the light-emitting layer 6, and the film thickness of the light-emitting layer 6 is 32 nm.

[0076] The hole blocking layer 7 is prepared after the light-emitting layer 6. The hole blocking layer 7 material (the material shown in Structural Formula V) is continuously vacuum-evaporated onto the light-emitting layer 6 (the evaporation conditions are: using a molybdenum crucible, evaporation rate of 0.1 nm / s, and vacuum degree of 4.0×10−5 Pa). The thickness of the vacuum-evaporated film of this material is 19 nm. After the evaporation is completed, immediately evaporate the material shown in Structural Formula VI to obtain the electron transport layer 8, and the thickness of the evaporated film is 79 nm. The electron injection layer 9 is formed on the electron transport layer 8 by a vacuum evaporation device to make a 0.8 nm thick lithium fluoride (LiF) layer as the electron injection layer 9.

[0077] The cathode reflective electrode layer 10 is formed on the electron injection layer 9 by vacuum evaporation. The cathode reflective electrode layer 10 is an aluminum (Al) layer with a film thickness of 146 nm.

[0078] After the organic electroluminescent device is completed as described above, the anode and the cathode are connected by a known driving circuit, and the luminous efficiency, luminous spectrum, and current-voltage characteristics of the device are measured.

[0079] Comparative Example 2 An organic electroluminescent device is prepared by the same method as in Comparative Example 1, except that: the main light-emitting material (Structural Formula IV) used in the light-emitting layer 6 of the organic electroluminescent device is changed to the compound of Structural Formula V.

[0080] Application Example 1 An organic electroluminescent device is prepared by the same method as in Comparative Example 1, except that: the main light-emitting material (Structural Formula IV) used in the light-emitting layer 6 of the organic electroluminescent device is changed to Compound 12.

[0081] Application Example 2 An organic electroluminescent device is prepared by the same method as in Comparative Example 1, except that: the main light-emitting material (Structural Formula IV) used in the light-emitting layer 6 of the organic electroluminescent device is changed to Compound 15.

[0082] Application Example 3 An organic electroluminescent device is prepared by the same method as in Comparative Example 1, except that: the main light-emitting material (Structural Formula IV) used in the light-emitting layer 6 of the organic electroluminescent device is changed to Compound 23.

[0083] Application Example 4 An organic electroluminescent device is prepared by the same method as in Comparative Example 1, except that: the main light-emitting material (Structural Formula IV) used in the light-emitting layer 6 of the organic electroluminescent device is changed to Compound 32.

[0084] Application Example 5 An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the main luminescent material (Structural Formula IV) used in the light-emitting layer 6 of the organic electroluminescent device was changed to Compound 33.

[0085] Application Example 6 An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the main luminescent material (Structural Formula IV) used in the light-emitting layer 6 of the organic electroluminescent device was changed to Compound 46.

[0086] Application Example 7 An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the main luminescent material (Structural Formula IV) used in the light-emitting layer 6 of the organic electroluminescent device was changed to Compound 53.

[0087] Application Example 8 An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that the main luminescent material (Structural Formula IV) used in the light-emitting layer 6 of the organic electroluminescent device was changed to Compound 58.

[0088] Application Example 9 An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that Structural Formula VI used in the electron transport layer 8 of the organic electroluminescent device was changed to Compound 12.

[0089] Application Example 10 An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that Structural Formula VI used in the electron transport layer 8 of the organic electroluminescent device was changed to Compound 33.

[0090] Application Example 11 An organic electroluminescent device was prepared by the same method as in Comparative Example 1, except that Structural Formula VI used in the electron transport layer 8 of the organic electroluminescent device was changed to Compound 58.

[0091] The test results of Application Examples 1-11 and Comparative Examples 1-2 at the same brightness (1000 cd / m 2 ), the same external environmental temperature (25.0 °C), and the same humidity (40.0%) are shown in Table 3.

[0092] Table 3 Test Results

[0093] According to the data comparison in Table 3, for the light-emitting device prepared by using the organic compound of the present invention as the OLED light-emitting material, its performance such as current efficiency, driving voltage, lifetime, and external quantum efficiency has more obvious advantages. Therefore, the compound prepared by using the present invention has great commercial value, broad market and industrialization prospects when applied in the organic electroluminescent device.

[0094] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of concise description, all possible combinations of the technical features in the above-described embodiments are not exhaustively listed. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope recorded in this specification.

[0095] For those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. The protection scope of the present invention shall be subject to 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 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.

2. The pyridazine anthracene luminescent material according to claim 1, characterized in that: The R is any one of biphenyl, deuterated biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, pyrenyl, chrysene, benzochrysene, fluorenyl, spirobifluorenyl, furanyl, carbazolyl, imidazolyl, thienyl, oxazolyl, thiazolyl, triazine and triphenylene.

3. The pyridazine anthracene luminescent material according to claim 1, characterized in that: The R is any one of the following structural formulas: ； ； ； 。 4. The pyridazine anthracene luminescent material according to claim 1, characterized in that: The structural formula of the pyridazine and anthracene luminescent material is any one of the following structural formulas: ； ； ； 。 5. 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 4.

6. An organic electroluminescent device according to claim 5, characterized in that: The pyridazine anthracene luminescent material is applied to the luminescent layer of an organic electroluminescent device.

7. An organic electroluminescent device according to claim 6, characterized in that: The pyridazine anthracene luminescent material is used as a luminescent host material in a luminescent layer of an organic electroluminescent device.

8. The organic electroluminescent device according to claim 5, characterized in that: The pyridazine anthracene-based luminescent material is used as an electron transport material in an electron transport layer.

9. The organic electroluminescent device according to claim 5, 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.

10. An electronic device, characterized in that: The electronic device comprises the organic electroluminescent device according to any one of claims 5 to 9.

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