An organic compound and its application

Abstract

The present invention relates to an organic compound and its application. The organic compound has a structure shown in formula (1). The compound of the present invention has a lower LUMO energy level, a low driving voltage of a prepared red light device, better device luminous efficiency and improved life. The above results show that the compound of the present invention can be used as a hole injection layer material in an organic electroluminescent device and has the possibility of being applied to the OLED industry.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, in particular to an organic luminescent material, and more particularly to an organic compound and its application in an organic electroluminescent device. Background Art

[0002] At present, organic electroluminescent devices (OLEDs), as a new generation of display technology, have received more and more attention in both display and lighting technology, and have a wide range of application prospects. However, compared with market application requirements, the performance of OLED devices such as luminous efficiency, driving voltage, and service life still needs to be further strengthened and improved.

[0003] Generally speaking, the basic structure of an OLED device is a thin film of organic functional materials with various functions sandwiched between metal electrodes, like a sandwich structure. Driven by electric current, holes and electrons are injected from the positive and negative electrodes respectively. After moving a certain distance, the holes and electrons are recombined in the light-emitting layer and released in the form of light or heat, thereby making the OLED emit light. However, organic functional materials are the core components of organic electroluminescent devices. The thermal stability, photochemical stability, electrochemical stability, quantum yield, film formation stability, crystallinity, color saturation, etc. of the materials are the main factors affecting the performance of the device.

[0004] Generally, in an organic light-emitting display device, a hole injection layer is introduced. The main function of this material is to improve some defects of the anode ITO and help holes to be injected from ITO into the device to reduce the driving voltage of the device and improve the stability of the device. At present, there are two main technologies using the hole injection layer. One of them is to use a single material such as HATCN, F4-TCNQ, F6TCNNQ, CuPc and other materials. Usually, such materials have a deeper LUMO energy level, but such materials will bring about a large lateral crosstalk, and in batch use, due to the film forming properties and crystallinity of the materials, the reproducibility and stability of the device are caused, which need to be improved; the second is to use a material doped with a deeper LUMO as a P-type dopant and a hole transport material with a matching HOMO energy level as a matrix. The technical solution mainly includes NDP-9, but the LUMO energy level of such materials needs to be further improved to reduce the device voltage, and there is also a problem of lateral crosstalk, which needs to be improved.

[0005] Now, some people have developed various compounds with deep LUMO as P-type dopants. For example, the invention patent document CN101330129B discloses a class of oxycarbon, pseudooxycarbon and radialene compounds in the mode of P-type dopants as hole injection layers for OLED devices; the invention patent document CN102439746B discloses a class of compounds containing Patent document CN109422666A discloses a type of OLED device containing trimerized indene OLED devices of compounds based on the compound; Patent document CN111454276A discloses a type of structure with quinone and two five-membered heterocyclic rings as P-type dopants; Patent documents CN112745333A, CN109912619, CN113087711A, CN113321620A mainly use structures such as dehydrobenzodioxazole, dehydrobenzodithiazole or dehydrobenzodiselenazole as P-type dopants; Patent document CN109928894A discloses a type of axialene compounds used as hole injection layers in the mode of P-type dopants for OLED devices; Patent document CN109836436B discloses a type of dithiophene structure as P-type dopant; Patent document CN110437103B discloses a type of cyclic structure as P-type dopant; Patent document CN110483529B discloses a type of condensed ring structure as P-type dopant, and in particular, discloses compounds Patent document CN110938085B discloses a type of radialene structure as a P-type dopant. However, the device performance of the above materials shows certain positive results in terms of LUMO energy level reduction and device performance improvement. However, in order to meet the growing device performance, especially the demand for voltage, efficiency and life, and the demand for improvement of red, green and blue lateral crosstalk, it is particularly important and urgent to develop high-performance hole injection layer materials. Summary of the invention

[0006] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a high-performance organic electroluminescent device and a novel material capable of realizing such an organic electroluminescent device.

[0007] The present inventors have conducted intensive studies to achieve the above-mentioned object and have found that a high-performance organic electroluminescent device can be obtained by using an organic compound represented by the following formula (1).

[0008] The organic compound has a structure shown in formula (1). The compound provided by the present invention not only has a deeper LUMO energy level and a low sublimation temperature, but also has the advantages of good optical and electrical stability, low driving voltage, long device life, low lateral conductivity, etc., and can be used in organic light-emitting devices, especially as a hole injection layer, and has the possibility of being applied to the AMOLED industry.

[0009] An organic compound having a structure shown in formula (1),

[0010]

[0011] Where Z is a single bond, O, S, SO, S0 2 ;

[0012] X 1 -X 6 Independently selected from X, C6-C30 aryl or C2-C30 heteroaryl substituted by X; wherein X is selected from F, CN, and C1-C4 fluoroalkyl substituted with all or part of fluorine;

[0013] Z 1 -Z 3 Independently selected from O, S, Se, NR 1 , CR 2 R 3 ;

[0014] Among them, R 1 -R 3 independently selected from the group consisting of hydrogen, deuterium, halogen, CN, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted cycloalkyl having C3-C20, substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C20 alkylsilyl, substituted or unsubstituted C6-C20 arylsilyl, substituted or unsubstituted C1-C6 alkylsulfoxide, substituted or unsubstituted C1-C6 alkylsulfone, substituted or unsubstituted C1-C6 alkylcarbonyl;

[0015] Among them, R 1 -R 3 At least one of them is a group having an electron-withdrawing group;

[0016] Among them, R 1 -R 3 The substituents are selected from F, CN, all or part of fluorine-substituted C1-C4 fluoroalkyl, all or part of fluorine-substituted C1-C4 alkylsulfoxide, all or part of fluorine-substituted C1-C4 alkylsulfone, all or part of fluorine-substituted C1-C4 alkylcarbonyl;

[0017] Wherein, the heteroalkyl group and heteroaryl group contain at least one O, N or S heteroatom.

[0018] Preferably: Z is a single bond, O, or SO.

[0019] As a preferred organic compound, Z is a single bond and has a structure shown in formula (2),

[0020]

[0021] in

[0022] X 1 -X 6 Independently selected from X, C6-C20 aryl or C2-C10 heteroaryl substituted by X; wherein X is selected from F, CN, and C1-C4 fluoroalkyl substituted with all or part of fluorine;

[0023] Z 1 -Z 3 Independently selected from O, S, NR 1 , CR 2 R 3 ;

[0024] Among them, R 1 -R 3 Independently selected from the group consisting of hydrogen, deuterium, halogen, CN, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted cycloalkyl with C3-C10, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C7-C20 aralkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, substituted or unsubstituted C1-C4 alkyl sulfoxide, substituted or unsubstituted C1-C4 alkyl sulfone, substituted or unsubstituted C1-C4 alkylcarbonyl.

[0025] As a preferred organic compound, Z 1 -Z 3 At least two are CR 2 R 3 .

[0026] As a preferred organic compound, Z 1 -Z 3 All CR 2 R 3 .

[0027] As preferred organic compounds, each CR 2 R 3 Among them, at least two are groups having electron withdrawing groups.

[0028] As a preferred organic compound, wherein the R 2 , R 3 All of them are groups with electron-withdrawing properties.

[0029] Among them, R 2 -R 3Independently selected from the group consisting of halogen, CN, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C7-C10 aralkyl, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C3-C12 heteroaryl, substituted or unsubstituted C1-C4 alkyl sulfoxide, substituted or unsubstituted C1-C4 alkyl sulfone, substituted or unsubstituted C1-C4 alkylcarbonyl.

[0030] Among them, R 2 -R 3 The substituents in are selected from F, CN, CF 3 CF 3 -sulfoxide, CF 3 -sulfone group;

[0031] Among them, X 1 -X 6 are independently selected from X.

[0032] As preferred organic compounds, X1-X6 are preferably F, CN, CF 3 .

[0033] As a preferred organic compound, the group having electron-withdrawing properties is F, CN, CF 3 , pyridine, pyrimidine, pyridazine, pyrazine, thiazole, oxazole, triazine, sulfoxide, sulfone, carbonyl or a C6-C12 aryl or C3-C12 heteroaryl containing one of the foregoing groups having electron-withdrawing properties.

[0034] As a preferred organic compound, the formula (1) is one of the following structural formulas:

[0035]

[0036]

[0037]

[0038]

[0039]

[0040] Another object of the present invention is to provide an electroluminescent device, which comprises: a cathode, an anode and an organic layer arranged between the cathode and the anode, wherein the organic layer comprises the above-mentioned organic compound.

[0041] The organic layer includes a hole injection layer, and the hole injection layer includes the above-mentioned organic compound; wherein the hole injection layer, in addition to the above-mentioned organic compound, also includes a triarylamine-containing or carbazole-containing hole transport material as a matrix material; the absolute value of the highest occupied orbital energy level (HOMO) of the triarylamine-containing or carbazole-containing hole transport material is between 4.8 and 6.8 eV.

[0042] The compound of the present invention has a lower LUMO energy level, and the prepared red light device has a low driving voltage, better device luminous efficiency and improved life. The above results show that the compound of the present invention can be used as a hole injection layer material in an organic electroluminescent device and has the potential to be applied to the OLED industry. DETAILED DESCRIPTION

[0043] The organic compound of the present invention has a structure shown in formula (1),

[0044]

[0045] in

[0046] Z is a single bond, O, S, SO, S0 2 ;

[0047] X 1 -X 6 Independently selected from X, C6-C30 aryl or C2-C30 heteroaryl substituted by X; wherein X is selected from F, CN, C1-C4 fluoroalkyl substituted with all or part of fluorine;

[0048] Z 1 -Z 3 Independently selected from O, S, Se, NR 1 , CR 2 R 3 ;

[0049] Among them, R 1 -R 3independently selected from the group consisting of hydrogen, deuterium, halogen, CN, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted cycloalkyl having C3-C20, substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C20 alkylsilyl, substituted or unsubstituted C6-C20 arylsilyl, substituted or unsubstituted C1-C6 alkylsulfoxide, substituted or unsubstituted C1-C6 alkylsulfone, substituted or unsubstituted C1-C6 alkylcarbonyl;

[0050] Among them, R 1 -R 3 At least one of them is a group having an electron-withdrawing group;

[0051] Among them, R 1 -R 3 The substituents are selected from F, CN, C1-C4 fluorinated fluoroalkyl, C1-C4 fluorinated alkylsulfoxide, C1-C4 fluorinated alkylsulfone, C1-C4 fluorinated alkylcarbonyl;

[0052] Wherein, the heteroalkyl group and heteroaryl group contain at least one O, N or S heteroatom.

[0053] As a preferred organic compound, Z is a single bond and has a structure shown in formula (2),

[0054]

[0055] Hereinafter, examples of each group of the compounds represented by formula (1) to formula (2) will be described.

[0056] In the present specification, the "carbon number a to b" in the expression "substituted or unsubstituted X group having a to b carbon atoms" refers to the carbon number when the X group is unsubstituted, and does not include the carbon number of the substituent when the X group is substituted.

[0057] The C1-C10 alkyl group is a straight-chain or branched alkyl group, specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers, n-nonyl and its isomers, n-decyl and its isomers, etc., preferably, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, and more preferably, propyl, isopropyl, isobutyl, sec-butyl and tert-butyl.

[0058] Examples of the C3-C20 cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, and 2-norbornyl, and cyclopentyl and cyclohexyl are preferred.

[0059] Examples of the C2-C10 alkenyl group include vinyl, propenyl, allyl, 1-butadienyl, 2-butadienyl, 1-hexatrienyl, 2-hexatrienyl, and 3-hexatrienyl, and propenyl and allyl are preferred.

[0060] The C1-C10 heteroalkyl group is a straight-chain or branched alkyl group, cycloalkyl group, etc. containing atoms other than carbon and hydrogen, and examples thereof include mercaptomethylmethyl, methoxymethyl, ethoxymethyl, tert-butoxymethyl, N,N-dimethylmethyl, butylene oxide, cyclopentyl, hexyl oxide, etc., and preferably methoxymethyl and cyclopentyl.

[0061] Specific examples of the aryl group include phenyl, naphthyl, anthracenyl, phenanthrenyl, tetraphenyl, pyrene, chrysene, benzo[c]phenanthrenyl, benzo[g]chrysene, fluorenyl, benzofluorenyl, dibenzofluorenyl, biphenyl, terphenyl, quaterphenyl, and fluoranthenyl, preferably phenyl and naphthyl.

[0062] Specific examples of the heteroaryl group include pyrrolyl, pyrazinyl, pyridyl, pyrimidinyl, triazine, indolyl, isoindolyl, imidazolyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, azadibenzofuranyl, azadibenzothiophenyl, diazadibenzofuranyl, diazadibenzothiophenyl, quinolyl, isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, Phenazinyl, phenothiazinyl, phenoxazinyl, oxazolinyl, oxadiazolyl, furazanyl, thienyl, benzothienyl, dihydroacridinyl, azacarbazolyl, diazacarbazolyl, quinazolinyl, etc., preferably pyridyl, pyrimidinyl, triazine, dibenzofuranyl, dibenzothienyl, azadibenzofuranyl, azadibenzothienyl, diazadibenzofuranyl, diazadibenzothienyl, carbazolyl, azacarbazolyl, diazacarbazolyl.

[0063] In this specification, the electron-withdrawing substituent refers to a group whose electron cloud density on the benzene ring is reduced after the substituent replaces the hydrogen on the benzene ring. Usually, the Hammett constant of this type of substituent is positive. In general, as specific examples of electron-withdrawing substituents, nitro, cyano, sulfonic acid, F, Cl, Br, I, trifluoromethyl, trifluoromethanesulfonyl, trifluoromethanesulfinyl, alkynyl, sulfone, sulfoxide, phosphono, aldehyde, keto, ester, carbonyl, pyrazinyl, pyridyl, pyrimidinyl, triazine, quinolyl, isoquinolyl, quinoxalinyl, and alkyl, cycloalkyl, aromatic, etc. containing the above groups can be cited. As a preferred substituent, its Hammett constant is ≥0.05, particularly preferably ≥0.3, and particularly preferably ≥0.5. As examples, CN, F, CF3, pyridyl, pyrimidinyl, and triazine are preferred.

[0064] The following embodiments are only for facilitating the understanding of the technical invention and should not be regarded as specific limitations of the present invention.

[0065] The raw materials and solvents involved in the synthesis of the compounds of the present invention were purchased from suppliers such as Alfa and Acros, which are well known to those skilled in the art.

[0066] Synthesis of compound CPD001

[0067]

[0068] Synthesis of compound CPD001-2:

[0069] CPD001-1 (50 g, 293.83 mmol), dicarbonylcyclopentadienylcobalt (2.64 g, 14.69 mmol), and 1,4-dioxane (500 ml) were added to a 1000 ml three-necked round-bottom flask, replaced with nitrogen three times, heated to 110 ° C and refluxed for 24 h, monitored by TLC (ethyl acetate: petroleum ether = 1:20), and the raw material CPD001-1 was consumed.

[0070] The 1,4-dioxane was removed by concentration, and dichloromethane (500 ml) was added. The product was washed with deionized water (200 ml*3), separated, concentrated, and purified by silica gel column chromatography (200-300 mesh silica gel, acetate: petroleum ether = 1:50 as eluent). After elution, the product was concentrated to obtain a colorless liquid, which was compound CPD001-2 (35.52 g, purity: 99.63%, yield: 61.00%), with a mass spectrum of 595.4 (M+H).

[0071] 1 H NMR (400 MHz, CDCl 3 )δ4.13(q,J=11.9Hz,12H),3.71(s,12H),1.21(t,J=11.8Hz,18H).

[0072] Synthesis of compound CPD001-4:

[0073] CPD001-2 (35.00 g, 58.86 mmol) and dry tetrahydrofuran (350 ml) were added to a 1000 ml three-necked round-bottom flask, cooled to 0°C, and then 60% sodium hydride (18.86 g, 470.88 mmol) was added in batches, stirred at 0°C for 30 minutes, and then CPD001-3 (50.10 g, 294.29 mmol) was added, and the mixture was returned to room temperature and stirred overnight for 24 hours. TLC monitoring (ethyl acetate: petroleum ether = 1:20) showed that the raw material CPD001-2 was completely consumed.

[0074] The temperature was lowered to 5°C, deionized water (100 ml) was added to quench the reaction, and the solvent was removed by concentration to precipitate a large amount of solid. The solid was filtered off with suction, rinsed with ice ethanol (100 ml), and recrystallized twice with 10 times ethanol. The filter cake was dried under vacuum at 50°C for 4 h to obtain a light yellow solid, which was compound CPD001-4 (37.5 g, purity: 99.57%, yield: 78.05%), mass spectrum: 817.22 (M+H).

[0075] 1 H NMR (400 MHz, CDCl 3 )δ5.49(s,6H),4.21(q,J=11.8Hz,12H),1.20(t,J=11.8Hz,18H).

[0076] Synthesis of compound CPD001-5:

[0077] CPD001-4 (15.00 g, 18.36 mmol), ethanol (150 ml), potassium hydroxide (10.30 g, 183.65 mmol) and deionized water (46 ml) were added into a 500 ml three-necked round-bottom flask, and then the system was heated to 80 °C for 10 h. TLC (methanol: dichloromethane = 1:20 as the developing solvent) was used to monitor the complete consumption of the raw material CPD001-4.

[0078] The reaction mixture was cooled to 5°C, and 10% hydrochloric acid was added to adjust the pH of the system to 6. A large amount of solid precipitated, which was filtered off with suction. The filter cake was slurried with a mixed solvent of deionized water (200 ml) and methanol (200 ml) at room temperature for 1 h, filtered off with suction, rinsed with deionized water (100 ml), rinsed with ice methanol (80 ml), and dried in vacuo at 50°C for 24 h to obtain a yellow solid CPD001-5 (10.86 g, purity: 99.87%, yield: 91.21%), mass spectrum: 649.25 (M+H).

[0079] Synthesis of compound CPD001-6:

[0080] CPD001-5 (10.00 g, 15.42 mmol), sodium bicarbonate (12.95 g, 154.20 mmol), selective fluorine reagent (43.70 g, 123.36 mmol), and tetrahydrofuran (100 ml) were added into a 500 ml three-necked round-bottom flask and stirred at room temperature for 28 h overnight. The raw material CPD001-5 was completely consumed by monitoring by TLC (methanol: dichloromethane = 1:20 as the developing solvent).

[0081] The reaction temperature was cooled to 5°C, methanol was added and the mixture was restored to room temperature and slurried for 30 minutes. The mixture was filtered and washed with ice methanol (40 ml). The mixture was dried under vacuum at 50°C to give a yellow solid CPD001-6 (4.96 g, purity: 99.90%, yield: 65.37%), mass spectrum: 493.46 (M+H).

[0082] Synthesis of compound CPD001:

[0083] Add CPD001-6 (4.90 g, 9.95 mmol), dichloromethane (75 ml), potassium hydroxide (6.70 g, 119.40 mmol), deionized water (30 ml), and potassium ferrocyanide (26.21 g, 79.60 mmol) into a 500 ml three-necked round-bottom flask and stir at room temperature for 24 h.

[0084] The filter cake was filtered, rinsed with dichloromethane (80 ml), recrystallized twice with 5 times chloroform, and dried under vacuum at 50°C for 8 hours to obtain a yellow-brown solid as the target compound CPD001 (3.22 g, purity: 99.90%, yield: 66.54%). 3.22 g of crude CPD001 was purified by sublimation to obtain sublimation-purified CPD001 (1.03 g, purity: 99.90%, yield: 31.98%), mass spectrum: 487.02 (M+H).

[0085] 13 C NMR (100 MHz, CDCl 3 )δ134.26,124.88,113.35,82.58.

[0086] 19 F NMR (377 MHz, CDCl 3 )δ-146.20.

[0087] Synthesis of compound CPD003

[0088]

[0089] Synthesis of compound CPD003-2:

[0090] Referring to the synthesis and purification method of compound CPD001-4, only the corresponding raw materials need to be changed to obtain a yellow solid compound CPD003-2 (28.16 g, purity: 99.63%, yield: 75.35%), mass spectrum: 1075.20 (M+H). Synthesis of compound CPD003-3:

[0091] Referring to the synthesis and purification method of compound CPD001-5, only the corresponding raw materials need to be changed to obtain a yellow solid compound CPD003-3 (17.47 g, purity: 99.71%, yield: 89.62%), mass spectrum: 907.22 (M+H). Synthesis of compound CPD003-4:

[0092] Referring to the synthesis and purification method of compound CPD001-6, it is only necessary to change the corresponding raw materials to obtain a yellow solid compound CPD003-4 (8.19 g, purity: 99.88%, yield: 55.36%), mass spectrum: 751.42 (M+H).

[0093] Synthesis of compound CPD003:

[0094] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the target compound CPD003 (5.18 g, purity: 99.91%, yield: 62.17%) as a yellow-brown solid. 5.18 g of crude CPD003 was purified by sublimation to obtain sublimation-purified CPD003 (2.03 g, purity: 99.91%, yield: 39.19%), mass spectrum: 745.02 (M+H).

[0095] 13 C NMR (100 MHz, CDCl 3 )δ170.22,124.97,119.76,111.43.

[0096] 19 F NMR (377 MHz, CDCl 3 )δ-61.80,-146.20.

[0097] Synthesis of compound CPD016

[0098]

[0099] Synthesis of compound CPD016-1:

[0100] CPD001-5 (16.20 g, 24.98 mmol) and triethylamine hydrofluoride (80.54 g, 499.60 mmol) were added to a stainless steel autoclave, and then sulfur tetrafluoride gas (53.98 g, 499.60 mmol) was introduced thereinto, and then the temperature was raised to 80°C for reaction for 24 hours.

[0101] The system was cooled to room temperature, the fume hood was turned on for strong exhaust, the autoclave was slowly depressurized and emptied, the reaction solution was slowly added dropwise to 5°C deionized water (500ml), naturally returned to room temperature and stirred for 1.5 hours, a large amount of dispersed solids were precipitated, filtered, washed with deionized water (200ml), washed with ice methanol (50ml), and vacuum dried at 50°C to obtain a yellow solid CPD016-1 (10.76g, purity: 99.89%, yield: 54.34%), mass spectrum: 793.04 (M+H).

[0102] Synthesis of compound CPD016:

[0103] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the target compound CPD016 (4.03 g, purity: 99.91%, yield: 60.51%) as a yellow-brown solid. 4.03 grams of crude CPD016 was purified by sublimation to obtain sublimation-pure CPD016 (1.38 g, purity: 99.91%, yield: 34.24%), mass spectrum: 787.04 (M+H).

[0104] 13 C NMR (100 MHz, CDCl 3 )δ172.08,121.05,120.10,118.42,113.35,107.82.

[0105] 19 F NMR (377 MHz, CDCl 3 )δ-59.80.

[0106] Synthesis of compound CPD031

[0107]

[0108] Synthesis of compound CPD031-2:

[0109] CPD031-1 (50.00 g, 0.58 mol), 3,4-dihydro-2H-pyran (146.37 g, 1.74 mol), pyridinium p-toluenesulfonate (4.37 g, 17.40 mmol), and dichloromethane (500 ml) were added to a 1000 ml three-necked round-bottom flask and monitored by TLC (ethyl acetate: petroleum ether = 1:20) for 2 hours. The raw material CPD031-1 was completely consumed.

[0110] Add dichloromethane (200 ml), wash with deionized water (300 ml*3), separate the liquids, concentrate, and purify by silica gel column chromatography (200-300 mesh silica gel, acetate: petroleum ether = 1:40 as eluent), and concentrate to obtain a light yellow liquid as compound CPD031-2 (132.94 g, purity: 99.83%, yield: 90.00%), mass spectrum: 255.16 (M+H).

[0111] Synthesis of compound CPD031-3:

[0112] CPD031-2 (120.00 g, 0.47 mol) and dry dichloromethane (1200 ml) were added to a 2000 ml three-necked round-bottom flask, and nitrogen was replaced three times. The system was cooled to 0°C with stirring, and trimethylsilyl cyanide (140.43 g, 1.42 mol) was then added dropwise, and finally tin tetrachloride (240 ml, 1.0 M solution in CH 2 Cl 2 , 0.24 mol), and then the reaction was restored to room temperature for overnight reaction. Under TLC monitoring (ethyl acetate: petroleum ether = 1:10), the raw material CPD031-2 was completely consumed.

[0113] An aqueous solution of potassium carbonate was added to quench the reaction, and the mixture was stirred at room temperature for 30 minutes. The mixture was separated and washed with deionized water (300 ml*2). The mixture was separated and subjected to silica gel column chromatography (200-300 mesh silica gel, ethyl acetate: petroleum ether = 1:20 as eluent). After elution, the mixture was concentrated to obtain a light yellow liquid, which was compound CPD031-3 (43.31 g, purity: 99.85%, yield: 88.16%), mass spectrum: 105.04 (M+H).

[0114] Synthesis of compound CPD031-4:

[0115] Referring to the synthesis and purification method of compound CPD001-2, it is only necessary to change the corresponding raw materials to obtain the target compound CPD031-4 (31.21 g, purity: 99.58%, yield: 57.72%), mass spectrum: 313.12 (M+H).

[0116] Synthesis of compound CPD031-5:

[0117] Referring to the synthesis and purification method of compound CPD001-4, only the corresponding raw materials need to be changed to obtain a yellow solid compound CPD031-5 (15.16 g, purity: 99.64%, yield: 73.33%), mass spectrum: 535.08 (M+H). Synthesis of compound CPD031:

[0118] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the target compound CPD031 (6.05 g, purity: 99.90%, yield: 55.19%) as a yellow-brown solid. 6.05 g of crude CPD031 was purified by sublimation to obtain sublimation-pure CPD031 (2.34 g, purity: 99.91%, yield: 38.67%), mass spectrum: 529.24 (M+H).

[0119] 13 C NMR (100 MHz, CDCl 3 )δ149.35,143.10,113.35,106.01,99.44,67.86

[0120] Synthesis of compound CPD032

[0121]

[0122] Synthesis of compound CPD032-1:

[0123] Referring to the synthesis and purification method of compound CPD001-4, it is only necessary to change the corresponding raw materials to obtain the target compound CPD032-1 (8.29 g, purity: 99.88%, yield: 71.41%), mass spectrum: 493.16 (M+H).

[0124] Synthesis of compound CPD032:

[0125] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the target compound CPD032 (5.83 g, purity: 99.92%, yield: 48.83%) as a yellow-brown solid. 5.83 g of crude CPD032 was purified by sublimation to obtain sublimation-purified CPD032 (1.69 g, purity: 99.92%, yield: 28.98%), mass spectrum: 487.02 (M+H).

[0126] 13 C NMR (100 MHz, CDCl 3 )δ150.30,138.39,114.48,107.85,80.81.

[0127] 19 F NMR (377MHz,CDCl3)δ-65.70.

[0128] Synthesis of compound CPD046

[0129]

[0130] Synthesis of compound CPD046-2:

[0131] Referring to the synthesis and purification method of compound CPD001-4, only the corresponding raw materials need to be changed to obtain a yellow solid compound CPD046-2 (25.33 g, purity: 99.50%, yield: 77.47%), mass spectrum: 1261.26 (M+H). Synthesis of compound CPD046-3:

[0132] Referring to the synthesis and purification method of compound CPD001-5, only the corresponding raw materials need to be changed to obtain a yellow solid compound CPD046-3 (13.44 g, purity: 99.75%, yield: 91.25%), mass spectrum: 1093.23 (M+H). Synthesis of compound CPD046-4:

[0133] Referring to the synthesis and purification method of compound CPD001-6, it is only necessary to change the corresponding raw materials to obtain a yellow solid compound CPD046-4 (8.53 g, purity: 99.91%, yield: 58.13%), mass spectrum: 937.24 (M+H).

[0134] Synthesis of compound CPD046:

[0135] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the target compound CPD046 (6.12 g, purity: 99.91%, yield: 50.14%) as a yellow-brown solid. 6.12 g of crude CPD046 was purified by sublimation to obtain sublimation-pure CPD046 (2.06 g, purity: 99.91%, yield: 33.66%), mass spectrum: 931.42 (M+H).

[0136] 13 C NMR (100 MHz, CDCl 3 )δ145.60,143.59,142.00,139.99,131.02,124.77,110.99,108.09,107.01,86.28.

[0137] 19 F NMR (377 MHz, CDCl3 )δ-138.50,-143.10,-146.20.

[0138] Synthesis of compound CPD058

[0139]

[0140] Synthesis of compound CPD058-2:

[0141] Referring to the synthesis and purification method of compound CPD001-4, only the corresponding raw materials need to be changed to obtain a yellow solid compound CPD058-2 (27.59 g, purity: 99.50%, yield: 80.01%), mass spectrum: 1141.27 (M+H). Synthesis of compound CPD058-3:

[0142] Referring to the synthesis and purification method of compound CPD001-5, only the corresponding raw materials need to be changed to obtain a yellow solid compound CPD058-3 (18.03 g, purity: 99.77%, yield: 93.21%), mass spectrum: 973.25 (M+H). Synthesis of compound CPD058-4:

[0143] Referring to the synthesis and purification method of compound CPD001-6, it is only necessary to change the corresponding raw materials to obtain a yellow solid compound CPD058-4 (8.26 g, purity: 99.89%, yield: 62.11%), mass spectrum: 817.20 (M+H).

[0144] Synthesis of compound CPD058:

[0145] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the target compound CPD058 (4.83 g, purity: 99.91%, yield: 42.92%) as a yellow-brown solid. 4.83 g of crude CPD058 was purified by sublimation to obtain sublimation-pure CPD058 (1.25 g, purity: 99.91%, yield: 25.87%), mass spectrum: 811.62 (M+H).

[0146] 13 C NMR (100 MHz, CDCl 3 )δ156.50,148.75,139.36,132.37,125.98,125.50,124.39,116.83,114.98,114.53.

[0147] 19 F NMR (377 MHz, CDCl 3 )δ-146.20.

[0148] Synthesis of Compound CPD070

[0149]

[0150] Synthesis of Compound CPD070-2:

[0151] Add CPD070-1 (50.00 g, 90.01 mmol), malononitrile (11.89 g, 180.03 mmol), and dichloromethane (500 ml) into a 1000-ml three-necked round-bottom flask. Then add pyridine (7.12 g, 90.01 mmol) and titanium tetrachloride (15.23 g, 90.01 mmol). Replace the air with nitrogen three times, and stir at room temperature overnight. Monitor by TLC (ethyl acetate: petroleum ether = 1:18). When the raw material CPD070-1 is completely consumed.

[0152] Add deionized water for washing (300 ml * 3), separate the layers, concentrate, and purify by silica gel column chromatography (200 - 300 mesh silica gel, ethyl acetate: petroleum ether = 1:30 as the eluent). Concentrate to obtain a light yellow liquid as Compound CPD070-2 (30.42 g, purity: 99.53%, yield: 56.00%). Mass spectrum: 598.56 (M+H).

[0153] Synthesis of Compound CPD070-3:

[0154] Add CPD070-2 (29.00 g, 48.05 mmol), sodium hydroxide (13.45 g, 336.36 mmol), methanol (290 ml), and deionized water (80 ml) into a 1000-ml three-necked round-bottom flask. Replace the air with nitrogen three times, heat to 60 °C and stir overnight. Monitor by TLC (ethyl acetate: petroleum ether = 1:8). When the raw material CPD070-2 is completely consumed.

[0155] Concentrate to remove the solvent, add dichloromethane (500 ml), wash with deionized water (150 ml * 3), separate the layers, concentrate, and purify by silica gel column chromatography (200 - 300 mesh silica gel, ethyl acetate: petroleum ether = 1:10 as the eluent). Concentrate to obtain a light yellow liquid as Compound CPD070-3 (12.17 g, purity: 99.64%, yield: 80.16%). Mass spectrum: 315.02 (M+H).

[0156] Synthesis of Compound CPD070-4:

[0157] CPD070-3 (12.00 g, 37.99 mmol), anhydrous cerium trichloride (18.72 g, 75.97 mmol), and methanol (120 ml) were added into a 500 ml three-necked round-bottom flask, the reaction system was cooled to 5 ° C, sodium borohydride (2.43 g, 75.97 mmol) was added in batches, and the reaction temperature was maintained at 5 ° C for 30 minutes. TLC monitoring (ethyl acetate: petroleum ether = 1:5) showed that the raw material CPD070-3 was completely consumed.

[0158] The solvent was removed by concentration, dichloromethane (500 ml) was added, and the mixture was washed with deionized water (150 ml*3), separated, and concentrated to obtain a light yellow liquid compound CPD070-4 (11.58 g, purity: 99.63%, yield: 95.25%), mass spectrum: 319.06 (M+H). The crude product was directly used for the next step.

[0159] Synthesis of compound CPD070-5:

[0160] CPD070-4 (11.00 g, 34.38 mmol) and dry dichloromethane (110 ml) were added into a 500 ml three-necked round-bottom flask, the reaction system was cooled to -10 °C, bis(2-methoxyethyl)aminosulfur trifluoride (18.94 g, 85.59 mmol) was slowly added dropwise, and the reaction was maintained at -10 °C for 10 minutes. TLC monitoring (ethyl acetate: petroleum ether = 1:5) showed that the raw material CPD070-4 was completely consumed.

[0161] 10 ml of methanol was added dropwise to quench the reaction, and the mixture was washed with deionized water (50 ml*3), separated, concentrated, and purified by silica gel column chromatography (200-300 mesh silica gel, acetate: petroleum ether = 1:10 as eluent). The mixture was concentrated to obtain a light yellow liquid, which was compound CPD070-5 (8.73 g, purity: 99.48%, yield: 78.36%), mass spectrum: 323.14 (M+H).

[0162] Synthesis of compound CPD070-6:

[0163] CPD070-5 (8.50 g, 26.24 mmol), potassium phosphate (16.71 g, 78.72 mmol), palladium acetate (176.74 mg, 0.79 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.75 g, 1.58 mmol), toluene (120 ml), and deionized water (40 ml) were added to a 500 ml three-necked round-bottom flask. The atmosphere was replaced with nitrogen three times, and the reaction system was heated to 120° C. and refluxed overnight for 16 hours. According to TLC monitoring (ethyl acetate: petroleum ether = 1:12), the raw material CPD070-5 was completely consumed.

[0164] The mixture was cooled to room temperature, washed with deionized water (50 ml*3), separated, concentrated, and purified by silica gel column chromatography (200-300 mesh silica gel, acetate: petroleum ether = 1:25 as eluent), and concentrated to obtain a light yellow liquid as compound CPD070-6 (3.94 g, purity: 99.58%, yield: 90.41%), mass spectrum: 167.03 (M+H).

[0165] Synthesis of compound CPD070-7:

[0166] CPD070-6 (18.00 g, 108.35 mmol), potassium peroxymonosulfonate (85.25 h, 238.37 mmol), ammonium bromide (23.35 g, 238.37 mmol), acetonitrile (200 ml), and deionized water (200 ml) were added to a 1000 ml three-necked round-bottom flask, replaced with nitrogen three times, stirred at room temperature for 6 h, monitored by TLC (ethyl acetate: petroleum ether = 1:8), and the raw material CPD070-6 was consumed.

[0167] The solvent was removed by concentration, dichloromethane (500 ml) was added, and the mixture was washed with deionized water (150 ml*3). The mixture was separated and concentrated. The mixture was purified by silica gel column chromatography (200-300 mesh silica gel, acetate: petroleum ether = 1:30 as eluent). The mixture was concentrated to obtain a light yellow liquid, which was compound CPD070-7 (24.40 g, purity: 99.61%, yield: 85.62%), with a mass spectrum of 263.06 (M+H).

[0168] Synthesis of compound CPD070-8:

[0169] CPD070-7 (15.00 g, 57.03 mmol), triphenylphosphine (17.95 h, 68.44 mmol), diethyl azodicarboxylate (11.92 g, 68.44 mmol), and dry THF (150 ml) were added to a 500 ml three-necked round-bottom flask, replaced with nitrogen three times, stirred at room temperature for 24 h, monitored by TLC (ethyl acetate: petroleum ether = 1:15), and the raw material CPD070-7 was completely consumed.

[0170] The solvent was removed by concentration, dichloromethane (700 ml) was added, and the mixture was washed with deionized water (200 ml*3). The mixture was separated and concentrated, and purified by silica gel column chromatography (200-300 mesh silica gel, acetate: petroleum ether = 1:35 as eluent). The mixture was concentrated to obtain a light yellow solid, which was compound CPD070-8 (18.02 g, purity: 99.59%, yield: 62.19%), with a mass spectrum of 507.20 (M+H).

[0171] Synthesis of compound CPD070-9:

[0172] CPD070-8 (16.00 g, 31.49 mmol) and glacial acetic acid (160 ml) were added into a 1000 ml three-necked round-bottom flask, and then concentrated nitric acid (160 ml) was added dropwise. The mixture was stirred at room temperature for 24 h. TLC monitoring (ethyl acetate: petroleum ether = 1:6) showed that the raw material CPD070-8 was completely consumed.

[0173] A light yellow solid was directly precipitated from the reaction solution, which was filtered off with suction. Deionized water (500 ml) was added to the filter cake and slurried at room temperature for 1 hour. The mixture was filtered off with suction, washed with deionized water (100 ml), and the filter cake was washed with ice methanol (100 ml). The mixture was dried under vacuum at 50°C to give a light yellow solid, which was compound CPD070-9 (12.93 g, purity: 99.52%, yield: 82.14%), with a mass spectrum of 499.24 (M+H).

[0174] Synthesis of compound CPD070-10:

[0175] CPD070-9 (10.00 g, 20.00 mmol), CPD070-6 (3.32 g, 20.00 mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (284.04 mg, 0.40 mmol), sodium carbonate (4.24 g, 40 mmol), toluene (150 ml), ethanol (50 ml), and deionized water (50 ml) were added to a 500 ml three-necked round-bottom flask, and the atmosphere was replaced with nitrogen three times. The system was then heated to 70 ° C and reacted for 5 hours. TLC monitoring (methanol: dichloromethane = 1:20) showed that the raw material CPD070-9 was completely consumed.

[0176] A yellow solid was directly precipitated from the reaction solution, which was filtered off with suction. Deionized water (500 ml) was added to the filter cake and slurried at room temperature for 1 hour. The mixture was filtered off with suction, washed with deionized water (100 ml), and the filter cake was washed with ice methanol (80 ml). The mixture was dissolved in 10 times chloroform and hot filtered through silica gel (20 g, 200-300 mesh silica gel). The mixture was concentrated and then recrystallized twice with 5 times chloroform. The mixture was dried under vacuum at 50°C to give a yellow solid as compound CPD070-9 (7.70 g, purity: 99.91%, yield: 76.32%), mass spectrum: 505.22 (M+H).

[0177] Synthesis of compound CPD070:

[0178] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the target compound CPD070 (4.43 g, purity: 99.91%, yield: 61.80%) as a yellow-brown solid. 4.43 g of crude CPD070 was purified by sublimation to obtain sublimation-purified CPD070 (2.01 g, purity: 99.91%, yield: 45.37%), mass spectrum: 503.16 (M+H)

[0179] 13 C NMR (100 MHz, CDCl 3 )δ147.72,144.12,143.07,124.68,113.35,111.90,92.09,90.60.

[0180] 19 F NMR (377 MHz, CDCl 3 )δ-117.90,-146.20.

[0181] Synthesis of compound CPD085

[0182]

[0183] Synthesis of compound CPD085-1:

[0184] CPD070-7 (16.00 g, 60.83 mmol), triethylamine (12.31 g, 121.66 mmol) and dichloromethane (160 ml) were added to a 500 ml three-necked round-bottom flask, and the atmosphere was replaced with nitrogen three times. The system was then cooled to 0°C, and methanesulfonyl chloride (10.45 g, 91.24 mmol) was added dropwise. The temperature was maintained and stirred for 1 hour. TLC monitoring (ethyl acetate: petroleum ether = 1:20) showed that the raw material CPD070-7 was completely consumed.

[0185] Deionized water was added for washing (60 ml*3), concentrated, and purified by silica gel column chromatography (200-300 mesh silica gel, acetate: petroleum ether = 1:30 as eluent), and concentrated to obtain a light yellow liquid as compound CPD085-1 (19.72 g, purity: 99.68%, yield: 95.04%), mass spectrum: 341.03 (M+H).

[0186] Synthesis of compound CPD085-2:

[0187] CPD085-1 (17.85 g, 52.33 mmol), sodium sulfide nonahydrate (25.13 g, 261.65 mmol), and N,N-dimethylformamide (180 ml) were added to a 500 ml three-necked round-bottom flask, and the atmosphere was replaced with nitrogen three times. The system was then heated to 50° C. and reacted overnight. According to TLC monitoring (ethyl acetate: petroleum ether=1:20), the raw material CPD085-1 was completely consumed.

[0188] The solvent was removed by concentration, dichloromethane (500 ml) was added, and deionized water (150 ml*3) was added for washing, and the mixture was concentrated. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, acetate: petroleum ether = 1:25 as eluent), and light yellow liquid was obtained as compound CPD085-2 (15.45 g, purity: 99.56%, yield: 56.36%), mass spectrum: 523.08 (M+H).

[0189] Synthesis of compound CPD085-3:

[0190] Referring to the synthesis and purification method of compound CPD070-9, only the corresponding raw materials need to be changed to obtain the target compound CPD085-3 (11.76 g, purity: 99.51%, yield: 86.15%) as a light yellow solid, mass spectrum: 531.02 (M+H). Synthesis of compound CPD085-4:

[0191] Referring to the synthesis and purification method of compound CPD070-10, only the corresponding raw materials need to be changed to obtain the target compound CPD085-4 (6.88 g, purity: 99.90%, yield: 75.11%) as a yellow solid, with a mass spectrum of 537.06 (M+H).

[0192] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the target compound CPD085 (4.05 g, purity: 99.91%, yield: 62.33%) as a yellow-brown solid. 4.05 g of crude CPD085 was purified by sublimation to obtain sublimation-pure CPD085 (1.88 g, purity: 99.91%, yield: 46.41%), mass spectrum: 535.06 (M+H).

[0193] 13 C NMR (100 MHz, CDCl 3 )δ144.12,142.16,126.14,113.35,112.40,97.72,92.08.

[0194] 19 F NMR (377 MHz, CDCl 3 )δ-146.12.

[0195] Synthesis of compound CPD094

[0196]

[0197] Synthesis of compound CPD094-1:

[0198] Referring to the synthesis and purification method of compound CPD070-2, only the corresponding raw materials need to be changed to obtain the target compound CPD094-1 (35.12 g, purity: 99.56%, yield: 57.68%) as a light yellow liquid, with a mass spectrum of 673.28 (M+H). Synthesis of compound CPD094-2:

[0199] Referring to the synthesis and purification method of compound CPD070-3, only the corresponding raw materials need to be changed to obtain the target compound CPD094-2 (16.73 g, purity: 99.68%, yield: 83.98%) as a light yellow liquid, with a mass spectrum of 390.21 (M+H). Synthesis of compound CPD094-3:

[0200] Referring to the synthesis and purification method of compound CPD070-4, only the corresponding raw materials need to be changed to obtain the target compound CPD094-3 (15.55 g, purity: 99.62%, yield: 93.34%) as a light yellow liquid, with a mass spectrum of 394.03 (M+H). Synthesis of compound CPD094-4:

[0201] Referring to the synthesis and purification method of compound CPD070-5, only the corresponding raw materials need to be changed to obtain the target compound CPD094-4 (13.10 g, purity: 99.50%, yield: 75.17%) as a light yellow liquid, with a mass spectrum of 398.02 (M+H). Synthesis of compound CPD094-5:

[0202] Referring to the synthesis and purification method of compound CPD070-6, only the corresponding raw materials need to be changed to obtain the target compound CPD094-5 (8.94 g, purity: 99.53%, yield: 88.78%) as a light yellow liquid, with a mass spectrum of 242.04 (M+H). Synthesis of compound CPD094-6:

[0203] Referring to the synthesis and purification method of compound CPD070-7, only the corresponding raw materials need to be changed to obtain the target compound CPD094-6 (18.98 g, purity: 99.63%, yield: 87.36%) as a light yellow liquid, with a mass spectrum of 338.12 (M+H). Synthesis of compound CPD094-7:

[0204] Referring to the synthesis and purification method of compound CPD085-1, only the corresponding raw materials need to be changed to obtain the target compound CPD094-7 (20.05 g, purity: 99.67%, yield: 95.34%) as a light yellow liquid, mass spectrum: 416.00 (M+H). Synthesis of compound CPD094-8:

[0205] Referring to the synthesis and purification method of compound CPD085-2, only the corresponding raw materials need to be changed to obtain the target compound CPD094-8 (16.33 g, purity: 99.61%, yield: 57.33%) as a light yellow liquid, mass spectrum: 673.01 (M+H). Synthesis of compound CPD094-9:

[0206] Referring to the synthesis and purification method of compound CPD070-9, only the corresponding raw materials need to be changed to obtain the target compound CPD094-9 (14.35 g, purity: 99.58%, yield: 84.10%) as a light yellow solid, with a mass spectrum of 713.14 (M+H). Synthesis of compound CPD094-10:

[0207] Referring to the synthesis and purification method of compound CPD070-10, only the corresponding raw materials need to be changed to obtain the target compound CPD094-10 (6.05 g, purity: 99.92%, yield: 61.11%) as a light yellow solid, with a mass spectrum of 794.26 (M+H).

[0208] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the target compound CPD094 (5.55 g, purity: 99.92%, yield: 58.74%) as a yellow-brown solid. 5.55 g of crude CPD094 was purified by sublimation to obtain sublimation-pure CPD094 (2.35 g, purity: 99.92%, yield: 42.34%), mass spectrum: 808.06 (M+H).

[0209] 13 C NMR (100 MHz, CDCl 3 )δ201.83,196.96,123.85,109.77,107.98.

[0210] 19 F NMR (377 MHz, CDCl 3 )δ-77.9,-146.21.

[0211] Application example: Fabrication of organic electroluminescent devices

[0212] A 50 mm*50 mm*1.0 mm glass substrate with an ITO (100 nm) anode electrode was ultrasonically cleaned in ethanol for 10 minutes, then dried at 150 degrees and heated to 400 °C. 2Plasma treatment for 30 minutes. The washed glass substrate is mounted on the substrate support of the vacuum evaporation device, and firstly, the compound HTM1 and P-dopant (ratio of 97%:3%, P-dopant is the comparative compound X or the compound of the present invention) are co-deposited on the surface of the anode electrode line in a covering electrode manner to form a film with a thickness of 10nm, followed by evaporation of a layer of HTM1 to form a film with a thickness of about 60nm, and then a layer of HTM2 is evaporated on the HTM1 film to form a film with a thickness of 10nm, and then, the main material 1 and the main material 2 and the doping compound (RD) are evaporated on the HTM2 film layer in a co-evaporation mode, with a film thickness of 40nm, and ETL: LiQ (35nm, ratio of 50%:50%) is evaporated on the light-emitting layer in a co-evaporation mode, and then Yb (1nm) is evaporated on the electron transport layer material, and finally a layer of metal Ag (15nm) is evaporated as an electrode.

[0213]

[0214]

[0215]

[0216] Evaluation: The above device was subjected to device performance test. In each embodiment and comparative example, a constant current power supply (Keithley 2400) was used to flow a fixed current density through the light-emitting element, and a spectroradiometer (CS 2000) was used to test the luminous spectrum. The voltage value and the time (LT95) at which the test brightness reached 95% of the initial brightness were measured at the same time. The results are as follows: The current efficiency and device life are calculated based on the values ​​of comparative compound 1 as 100%.

[0217]

[0218] From the data comparison in the above table, it can be seen that the organic electroluminescent device using the compound of the present invention as a P-type dopant shows more superior performance in driving voltage, luminous efficiency and device life than the comparative compounds 1, 2 and 3 in the device with the same color code.

[0219] LUMO energy level test: The electrochemical properties of the compounds were determined by cyclic voltammetry (CV). The test was performed using a CS300 electrochemical workstation produced by Cost Instrument Co., Ltd. and a three-electrode working system: a platinum disk electrode as the working electrode, an Ag / AgCl saturated KCl electrode as the reference electrode, and a platinum wire electrode as the auxiliary electrode. Anhydrous DMF was used as the solvent and 0.1 mol / L tetrabutylammonium hexafluorophosphate as the supporting electrolyte. The compounds to be tested were prepared into 10 -3mol / L solution, nitrogen was introduced into the solution for 10 min to remove oxygen before testing. Instrument parameter settings: scanning rate was 100 mV / s, ferrocene was used for potential calibration, and the absolute energy level of ferrocene in vacuum was set to -4.8 eV: The corresponding calculation formula is as follows: LUMO = -[E red (Sample)-E(Fc / Fc + )+4.8]eV, the LUMO energy levels of the compounds of the present invention and the comparative compounds were obtained by testing and calculation:

[0220]

[0221]

[0222] From the data comparison in the above table, it can be seen that the compound of the present invention has a lower LUMO energy level (<-5.0 eV), which can form a good match with the HOMO energy level of the hole transport material, can effectively form holes, increase the hole concentration, improve the hole injection and transport efficiency, and ultimately reduce the operating voltage of the device to improve the luminous efficiency.

[0223] The present invention has a lower LUMO energy level than the prior art by specially matching the substituents, and the prepared red light device has a low driving voltage, better device luminous efficiency and improved life. The above results show that the present invention compound can be used as a hole injection layer material in an organic electroluminescent device and has the potential to be applied to the OLED industry.

Claims

1. An organic compound having a structure represented by formula (1), in: Z is selected from O, S or SO; X 1 -X 6 Independently selected from X; wherein X is selected from F, CN or all fluorine-substituted C1-C4 fluoroalkyl; Z 1 -Z 3 Independently selected from CR 2 R 3 ; Among them, R 2 -R 3 Independently selected from the group consisting of halogen, CN, substituted C1-C20 alkyl, substituted C3-C20 cycloalkyl, substituted C6-C30 aryl, substituted C3-C30 heteroaryl, substituted C1-C6 alkyl sulfoxide, substituted C1-C6 alkyl sulfone or substituted C1-C6 alkylcarbonyl; Among them, R 2 -R 3 The substituents are selected from F, CN, all fluorine-substituted C1-C4 fluoroalkyl, all fluorine-substituted C1-C4 alkylsulfoxide, all fluorine-substituted C1-C4 alkylsulfone or all fluorine-substituted C1-C4 alkylcarbonyl; Wherein, the heteroaryl group contains at least one O, N or S heteroatom.

2. The organic compound according to claim 1, wherein Z is selected from O or SO.

3. An organic compound having one of the following structural formulas:

4. An electroluminescent device, include: A cathode, an anode and an organic layer arranged between the cathode and the anode, wherein the organic layer contains the organic compound described in any one of claims 1-3, wherein the organic layer includes a hole injection layer, and the organic compound described in any one of claims 1-3 is used as a hole injection material in the hole injection layer. 5 . The electroluminescent device according to claim 4 , wherein the hole injection layer comprises, in addition to the organic compound according to any one of claims 1 to 3 , at least one hole transport material containing triarylamine or carbazole as a host material. 6 . The electroluminescent device according to claim 5 , wherein the absolute value of the highest occupied molecular orbital energy level HOMO of the hole transport material containing triarylamine or carbazole is 4.8-6.8 eV.

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