Organic electroluminescent material and device thereof

Abstract

The present invention relates to an organic electroluminescent material and a device thereof. The organic electroluminescent material has a structure shown in formula (1). The organic electroluminescent material provided by the present invention has the advantages of high optical and electrical stability, low sublimation temperature, low driving voltage, high luminous efficiency, long device life, etc., and can be used as a main material in an OLED light-emitting device. At the same time, it has a low melting point, and as a molten material, it is beneficial to the stability of material evaporation. As a main material, the material has the possibility of being applied to the AMOLED industry.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and in particular to a compound formed by connecting an indole-pyrrole fused nitrogen macrocycle with an N heterocycle and similar structures, and an organic electroluminescent device containing the compound. 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 current, holes and electrons are injected from the positive and negative poles 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 generating the light emission of the OLED. However, the properties of phosphorescent OLEDs are not only determined by the triplet light emitter used. Other types of materials, such as host materials, are also very important. The host material plays a significant role in reducing the driving voltage of the device, improving the luminous efficiency of the device, and increasing the service life of the device. Therefore, it is necessary to continue to develop new host materials to further improve the performance of organic electroluminescent devices.

[0004] Patent document 1 (CN108391433B) records A nitrogen heteroaromatic ring structural unit bonded to a specific position of quinazoline or quinoxaline is used as a red light host material. The thermal stability and device life of this type of material need to be further improved; Patent document 2 (CN114591341A) records The main material of the indole and carbazole structural unit, the device efficiency and life of this type of material also need to be improved; Patent document 3 (US20220289681A1) records A red main body material composed of an indole-fused nitrogen macrocyclic structural unit and a triazine having a similar structure, which is different from the present invention, and the device efficiency of such a material as a main body material needs to be further improved; Patent document 4 (KR101877961B1) records The device life of the bipolar host material of indolecarbazole with similar structure as green light host material needs to be further improved. Summary of the invention

[0005] In order to solve the above defects, the present invention provides a compound formed by connecting indole and pyrrole fused nitrogen macrocycles with N heterocycles and similar structures, and an organic electroluminescent device containing the compound.

[0006] An organic electroluminescent material of the present invention has a structure shown in formula (1). The organic electroluminescent material provided by the present invention has the advantages of high optical and electrical stability, low sublimation temperature, low driving voltage, high luminous efficiency, long device life, etc., and can be used as a main material in OLED light-emitting devices. At the same time, it has a low melting point, which is beneficial to the stability of material evaporation as a molten material. The compound, as a main material, has the possibility of being applied to the AMOLED industry.

[0007] An organic electroluminescent material having a structure shown in formula (1),

[0008]

[0009] Wherein, L is selected from any one of a single bond, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C20 heteroaryl group;

[0010] X 1 To X 3 Each independently represents N or CR a , Ring A, Ring B and Ring C are identically or differently selected from aromatic rings having 5 to 18 carbon atoms, or heteroaromatic rings having 3 to 18 carbon atoms each time they appear;

[0011] Wherein, E has a structure represented by formula (2):

[0012]

[0013] Among them, A 1 To A 5 Same or different, A 1 To A 5 Each independently selected from N or CR 1 ;; and A 1 To A 5 At least one of them is N, and at least one is C-CN, * represents the connection point with formula (1);

[0014] Among them, R a , R b , R c , R d and R 1Each occurrence is the same or different and is independently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 10 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 10 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 10 carbon atoms, substituted or unsubstituted an aryl group having 0 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, a substituted or unsubstituted acyl group having 0 to 20 carbon atoms, a carbonyl group, a carboxylic acid group, a substituted or unsubstituted ester group having 0 to 20 carbon atoms, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a substituted or unsubstituted sulfinyl group having 0 to 20 carbon atoms, a substituted or unsubstituted sulfonyl group having 0 to 20 carbon atoms, a phosphino group; or an adjacent R a , adjacent Rb, adjacent Rc, and adjacent Rd can be connected to form a ring;

[0015] The substitution is substitution with deuterium, halogen, cyano, alkyl with 1 to 6 carbon atoms, or aryl with 6 to 30 carbon atoms.

[0016] Wherein, m, n, and k are each independently an integer of 1 to 4;

[0017] The heteroatoms in the heteroaromatic ring, heteroalkyl group, heterocyclic group and heteroaryl group are independently selected from O, S, N, Si, Ge or P.

[0018] In some embodiments, the organic electroluminescent material has a structure shown in formula (3),

[0019]

[0020] Among them, X 1 To X 3 Each independently represents N or CR a ,Y 1 To Y 10 Same or different, Y 1 To Y 10 are independently selected from N or CR; Ra is consistent with the above definition;

[0021] R is the same as defined above for Rb, Rc, and Rd, and each occurrence of R is the same or different and is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 10 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 10 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted a heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, a substituted or unsubstituted acyl group having 0 to 20 carbon atoms, a carbonyl group, a carboxylic acid group, a substituted or unsubstituted ester group having 0 to 20 carbon atoms, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a substituted or unsubstituted sulfinyl group having 0 to 20 carbon atoms, a substituted or unsubstituted sulfonyl group having 0 to 20 carbon atoms, and a phosphino group; adjacent R and adjacent Ra can be connected to form a ring, and the substitution is substituted by deuterium, halogen, cyano, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

[0022] In some embodiments, Y 1 To Y 10 Each is independently denoted as CR.

[0023] In some embodiments, A in formula (2) 1 To A 5 There are two Ns in A 1 To A 5 At least one of them is C-CN.

[0024] In some embodiments, the organic electroluminescent material is one of the structures shown in formula (4)-(27):

[0025]

[0026]

[0027] In some embodiments, E represents a structure consisting of one of the following formulae (28)-(34):

[0028]

[0029] Among them, A in formula (28)-(34) 1 To A5 CR 1 , R1 is consistent with the above definition.

[0030] In some embodiments, L is a single bond, a substituted or unsubstituted C6-C10 aryl group.

[0031] In some embodiments, L is substituted or unsubstituted phenyl.

[0032] In some embodiments, R 1 It is a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 18 carbon atoms.

[0033] In some embodiments, R 1 The same or different groups at each occurrence are selected from the group consisting of phenyl, deuterated phenyl, methylphenyl, fluorophenyl, tert-butylphenyl, trideuterated methylphenyl, biphenyl, naphthyl, deuterated naphthyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, carbazolyl, pyridyl, pyrimidinyl, 4-cyanophenyl, 3-cyanophenyl and triphenylene.

[0034] In some embodiments, the organic electroluminescent material has one of the following structural formulas, or a corresponding partially or completely deuterated or fluorinated one,

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046] An organic electroluminescent device, characterized by comprising the above-mentioned organic electroluminescent material.

[0047] The organic electroluminescent device comprises a light-emitting layer, and the light-emitting layer comprises the organic electroluminescent material.

[0048] The material of the present invention has the advantages of high optical and electrical stability, low sublimation temperature, low driving voltage, high luminous efficiency, long device life, etc., and can be used as a main material in OLED light-emitting devices. At the same time, it has a low melting point, which is beneficial to the stability of material evaporation as a molten material. As a main material, the material has the possibility of being applied to the AMOLED industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 For compound CPD125 1 HNMR spectrum,

[0050] Figure 2 For compound CPD143 1 HNMR spectrum. DETAILED DESCRIPTION

[0051] The compound of the present invention, an organic electroluminescent material, has a structure shown in formula (1):

[0052]

[0053] Wherein, L is selected from any one of a single bond, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C20 heteroaryl group;

[0054] X 1 To X 3 Each independently represents N or CR a , Ring A, Ring B and Ring C are identically or differently selected from a carbocyclic ring having 5 to 18 carbon atoms, or a heterocyclic ring having 3 to 18 carbon atoms each time they appear;

[0055] Wherein, E has a structure represented by formula (2):

[0056]

[0057] Among them, A 1 To A 5 are the same or different selected from N and CR 1 A 1 To A 5 At least one of them is N, and at least one is C-CN, * represents the connection point with formula (1);

[0058] Among them, R a , R b , R c , R d and R 1The group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 10 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 10 carbon atoms, substituted or unsubstituted substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, substituted or unsubstituted acyl groups having 0 to 20 carbon atoms, carbonyl groups, carboxyl groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, substituted or unsubstituted sulfinyl groups having 0 to 20 carbon atoms, substituted or unsubstituted sulfonyl groups having 0 to 20 carbon atoms, phosphino groups, and combinations thereof; adjacent substituents R a Between b Between c Between d can be optionally connected to form a ring;

[0059] The substitution is substitution with deuterium, halogen, cyano, alkyl with 1 to 6 carbon atoms, or aryl with 6 to 30 carbon atoms.

[0060] Wherein, m, n, and k are each independently an integer of 1 to 4;

[0061] The heteroatoms in the heteroaromatic ring, heteroalkyl group, heterocyclic group and heteroaryl group are independently selected from O, S, N, Si, Ge or P.

[0062] Hereinafter, examples of each group of the compound represented by formula (1) will be described.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] Adjacent substituent R aBetween b Between c Between d "They can be optionally connected to form a ring" means that when adjacent ring atoms on the A, B or C ring are respectively connected with Rb, Rc or Rd groups, the Rb, Rc or Rd groups on the adjacent ring atoms can be connected to form a ring; when adjacent ring atoms on the ring formed by X1, X2, and X3 are connected with Ra groups, the Ra groups on the adjacent ring atoms can be connected to form a ring.

[0071] 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.

[0072] 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.

[0073] Synthesis of compound CPD001

[0074]

[0075] Synthesis of compound CPD001-3

[0076] Compound CPD001-1 (40.00 g, 198.78 mmol), CPD001-2 (37.36 g, 238.54 mmol), potassium carbonate (54.95 g, 397.56 mmol), and ethanol (600 ml) were added to a 1000 ml three-necked round-bottom flask, replaced with vacuum nitrogen three times, and heated to 80 ° C for overnight reaction. TLC (ethyl acetate: n-hexane = 1:5 as the developing solvent) monitored the complete consumption of the raw material CPD001-1. After cooling to room temperature, the ethanol was removed by vacuum concentration at 65 ° C. 500 ml of deionized water was added, and the mixture was slurried at 80 ° C oil temperature for 1 hour, filtered, and the same operation was repeated once more. The white solid was dried at 100 ° C overnight to obtain compound CPD001-3 (46.21 g, purity: 99.41%, yield: 85.06%), mass spectrum: 274.10 (M+H).

[0077] Synthesis of compound CPD001-4

[0078] Compound CPD001-3 (45.00 g, 164.66 mmol) and phosphorus oxychloride (150 ml, 397.56 mmol) were added to a 500 ml three-necked round-bottom flask, and the temperature was raised to 100°C for 4 hours. TLC (ethyl acetate: n-hexane = 1:5 as the developing solvent) monitored the complete consumption of the raw material CPD001-3. After cooling to room temperature, the phosphorus oxychloride was removed by concentrating under reduced pressure at 70°C. Dichloromethane (500 ml) was added to dissolve the material, and then the dichloromethane solution was slowly added dropwise to 1000 ml of deionized water, stirred at room temperature for 1 hour, allowed to stand for separation, and the organic phase was washed with deionized water (300 ml * 3); the organic phase was purified by silica gel column chromatography (300 g, 200-300 mesh, ethyl acetate: n-hexane = 1:10 as eluent), and after elution, it was concentrated under reduced pressure at 70 ° C for 2 hours to obtain a white solid as compound CPD001-4 (39.60 g, purity: 99.56%, yield: 82.44%), mass spectrum: 292.64 (M+H).

[0079] Synthesis of compound CPD001

[0080] Compound CPD001-5 (20.38 g, 61.70 mmol) and N,N-dimethylformamide (300 ml) were added to a 500 ml three-necked round-bottom flask, and the atmosphere was replaced with nitrogen three times under vacuum. Sodium hydride (2.47 g, 61.70 mmol) with a mass fraction of 60% was slowly added under stirring at room temperature, and stirred at room temperature for 30 minutes. Then CPD001-4 (15.00 g, 51.42 mmol) was slowly added, and the temperature was raised to 100°C for overnight reaction. TLC (ethyl acetate: n-hexane = 1:10 as the developing solvent) was used to monitor the complete consumption of the raw material CPD001-4. The reaction mixture was cooled to room temperature, and the reaction solution was slowly added dropwise to 1000 ml of deionized water. The mixture was stirred at room temperature for 1.5 hours to precipitate a large amount of yellow solid. The mixture was filtered, and the filter cake was washed with 300 ml of deionized water and dried under vacuum at 80°C for 2 hours. The mixture was crystallized twice with toluene and methanol to obtain a yellow solid compound CPD001 (15.06 g, purity: 99.95%, yield: 50.00%). 15.06 g of crude CPD001 was purified by sublimation to obtain sublimation pure CPD001 (12.51 g, purity: 99.95%, yield: 83.07%), with a mass spectrum of 586.24 (M+H). 1 H NMR (400 MHz, CDCl 3)δ8.25-8.14(m,4H),7.89-7.79(m,2H),7.72(dd,J=15.0,2.9Hz,1H),7.59-7.42( m,8H),7.42-7.36(m,2H),7.21-7.15(m,3H),7.10-7.05(m,2H),7.04-6.97(m,1H).

[0081] Synthesis of compound CPD009

[0082]

[0083] Synthesis of compound CPD009-2

[0084] Referring to the synthesis and purification method of compound CPD001-3, only the corresponding raw materials need to be changed to obtain the target compound CPD009-2 (32.55 g, purity: 99.31%, yield: 81.01%) as a white solid, with a mass spectrum of 324.26 (M+H).

[0085] Referring to the synthesis and purification method of compound CPD001-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD009-3 (27.63 g, purity: 99.59%, yield: 83.33%), mass spectrum: 342.07 (M+H).

[0086] Synthesis of compound CPD009

[0087] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD009 (14.25 g, purity: 99.94%, yield: 51.66%). 14.25 grams of crude CPD009 was sublimated and purified to obtain sublimation pure CPD009 (11.29 g, purity: 99.94%, yield: 79.23%), mass spectrum: 636.22 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.65(s,1H),8.49(dd,J=15.0,3.0Hz,1H),8.21-8.14(m,3H),8.10-8.06(m,1H),8.02-7.98(m,1H),7.86- 7.82(m,2H),7.74-7.70(m,1H),7.68-7.47(m,6H),7.45-7.40(m,3H),7.21-7.13(m,3H),7.13-6.97(m,3H).

[0088] Synthesis of compound CPD019

[0089]

[0090] Synthesis of compound CPD019-4

[0091] Compound CPD019-1 (30.00 g, 206.67 mmol), CPD019-2 (37.66 g, 206.67 mmol), CPD019-3 (37.23 g, 620.00 mmol), potassium carbonate (85.69 g, 620.00 mmol), N, N-dimethylformamide (500 ml) were added to a 1000 ml three-necked round-bottom flask, replaced with vacuum nitrogen three times, and heated to 80 ° C for overnight reaction. TLC (ethyl acetate: n-hexane = 1:5 as the developing solvent) monitored that the raw materials CPD019-1 and CPD019-2 were completely consumed. After cooling to room temperature, the mixture was concentrated under reduced pressure at 65 ° C to remove N, N-dimethylformamide. Add 500 ml of deionized water, heat and beat with oil at 70°C for 1 hour, filter, wash the filter cake with 500 ml of deionized water, wash with 100 ml of ethanol, and dry in vacuo at 100°C overnight to obtain a white solid, compound CPD019-4 (44.87 g, purity: 99.21%, yield: 62.14%), mass spectrum: 350.12 (M+H).

[0092] Synthesis of compound CPD019-5

[0093] Referring to the synthesis and purification method of compound CPD001-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD019-5 (30.06 g, purity: 99.42%, yield: 80.09%), mass spectrum: 368.12 (M+H).

[0094] Synthesis of compound CPD019

[0095] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD019 (17.51 ​​g, purity: 99.93%, yield: 53.85%). 17.51 ​​g of crude CPD019 was sublimated and purified to obtain sublimation pure CPD019 (14.20 g, purity: 99.93%, yield: 81.10%), mass spectrum: 662.24 (M+H). 1 H NMR (400 MHz, CDCl 3)δ8.34-8.26(m,2H),8.22-8.15(m,2H),7.90-7.79(m,4H),7.79 -7.67(m,3H),7.61-7.34(m,10H),7.26-7.11(m,3H),7.11-6.95(m,3H).

[0096] Synthesis of compound CPD033

[0097]

[0098] Synthesis of compound CPD033-2

[0099] Referring to the synthesis and purification method of compound CPD019-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD033-2 (18.88 g, purity: 99.32%, yield: 65.33%), mass spectrum: 279.22 (M+H).

[0100] Synthesis of compound CPD033-3

[0101] Referring to the synthesis and purification method of compound CPD001-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD033-3 (15.23 g, purity: 99.55%, yield: 86.78%), mass spectrum: 297.08 (M+H).

[0102] Synthesis of compound CPD033

[0103] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD033 (11.44 g, purity: 99.95%, yield: 56.12%). 11.44 grams of crude CPD033 was purified by sublimation to obtain sublimation pure CPD033 (8.68 g, purity: 99.95%, yield: 75.88%), mass spectrum: 591.24 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.19(dd,J=7.4,1.5Hz,2H),7.85-7.83(m,2H),7.72(dd,J=7.5,1.4Hz,1H),7.60-.47(m,4H),7.47-7.42(m,1H ),7.40(dd,J=7.4,1.7Hz,2H),7.24-7.15(m,3H),7.10(t,J=7.5Hz,1H),7.05(t,J=7.5Hz,1H),7.01-6.99(m,1H).

[0104] Synthesis of compound CPD053

[0105]

[0106] Synthesis of compound CPD053-2

[0107] Compound CPD001-4 (20.00 g, 68.55 mmol), CPD053-1 (10.55 g, 75.41 mmol), tetrakis(triphenylphosphine)palladium (3.96 g, 3.43 mmol), potassium carbonate (18.95 g, 137.11 mmol), tetrahydrofuran (300 ml), and deionized water (100 ml) were added to a 1000 ml three-necked round-bottom flask, replaced with vacuum nitrogen three times, and heated to 65°C for 4 hours. TLC (ethyl acetate: n-hexane = 1:10 as the developing solvent) monitored the complete consumption of the raw material CPD001-4. After cooling to room temperature, the solvent was removed by concentrating under reduced pressure at 65°C. 500 ml of dichloromethane was added to dissolve the material, and the mixture was washed with deionized water (250 ml * 3), separated and concentrated; the organic phase was purified by silica gel column chromatography (350 g, 200-300 mesh, ethyl acetate: n-hexane = 1:20 as eluent), and after elution, it was concentrated under reduced pressure at 70 ° C for 2 hours to obtain a white solid compound CPD053-2 (20.90 g, purity: 99.46%, yield: 86.78%), mass spectrum: 352.12 (M+H)

[0108] Synthesis of compound CPD053

[0109] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD053 (21.20 g, purity: 99.93%, yield: 75.06%). 21.20 g of crude CPD053 was purified by sublimation to obtain sublimation pure CPD053 (17.54 g, purity: 99.95%, yield: 82.74%), mass spectrum: 662.13 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.41-8.29(m,2H),8.25-8.15(m,2H),7.95-7.90(m,4H),7.88 -7.79(m,2H),7.72(dd,J=15.0,2.9Hz,1H),7.61-7.45(m,7H),7.45-7.35(m,3H),7.21-7.18(m,3H),7.14-6.97(m,3H).

[0110] Synthesis of compound CPD074

[0111]

[0112] Synthesis of compound CPD074-2

[0113] Referring to the synthesis and purification method of compound CPD019-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD074-2 (15.23 g, purity: 99.33%, yield: 64.05%), mass spectrum: 350.22 (M+H).

[0114] Synthesis of compound CPD074-3

[0115] Referring to the synthesis and purification method of compound CPD001-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD074-3 (14.55 g, purity: 99.56%, yield: 81.36%), mass spectrum: 368.24 (M+H).

[0116] Synthesis of compound CPD074-4

[0117] Referring to the synthesis and purification method of compound CPD053-2, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD074-4 (15.65 g, purity: 99.46%, yield: 83.25%), mass spectrum: 428.16 (M+H).

[0118] Synthesis of compound CPD074

[0119] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD074 (16.86 g, purity: 99.94%, yield: 72.11%). 16.86 grams of crude CPD074 was purified by sublimation to obtain sublimation pure CPD074 (13.30 g, purity: 99.94%, yield: 78.89%), mass spectrum: 738.26 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.22-8.16(m,2H),8.11(t,J=2.9Hz,1H),7.98-7.89(m,5H),7.87-7.81(m,2H),7.79-7 .66(m,4H),7.63-7.59(m,1H),7.57-7.36(m,10H),7.21-7.13(m,3H),7.13-6.97(m,3H).

[0120] Synthesis of compound CPD089

[0121]

[0122] Synthesis of compound CPD089-2

[0123] Referring to the synthesis and purification method of compound CPD053-2, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD089-2 (18.25 g, purity: 99.53%, yield: 84.22%), mass spectrum: 352.16 (M+H).

[0124] Synthesis of compound CPD089

[0125] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD089 (17.47 g, purity: 99.96%, yield: 75.62%). 17.47 grams of crude CPD089 was sublimated and purified to obtain sublimation pure CPD089 (14.01 g, purity: 99.96%, yield: 80.20%), mass spectrum: 662.23 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.40-8.29(m,2H),8.25-8.14(m,3H),7.89-7.80(m,2H),7.80-7.67(m,2H),7.66-7.59(m, 2H),7.58-7.35(m,10H),7.25-7.12(m,3H),7.07(dd,J=14.9,10.4Hz,2H),7.02-6.96(m,1H).

[0126] Synthesis of compound CPD100

[0127]

[0128] Synthesis of compound CPD100-2

[0129] Referring to the synthesis and purification method of compound CPD019-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD100-2 (19.45 g, purity: 99.42%, yield: 62.96%), mass spectrum: 292.06 (M+H).

[0130] Synthesis of compound CPD100-3

[0131] Referring to the synthesis and purification method of compound CPD001-4, it is only necessary to change the corresponding raw materials to obtain the white solid as the target compound CPD100-3 (18.08 g, purity: 99.51%, yield: 88.05%), mass spectrum: 310.05 (M+H).

[0132] Synthesis of compound CPD100-5

[0133] Referring to the synthesis and purification method of compound CPD053-2, it is only necessary to change the corresponding raw materials to obtain the white solid target compound CPD100-5 (17.06 g, purity: 99.63%, yield: 85.33%), mass spectrum: 353.21 (M+H).

[0134] Synthesis of compound CPD100

[0135] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD100 (18.96 g, purity: 99.93%, yield: 78.09%). 18.96 grams of crude CPD100 was sublimated and purified to obtain sublimation pure CPD100 (15.74 g, purity: 99.95%, yield: 83.02%), mass spectrum: 663.22 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ9.10(s,1H),8.77-8.64(m,1H),8.33(dt,J=15.0,3.0Hz,1H),8.25-8.13(m,3H),7.91-7.76(m,3H),7.76 -7.59(m,3H),7.59-7.45(m,5H),7.45-7.34(m,3H),7.22-7.12(m,3H),7.07(dd,J=14.9,10.4Hz,2H),7.03-6.95(m,1H).

[0136] Synthesis of compound CPD125

[0137]

[0138] Synthesis of compound CPD125-2

[0139] Referring to the synthesis and purification method of compound CPD053-2, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD125-2 (17.63 g, purity: 99.40%, yield: 85.23%), mass spectrum: 352.12 (M+H).

[0140] Synthesis of compound CPD125

[0141] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD125 (15.05 g, purity: 99.96%, yield: 74.63%). 15.05 g of crude CPD125 was purified by sublimation to obtain sublimation pure CPD125 (12.24 g, purity: 99.96%, yield: 81.33%), mass spectrum: 662.23 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.01-7.93(m,5H),7.86-7.74(m,6H),7.65(d,J=7.7Hz,1H),7.55-7.46(m,3H),7.38(t,J=6 .6Hz,3H),7.28-7.22(m,4H),7.20-7.12(m,3H),7.09(d,J=8.0Hz,1H),6.89(d,J=8.0Hz,1H).

[0142] Synthesis of compound CPD127

[0143]

[0144] Synthesis of compound CPD127-2

[0145] Referring to the synthesis and purification method of compound CPD019-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD127-2 (19.89 g, purity: 99.36%, yield: 65.18%), mass spectrum: 368.11 (M+H).

[0146] Synthesis of compound CPD127-3

[0147] Referring to the synthesis and purification method of compound CPD001-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD127-3 (17.85 g, purity: 99.54%, yield: 85.36%), mass spectrum: 386.08 (M+H).

[0148] Synthesis of compound CPD127-5

[0149] Referring to the synthesis and purification method of compound CPD053-2, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD127-5 (16.63 g, purity: 99.71%, yield: 82.55%), mass spectrum: 504.08 (M+H).

[0150] Synthesis of compound CPD127

[0151] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD127 (16.52 g, purity: 99.94%, yield: 72.21%). 16.52 g of crude CPD127 was purified by sublimation to obtain sublimation pure CPD127 (12.99 g, purity: 99.95%, yield: 78.64%), mass spectrum: 814.30 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.34-8.26(m,2H),8.23-8.15(m,2H),8.00-7.88(m,4H),7.88-7.78(m,3H),7.78-7. 69(m,5H),7.56-7.35(m,11H),7.30-7.23(m,2H),7.21-7.18(m,3H),7.13-6.94(m,3H).

[0152] Synthesis of compound CPD143

[0153]

[0154] Synthesis of compound CPD143-2

[0155] Referring to the synthesis and purification method of compound CPD019-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD143-2 (25.36 g, purity: 99.21%, yield: 61.18%), mass spectrum: 274.08 (M+H).

[0156] Synthesis of compound CPD143-3

[0157] Referring to the synthesis and purification method of compound CPD001-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD143-3 (24.58 g, purity: 99.61%, yield: 86.41%), mass spectrum: 292.06 (M+H).

[0158] Synthesis of compound CPD143-4

[0159] Referring to the synthesis and purification method of compound CPD053-2, it is only necessary to change the corresponding raw materials to obtain the white solid as the target compound CPD143-4 (20.35 g, purity: 99.68%, yield: 81.41%), mass spectrum: 352.08 (M+H).

[0160] Synthesis of compound CPD143

[0161] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD143 (14.04 g, purity: 99.95%, yield: 68.57%). 14.04 g of crude CPD143 was purified by sublimation to obtain sublimation pure CPD143 (10.99 g, purity: 99.95%, yield: 78.27%), mass spectrum: 662.24 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.47(d,J=7.1Hz,1H),8.05(dd,J=17.1,8.0Hz,2H),7.85-7.57(m,9H),7.46 -7.21(m,11H),7.17-7.12(m,2H),6.89(d,J=8.0Hz,1H),6.72(d,J=8.0Hz,1H).

[0162] Synthesis of compound CPD159

[0163]

[0164] Synthesis of compound CPD159-3

[0165] Referring to the synthesis and purification method of compound CPD019-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD159-3 (18.88 g, purity: 99.21%, yield: 62.74%), mass spectrum: 284.16 (M+H).

[0166] Synthesis of compound CPD159-4

[0167] Referring to the synthesis and purification method of compound CPD001-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD159-4 (17.60 g, purity: 99.50%, yield: 87.54%), mass spectrum: 302.24 (M+H).

[0168] Synthesis of compound CPD159-5

[0169] Referring to the synthesis and purification method of compound CPD053-2, it is only necessary to change the corresponding raw materials to obtain the white solid as the target compound CPD159-5 (16.32 g, purity: 99.75%, yield: 82.95%), mass spectrum: 362.02 (M+H).

[0170] Synthesis of compound CPD159

[0171] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD159 (14.44 g, purity: 99.92%, yield: 67.50%). 14.44 g of crude CPD159 was purified by sublimation to obtain sublimation pure CPD159 (11.31 g, purity: 99.95%, yield: 78.32%), mass spectrum: 672.29 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.23-8.16(m,2H),7.94-7.89(m,2H),7.84-7.68(m,2H),7.56-7.45(m,2H),7.45-7.36(m,3H),7.26-7.08(m,4H),7.07-6.98(m,2H).

[0172] Synthesis of compound CPD165

[0173]

[0174] Synthesis of compound CPD165-2

[0175] Referring to the synthesis and purification method of compound CPD001-3, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD165-2 (20.63 g, purity: 99.50%, yield: 84.21%), mass spectrum: 292.07 (M+H).

[0176] Synthesis of compound CPD165-3

[0177] Referring to the synthesis and purification method of compound CPD001-4, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD165-3 (18.95 g, purity: 99.57%, yield: 86.46%), mass spectrum: 310.06 (M+H).

[0178] Synthesis of compound CPD165-5

[0179] Referring to the synthesis and purification method of compound CPD053-2, it is only necessary to change the corresponding raw materials to obtain the white solid as the target compound CPD165-5 (20.08 g, purity: 99.64%, yield: 81.07%), mass spectrum: 442.13 (M+H).

[0180] Synthesis of compound CPD165

[0181] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD165 (17.41 g, purity: 99.93%, yield: 66.48%). 17.41 grams of crude CPD165 was sublimated and purified to obtain sublimation pure CPD165 (14.63 g, purity: 99.95%, yield: 84.03%), mass spectrum: 802.25 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.51(dd,J=14.9,3.0Hz,1H),8.40-8.29(m,2H),8.24-8.11(m,2H),8.04-7.88(m,5H),7.8 8-7.77(m,2H),7.75-7.69(m,3H),7.62-7.29(m,12H),7.29-7.14(m,2H),7.10-7.02(m,2H).

[0182] Synthesis of compound CPD180

[0183]

[0184] Synthesis of compound CPD180-1

[0185] Referring to the synthesis and purification method of compound CPD053-2, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD180-1 (24.16 g, purity: 99.74%, yield: 80.43%), mass spectrum: 428.15 (M+H).

[0186] Synthesis of compound CPD180

[0187] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD180 (18.96 g, purity: 99.94%, yield: 65.36%). 18.96 grams of crude CPD180 was sublimated and purified to obtain sublimation pure CPD180 (15.19 g, purity: 99.94%, yield: 80.11%), mass spectrum: 788.06 (M+H). 1 H NMR (400 MHz, CDCl 3)δ8.67(d,J=2.9Hz,1H),8.54(dd,J=14.8,3.1Hz,1H),8.42-8.10(m,3H),7.94-7.90(m,2H),7 .89-7.77(m,6H),7.76-7.72(m,2H),7.67-7.34(m,13H),7.21-7.15(m,3H),7.10-6.95(m,2H).

[0188] Synthesis of compound CPD220

[0189]

[0190] Synthesis of compound CPD220

[0191] Referring to the synthesis and purification method of compound CPD001, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD220 (17.53 g, purity: 99.95%, yield: 61.23%). 17.53 g of crude CPD220 was purified by sublimation to obtain sublimation pure CPD220 (13.94 g, purity: 99.95%, yield: 79.52%), mass spectrum: 752.24 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.41-8.26(m,3H),8.24-8.14(m,2H),8.02-7.88(m,3H),7.88-7.76(m,3H),7.72(dd,J=1 5.0,2.9Hz,1H),7.59-7.44(m,9H),7.44-7.26(m,3H),7.25-7.12(m,3H),7.12-6.98(m,2H).

[0192] Application example: Fabrication of organic electroluminescent devices

[0193] A 50 mm*50 mm*1.0 mm glass substrate with an ITO (100 nm) transparent electrode was ultrasonically cleaned in ethanol for 10 minutes, then dried at 150 degrees and heated to room temperature. 2Plasma treatment for 30 minutes. The washed glass substrate was mounted on a substrate support of a vacuum evaporation device, and the compound NDP-9 and the compound HTM 1 were evaporated at a weight ratio of 97:3 to form a hole injection layer with a thickness of 10 nm, followed by evaporation of a layer of HTM1 to form a thin film with a thickness of 60 nm as HTL1, and then a layer of HTM2 was evaporated on the HTM1 thin film to form a thin film with a thickness of 10 nm as HTL2, and then, a light-emitting layer with a thickness of 40 nm (main material: doping material = 97%: 3%) was evaporated on the HTM2 film layer by a co-evaporation mode, wherein the main materials were the compound of the present invention and comparative compound 1-5, respectively. ETL and LiQ were co-evaporated (35 nm) as an electron transport material on the light-emitting layer at a weight ratio of 50:50, and then LiQ (1 nm) was evaporated on the electron transport material layer as an electron injection material, and then Mg / Ag (100 nm, 1:9) was evaporated as a cathode material by a co-evaporation mode.

[0194]

[0195] evaluate:

[0196] The device was tested for device performance, and the compounds of the embodiments of the present invention and comparative examples 1-5 were used as the main materials for comparison. A constant current power supply (Keithley 2400) was used to flow a fixed current density through the light-emitting element, and the luminous spectrum was tested using a spectroscopic radiation system (CS2000). At the same time, the voltage value, current efficiency, spectrum, and the time when the test brightness is 95% of the initial brightness (LT95) were measured. The results are shown in Table 1:

[0197]

[0198]

[0199] Sublimation temperature comparison: Sublimation temperature is defined as: at 10- 7 Torr vacuum, sublimation rate of 1 angstrom per second corresponding to the temperature. The test results are as follows:

[0200] Material Sublimation temperature / ℃ CPD001 254 CPD125 261 CPD143 263 Comparative Compound 2 278 Comparative Compound 3 274 Comparative Compound 4 281

[0201] From the comparison of the data in the above table, it can be seen that the main material of the present invention has a lower sublimation temperature, which is conducive to industrial application.

[0202] The material of the present invention has the advantages of high optical and electrical stability, low sublimation temperature, low driving voltage, high luminous efficiency, long device life, etc., and can be used as a main material in OLED light-emitting devices. At the same time, it has a low melting point, which is beneficial to the stability of material evaporation as a molten material. The compound, as a main material, has the possibility of being applied to the AMOLED industry.

Claims

1. An organic electroluminescent material having one of the following structures: in, L is a single bond, or a substituted or unsubstituted phenyl group, wherein the substitution is substituted by deuterium, halogen, cyano, or an alkyl group having 1 to 6 carbon atoms; Wherein, E has one of the structures represented by the following formulas (28)-(34): Among them, A 1 To A 5 Same or different, A 1 To A 5 Independently selected from CR 1 ; * represents the connection point with formula (4), (6), (7), (14), (22), (23), (24); Where R 1 is selected, identically or differently at each occurrence, from the group consisting of phenyl, deuterated phenyl, methylphenyl, fluorophenyl, tert-butylphenyl, trideuterated methylphenyl, biphenyl, naphthyl, deuterated naphthyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, pyridyl, 4-cyanophenyl, and 3-cyanophenyl.

2. An organic electroluminescent material having one of the following structural formulas, or a partially or completely deuterated or fluorinated organic material: 。 3. An organic electroluminescent device, It is characterized in that The invention comprises a light-emitting layer, wherein the light-emitting layer comprises the organic electroluminescent material according to any one of claims 1 to 2.

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