Anthracene compound and application thereof in organic electroluminescent device

Abstract

The application discloses an anthracene compound and application thereof in an organic electroluminescent device, and has a chemical structure as shown in the formula (1), R1-R8 are selected from hydrogen, deuterium, tritium, fluorine, chlorine, bromine, a cyano group, an isonitrile group, a trifluoromethyl group, a nitro group, a substituted or unsubstituted alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, a keto group, an alkoxycarbonyl group or an aryloxycarbonyl group and the like; L1 and L2 are selected from a substituted or unsubstituted C6-C30 arylene group or a C2-C30 heteroarylene group; A1 and A2 are selected from a substituted or unsubstituted C6-C40 aryl group or a C2-C40 heteroaryl group or a group as shown in the formula (2). The anthracene compound of the application is used in an OLED device as a light-emitting host material and the like, has a simple synthesis process and can effectively improve the light-emitting efficiency and service life of the device.

Description

Technical Field

[0001] This invention relates to the field of organic light-emitting materials, specifically to an anthracene compound and its application in organic electroluminescent devices. Background Technology

[0002] Organic light-emitting diode (OLED) displays have garnered significant attention from both academia and industry in recent years. As self-emissive electronic devices, OLEDs possess the following characteristics: high brightness, wide viewing angles, fast response times, excellent color reproduction and contrast, and the ability to be driven at relatively low voltages. Consequently, OLED displays are increasingly being used in various electronic products.

[0003] To achieve full-color display in OLED displays, the typical technical approach involves arranging OLED devices of red, green, and blue light in a periodic matrix, controlling the brightness ratio of each color to display different colors. However, due to the short wavelength of blue light, organic materials need to withstand high photon energy, resulting in blue light devices typically having the shortest lifespan among the three light-emitting devices, making it a key factor limiting the lifespan of OLED displays. Currently, compounds based on 9,10-disubstituted anthracene are widely used as host materials for the emissive layer of blue OLEDs, possessing suitable frontier orbital energy levels, singlet and triplet states, and good chemical stability. Nevertheless, further development of new materials is still necessary to improve device efficiency and lifespan. Summary of the Invention

[0004] Based on this, the present invention provides an anthracene compound having the chemical structure shown in formula (1):

[0005]

[0006] In formula (1), R1-R8 may be the same as or different from each other, and are independently selected from hydrogen, deuterium, tritium, fluorine, chlorine, bromine, cyano, isonitrile, trifluoromethyl, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C1-C15 alkoxy, substituted or unsubstituted C1-C15 alkylthio, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C1-C30 ketone, substituted or unsubstituted C2-C30 alkoxycarbonyl, substituted or unsubstituted C6-C30 aryloxycarbonyl;

[0007] L1 and L2 may be the same or different, and are independently selected from single bonds, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene;

[0008] A1 and A2 may be the same or different, and are independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C2-C40 heteroaryl, or groups shown in formula (2), while simultaneously satisfying that at least one of A1 and A2 is selected from groups shown in formula (2):

[0009]

[0010] In equation (2), R x and R y The same or different, independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, or the group shown in formula (3), or R x and R y They connect to form a helical ring structure:

[0011]

[0012] R a and R b Each occurrence may be identical or different from the others, and is independently selected from hydrogen, deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C1-C15 alkoxy, substituted or unsubstituted C1-C15 alkylthio, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 ketone, substituted or unsubstituted C2-C30 alkoxycarbonyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or adjacent R a or R b They are bonded together to form a ring structure, m and n may be the same or different, and are independently selected from 0, 1, 2, 3, 4, 5 or 6;

[0013] In equation (3), R z Each occurrence may be identical or different from the others, and is independently selected from hydrogen, deuterium, fluorine, chlorine, bromine, cyano, isonitrile, trifluoromethyl, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C1-C15 alkoxy, substituted or unsubstituted C1-C15 alkylthio, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C1-C30 ketone, substituted or unsubstituted C2-C30 alkoxycarbonyl, substituted or unsubstituted C6-C30 aryloxycarbonyl, or adjacent R z They bond to each other to form a ring structure, and p is selected from 0, 1, 2, 3 or 4;

[0014] G1, G2, and G3 may be the same as or different from each other, and are independently selected from non-existent, substituted, or unsubstituted C6-C12 aromatic rings or any ring structure shown in formulas (4)-(6), while simultaneously satisfying that at least one of G1, G2, and G3 is selected from any ring structure shown in formulas (4)-(6):

[0015]

[0016] In equations (4)-(6), Z is either the same or different each time it appears, and is selected from O, S, N(R). i ) or C(R d R e ), R i R d and R e They may be the same as or different from each other, and are independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl.

[0017] * represents a connection site, which is connected to the corresponding carbon atom, where *1 or *2 is connected to formula (1);

[0018] The “substituted or unsubstituted…” in the phrase “substituted…” means substituted by one or more substituents independently selected from the group consisting of deuterium, fluorine, chlorine, bromine, cyano, nitro, C1-C15 alkyl, C3-C15 cycloalkyl, C1-C15 alkoxy, C1-C15 alkylthio, C6-C25 aryl, and C2-C25 heteroaryl.

[0019] The present invention also provides the application of the aforementioned anthracene compounds in organic electroluminescent devices, for example, as the light-emitting host material of organic electroluminescent devices.

[0020] The present invention also provides an organic electroluminescent device, comprising a substrate, a first electrode, an organic functional layer, and a second electrode, wherein the organic functional layer comprises at least one layer selected from a light-emitting layer, an electron transport layer, or a hole transport layer, and the material comprises one or more of the aforementioned anthracene compounds.

[0021] The present invention also provides a display or lighting device, including the aforementioned organic electroluminescent device.

[0022] Compared with existing technologies, this invention has the following advantages: Anthracene-based compounds possess high singlet and triplet energy levels, making them suitable for use as host materials for emitting layers, especially for blue light-emitting devices. This invention introduces cycloalkyl or heterocycloalkyl groups based on the excellent carrier transport properties of the fluorene group. On the one hand, this can regulate the electron cloud distribution of the molecule, further improving the carrier transport rate; on the other hand, it can appropriately increase the steric hindrance of the molecule, raise the glass transition temperature, and suppress the crystallization tendency of the molecule during vacuum deposition, which is beneficial for forming a uniform amorphous thin film, thus facilitating the acquisition of OLED devices with excellent luminous efficiency and lifespan. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the top-emitting organic electroluminescent device in the embodiment; wherein: 101, substrate layer; 102, first electrode (anode); 103, hole injection layer; 104, first hole transport layer; 105, second hole transport layer; 106, organic light-emitting layer; 107, hole blocking layer; 108, electron transport layer; 109, second electrode (cathode); 110, capping layer. Detailed Implementation

[0024] This invention provides an anthracene compound having the chemical structure shown in formula (1):

[0025]

[0026] In formula (1), R1-R8 may be the same as or different from each other, and are independently selected from hydrogen, deuterium, tritium, fluorine, chlorine, bromine, cyano, isonitrile, trifluoromethyl, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C1-C15 alkoxy, substituted or unsubstituted C1-C15 alkylthio, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C1-C30 ketone, substituted or unsubstituted C2-C30 alkoxycarbonyl, substituted or unsubstituted C6-C30 aryloxycarbonyl;

[0027] L1 and L2 may be the same or different, and are independently selected from single bonds, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene;

[0028] A1 and A2 may be the same or different, and are independently selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C2-C40 heteroaryl, or groups shown in formula (2), while simultaneously satisfying that at least one of A1 and A2 is selected from groups shown in formula (2):

[0029]

[0030] In equation (2), R x and R y The same or different, independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, or the group shown in formula (3), or R x and R y They connect to form a helical ring structure:

[0031]

[0032] R a and R b Each occurrence may be identical or different from the others, and is independently selected from hydrogen, deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C1-C15 alkoxy, substituted or unsubstituted C1-C15 alkylthio, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 ketone, substituted or unsubstituted C2-C30 alkoxycarbonyl, substituted or unsubstituted C6-C30 aryloxycarbonyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, or adjacent R a or R b They are bonded together to form a ring structure, m and n may be the same or different, and are independently selected from 0, 1, 2, 3, 4, 5 or 6;

[0033] In equation (3), R z Each occurrence may be identical or different from the others, and is independently selected from hydrogen, deuterium, fluorine, chlorine, bromine, cyano, isonitrile, trifluoromethyl, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C1-C15 alkoxy, substituted or unsubstituted C1-C15 alkylthio, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C1-C30 ketone, substituted or unsubstituted C2-C30 alkoxycarbonyl, substituted or unsubstituted C6-C30 aryloxycarbonyl, or adjacent R z They bond to each other to form a ring structure, and p is selected from 0, 1, 2, 3 or 4;

[0034] G1, G2, and G3 may be the same as or different from each other, and are independently selected from non-existent, substituted, or unsubstituted C6-C12 aromatic rings or any ring structure shown in formulas (4)-(6), while simultaneously satisfying that at least one of G1, G2, and G3 is selected from any ring structure shown in formulas (4)-(6):

[0035]

[0036] In equations (4)-(6), Z is either the same or different each time it appears, and is selected from O, S, N(R). i ) or C(R d R e ), R i R d and R e They may be the same as or different from each other, and are independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl.

[0037] * represents a connection site, which is connected to the corresponding carbon atom, where *1 or *2 is connected to formula (1);

[0038] The “substituted or unsubstituted…” in the phrase “substituted…” means substituted by one or more substituents independently selected from the group consisting of deuterium, fluorine, chlorine, bromine, cyano, nitro, C1-C15 alkyl, C3-C15 cycloalkyl, C1-C15 alkoxy, C1-C15 alkylthio, C6-C25 aryl, and C2-C25 heteroaryl.

[0039] In some embodiments, in formula (1), A1 and A2 are independently selected from substituted or unsubstituted C6-C40 aryl groups, substituted or unsubstituted C2-C40 heteroaryl groups, groups with any structure shown in formula (7), or groups with any structure shown in formula (8):

[0040]

[0041] In equation (7), R x and R y At least one of the structures shown in equation (3), wherein G3 is selected from any one of the ring structures shown in equations (4)-(6), and R a R b The definitions of m, n, *1, and *2 are as described above;

[0042]

[0043] In equation (8), R x R y R a R b R z The definitions of Z, m, n and p are as described above.

[0044] In some embodiments, G1, G2, and G3 may be the same as or different from each other, and are independently selected from any group of the structure shown in formula (9):

[0045]

[0046]

[0047]

[0048] In equation (9), R c The group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, benzyl, methylphenyl, ethylphenyl, tert-butylphenyl, biphenyl or naphthyl; the hydrogen atom on any of the groups in the structure shown in formula (9) can be replaced by deuterium.

[0049] In some embodiments, R x and R y The same or different groups, independently selected from the following groups, substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, or groups selected from formula (3), wherein G3 is as described in claim 3, R z and p as described in claim 1;

[0050] Or the R x and R y They can be connected to form a spiral ring structure as shown in equation (10):

[0051]

[0052] In equation (10), R f R g and R h They may be the same or different from each other, and are independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl. *a indicates a bonding site, which is bonded to the 9,9'-position of the fluorenyl group to form a spirocyclic structure.

[0053] In the above structure, any hydrogen atom on the benzene ring can be replaced by one of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthyl, pyridyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, or quinoxalinyl; any hydrogen atom on the alkyl group can be replaced by one of deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0054] In some embodiments, in formula (1), A1 and A2 are the same as or different from each other, and are selected from the groups shown in formula (2) or the groups shown in formula (11):

[0055]

[0056] In equation (11), X is either the same or different from each other each time it appears, and is independently selected from N, CH, C(R). 10 ) or C*, R 10 Selected from deuterium, fluorine, chlorine, bromine, cyano, nitro, C1-C12 alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, C1-C12 alkylthio, C6-C30 aryl, C2-C30 heteroaryl, * indicates the bonding site with anthracene;

[0057] Y is selected from O, S, N(R) 11 ), C(R 12 R 13 ) or Si(R 14 R 15 ), R 11 ~R 15 Each is independently selected from C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C2-C30 heteroaryl, or R 12 and R 13 They bond to form C5-C12 aliphatic rings or C12-C30 aromatic fused rings.

[0058] In some embodiments, in formula (1), A1 and A2 are the same as or different from each other, and are selected from the groups shown in formula (2) or the groups shown in formula (12):

[0059]

[0060]

[0061] In formula (12), any one and only one carbon atom on an aromatic ring is a bonding site, or any hydrogen atom can be replaced by one of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, methoxy, ethoxy, methylthio, ethylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthyl, pyridyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, or quinoxalinyl.

[0062] In some embodiments, in formula (1), L1 and L2 are independently selected from single bonds or groups with any structure as shown in formula (13):

[0063]

[0064] In equation (13), U is either the same or different from each other each time it appears, and is independently selected from N, CH, and C(R). 16 ) or C*, simultaneously satisfying that there are exactly two Us that are C*, R 16 Selected from deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, C1-C12 alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, C1-C12 alkylthio, C6-C30 aryl, C2-C30 heteroaryl; * indicates a bonding site, one of which is attached to an anthracene group, and the other is attached to A1 or A2;

[0065] V is selected from O, S, N(R) 17 ), C(R 18 R 19 ) or Si(R 20 R 21 ), R 17 ~R 21 Independently selected from C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C2-C30 heteroaryl, or R p and R q They bond to form C5-C12 aliphatic rings or C12-C30 aromatic fused rings.

[0066] In some embodiments, L1 and L2 may be the same or different, and are independently selected from single bonds or groups with any structure as shown in formula (14):

[0067]

[0068]

[0069] In formula (14), any two and only two carbon atoms on the aromatic rings are bonding sites, or any hydrogen atom can be replaced by one of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthyl, pyridyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, or quinoxalinyl.

[0070] In some embodiments, in formula (1), R1-R8 may be the same as or different from each other, and are independently selected from hydrogen, deuterium, tritium, fluorine, chlorine, bromine, cyano, isonitrile, trifluoromethyl, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or aryl or heteroaryl as shown in formula (15):

[0071]

[0072] In formula (15), any one and only one carbon atom on an aromatic ring is a bonding site; or any hydrogen atom can be replaced by one of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, methoxy, ethoxy, methylthio, ethylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthyl, pyridyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, or quinoxalinyl.

[0073] Preferably, in each of the aforementioned chemical structures of the present invention, the hydrogen atom at each position can be replaced by deuterium.

[0074] In some embodiments, the anthracene compounds represented by formula (1) are selected from the following chemical structures:

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081] The synthesis method of the anthracene compounds of the present invention will be specifically described below with reference to the synthesis examples. Compounds whose synthesis methods are not mentioned in the present invention are obtained through commercial means.

[0082] Example 1

[0083] Synthesis of compound H3:

[0084]

[0085] The method for synthesizing 9,10-diboronic anthracene (including deuterated or non-deuterated) is described in non-patent literature: Dyes and Pigments (2010), 85(3), 93-98.

[0086] Synthesis of compound ii-H3:

[0087] Under a nitrogen atmosphere, 9,10-diboronic anthracene-D8 (5.5 g, 20.0 mmol, 1 eq), 1-bromonaphthalene-D7 (4.3 g, 20.0 mmol, 1 eq), potassium carbonate (6.9 g, 50.0 mmol, 2.5 eq), tetrakis(triphenylphosphine)palladium (231.1 mg, 0.2 mmol, 1% eq), and degassed toluene (90 mL), ethanol (60 mL), and water (30 mL) were added sequentially to a three-necked flask. Stirring was started, and the mixture was refluxed under a nitrogen atmosphere for 8 hours. Thin-layer chromatography analysis showed that virtually no reactants remained. The reaction mixture was cooled to room temperature and poured into 100 mL of ethyl acetate, allowing it to stand for phase separation. The organic phase was collected, and the aqueous phase was extracted with ethyl acetate (3 x 30 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was recrystallized from the mixed solvent of ethanol and n-hexane to give compound ii-H3 (5.0 g, yield 68.8%).

[0088] Synthesis of compound iv-H3:

[0089] Compound iv-H3 was synthesized using the same method as compound iv-H3, except that 2-bromo-9-fluorenone (compound iii-H3) and compound ii-H3 were used to replace 9,10-diboronic anthracene-D8 and 1-bromonaphthalene-D7, respectively. The yield was 75.5%.

[0090] Synthesis of compound vi-H3:

[0091] Under a nitrogen atmosphere, compound iv-H3 (10.0 g, 10.0 mmol, 1 eq), p-toluenesulfonyl hydrazine (2.8 g, 15.0 mmol, 1.5 eq), and anhydrous toluene (100 mL) were added sequentially to a dry three-necked flask. After thorough stirring, the reaction mixture was heated to 80 °C and stirred for 2 hours under a nitrogen atmosphere. Subsequently, potassium carbonate (2.8 g, 20.0 mmol, 2 eq) and compound v-H3 (3.5 g, 15.0 mmol, 1.5 eq) were added sequentially to the reaction mixture, and the reaction was continued at 110 °C for 6 hours. Thin-layer chromatography analysis revealed virtually no remaining reactants. The reaction system was cooled to room temperature, and 90 mL of saturated sodium bicarbonate aqueous solution was slowly added. After standing and separating the phases, the organic phase was collected using a separatory funnel. The aqueous phase was extracted with toluene (3 × 30 mL) and combined with the aforementioned organic phase. The resulting organic phase was washed sequentially with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was purified by rapid silica gel column chromatography (using a hexane / toluene mixture as the mobile phase) to obtain compound vi-H3 (5.2 g, yield 77.6%).

[0092] Synthesis of compound H3:

[0093] Under a nitrogen atmosphere, compound iv-6 (4.7 g, 7.0 mmol, 1 eq), bis(di-benzylacetone)palladium (198.5 mg, 0.35 mmol, 5% eq), triphenylphosphine (183.6 mg, 0.7 mmol, 10% eq), potassium tert-butoxide (942.6 mg, 8.4 mmol, 1.2 eq), compound vii-H3 (2.2 g, 8.4 mmol, 1.2 eq), and anhydrous toluene (70 mL) were added sequentially to a dry three-necked flask. After thorough stirring, the mixture was heated to 100 °C under a nitrogen atmosphere and reacted for 12 hours. Thin-layer chromatography analysis revealed virtually no remaining reactants. The reaction system was cooled to room temperature, and the reaction was quenched with 50 mL of deionized water. After standing and separating the layers, the organic phase was collected using a separatory funnel. The aqueous phase was extracted with toluene (3 × 30 mL) and combined with the aforementioned organic phase. The resulting organic phases were washed sequentially with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was purified sequentially by rapid silica gel column chromatography (mobile phase: hexane / toluene mixture) and recrystallization to obtain compound H3 (4.0 g, yield 66.7%). The overall yield of the four-step reaction was 26.9%. Mass spectrometry (m / z) = 856.56 [M+H] +

[0094] Examples 2-8 synthesized compounds (x) as shown in Table 1 below, following the preparation method of compound H3 in Example 1: H12, H24, H36, H51, H54, H71, H87. The difference was that the starting materials ix, iii-x, vx, and vii-x were used in equivalent amounts to replace compounds i-H3, iii-H3, v-H3, and vii-H3, respectively. The main starting materials used, the intermediates synthesized, the yields, and the mass spectrometry characterization data are shown in Table 1.

[0095] Table 1

[0096]

[0097] Example 9

[0098] Synthesis of compound H97

[0099]

[0100] Compound H97 was synthesized using the same method as in Example 1 for preparing compound H3, except that compounds i-H3, iii-H3, v-H3, and vii-H3 were replaced by equivalent amounts of the starting materials i-H97, iii-H97, v-H97, and vii-H97, respectively. The overall yield of the four-step reaction was 27.8%, and the mass spectrometry (m / z) result was 703.33 [M+H]. + .

[0101] The synthesis method of compound iii-H97 can be found in non-patent literature Org. Lett. 2021, 23, 8688-8693, and the specific steps are as follows:

[0102]

[0103] Under a nitrogen atmosphere, m-chloroperoxybenzoic acid (9.5 g, 55.0 mmol, 1.1 eq) was added to a dry three-necked flask and dissolved in anhydrous dichloromethane (250 mL). Then, p-bromoiodobenzene (compound viiii-H97, 14.1 g, 50.0 mmol, 1 eq) and boron trifluoride diethyl ether (17.7 g, 125.0 mmol, 2.5 eq) were added sequentially at room temperature, and the reaction system was observed to turn yellow. The reaction system was stirred at room temperature for 1 hour, then cooled to 0 °C, and p-bromophenylboronic acid (compound ix-H97, 11.0 g, 55 mmol, 1.1 eq) was slowly added. After the addition was complete, the reaction system was slowly restored to room temperature and stirred for another 30 minutes. The reaction system was then cooled to 0 °C, and trifluoromethanesulfonic acid (8.3 g, 55.0 mmol, 1.1 eq) was added dropwise, while stirring was continued at 0 °C for 15 minutes. After the reaction was complete, most of the solvent was removed by rotary evaporation, and anhydrous diethyl ether was added to precipitate the solid. The solid was collected and dried under vacuum to give compound x-H97. The obtained solid was used directly in the next reaction without further processing.

[0104] Under a nitrogen atmosphere, 5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (compound xi-97, 3.5 g, 20.0 mmol, 1 eq), compound x-H97 (50.0 mmol, 2.5 eq), palladium acetate (449 mg, 2.0 mmol, 10% eq), sodium tert-butoxide (1.9 g, 20.0 mmol, 1 eq), and anhydrous xylene (Xylene, 120 mL) were added sequentially to a dry three-necked flask. The mixture was thoroughly combined, and the reaction was carried out at 110 °C for 24 hours under a nitrogen atmosphere. Thin-layer chromatography analysis showed that virtually no reactants remained, and most of the solvent was removed by vacuum distillation. Subsequently, ethyl acetate (80 mL) and deionized water (100 mL) were added sequentially to the reaction flask, and the mixture was allowed to stand for separation. The organic phase was collected, and the aqueous phase was extracted with ethyl acetate (3 × 30 mL). The combined organic phases were dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was separated by rapid silica gel column chromatography (using a mixed solvent of n-hexane and ethyl acetate as the mobile phase) to obtain 9-fluorenone derivative iii-H97 (5.0 g, yield 79.8%).

[0105] Examples 10-13 synthesized the following compounds (x) according to the preparation method of compound H97 in Example 9: H116, H129, H164, H173, except that the starting materials ix, vx, vii-x, viiii-x and xi-x were used in equivalent amounts to replace compounds i-H97, v-H97, vii-H97, viiii-H97 and xi-H97, respectively. The main starting materials used, the intermediates synthesized, the yields and mass spectrometry characterization data are shown in Table 2.

[0106] Table 2

[0107]

[0108]

[0109] Example 14

[0110] Synthesis of compound H102

[0111]

[0112] First, compound iv-102 was synthesized following the preparation method of compound iv-H97. The synthesis steps for compounds vi-H102 and H102 are as follows:

[0113] Synthesis of compound vi-H102:

[0114] Under a nitrogen atmosphere, compound iv-102 (5.8 g, 10.0 mmol, 1 eq) and anhydrous tetrahydrofuran (100 mL) were added sequentially to a three-necked flask. After thorough mixing, the reaction system was cooled to 0 °C. At 0 °C, methyl magnesium bromide (compound v-H102, 11.0 mL, 11.0 mmol, 1.0 M solution in THF, 1.1 eq) was added dropwise to the reaction system. After the addition was complete, the mixture was slowly heated to room temperature and reacted for 12 hours. Thin-layer chromatography analysis showed that there was essentially no raw material remaining. Toluene (80 mL) and a mixed solution of saturated hydrochloric acid (5 mL) and deionized water (100 mL) were added sequentially to the reaction solution. After stirring for 5 minutes, the mixture was allowed to stand and separate into layers. The organic phase was collected using a separatory funnel, and the aqueous phase was extracted with toluene (3 × 40 mL). The combined organic phases were washed three times with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was used directly in the next reaction without further processing.

[0115] Synthesis of compound H102:

[0116] Under a nitrogen atmosphere, compound vi-H102 (10.0 mmol, 1 eq), bromobenzene (compound vii-H102, 2.1 mL, 20.0 mmol, 2 eq), and anhydrous dichloromethane (80 mL) were added sequentially to a three-necked flask. After thorough mixing, the reaction system was cooled to 0 °C. Boron tribromide (1.4 mL, 15.0 mmol, 1.5 eq) was added dropwise to the reaction system at 0 °C. After the addition was complete, the mixture was slowly heated to room temperature and reacted for 12 hours. Thin-layer chromatography analysis showed that there was essentially no reactant remaining. The reaction system was then cooled to 0 °C, and methanol was slowly added to quench the reaction. The solvent was removed by vacuum distillation of the resulting reaction solution. The crude product was separated by rapid silica gel column chromatography (mobile phase: n-hexane / toluene mixed solvent) to obtain compound H102 (5.2 g). The overall yield of the four-step reaction was 30.0%. Mass spectrometry (m / z) = 651.27 [M+H] +

[0117] Examples 14-18: The following compounds (x) were synthesized according to the preparation method of compound H102 in Example 14: H136, H144, H155, H183. The difference was that the starting materials ix, vx, vii-x, viiii-x and xi-x were used to replace compounds i-H102, v-H102, vii-H102, viiii-H102 and xi-H102 in equivalent amounts. The main starting materials used, the intermediates synthesized, the yields and mass spectrometry characterization data are shown in Table 3.

[0118] Table 3

[0119]

[0120] Example 19

[0121] Synthesis of compound H2O3

[0122]

[0123] First, compound iv-203 was synthesized following the preparation method of compound iv-H97. Except for the difference in the starting materials, the molar ratio of compound iv-H203 to 9,10-diboronic acid-based anthracene was 2:1. The synthetic steps for compound H203 are as follows:

[0124] Under a nitrogen atmosphere, 2-bromo-1,1'-biphenyl (compound v-H2O3, 10.2 g, 44.0 mmol, 2.2 eq) and anhydrous tetrahydrofuran (80 mL) were added sequentially to a three-necked flask. After thorough stirring, the reaction system was cooled to -78 °C. At this temperature, n-butyllithium (17.6 mL, 44.0 mmol, 2.5 M solution in hexane, 2.2 eq) was slowly added dropwise. After the addition was complete, the reaction was maintained at -78 °C for 1 hour. Subsequently, at -78 °C, an anhydrous tetrahydrofuran solution (50 mL) of compound iv-H2O3 (12.9 g, 20.0 mmol, 1 eq) was added dropwise to the reaction flask. After the addition was complete, the reaction system was slowly restored to room temperature. Then, a saturated ammonium chloride aqueous solution (100 mL) was slowly added to the reaction flask to quench the reaction, and most of the solvent was removed by vacuum distillation. Next, glacial acetic acid (60 mL) was slowly added to the reaction flask, followed by saturated hydrochloric acid (10 mL). Stirring was started, and the temperature was raised to 70 °C, with the reaction proceeding for 6 hours. As the reaction continued, a solid was observed to precipitate. The reaction system was brought back to room temperature, filtered, and the filter cake was collected. The obtained solid was washed thoroughly with saturated sodium bicarbonate aqueous solution, deionized water, and methanol, followed by rapid silica gel column chromatography (mobile phase: n-hexane / toluene mixed solvent) to obtain compound H2O3 (11.0 g). The overall yield was 33.3%. Mass spectrometry (m / z) = 915.39 [M+H] +

[0125] Examples 20-26 synthesized the following compounds (x) according to the preparation method of compound H203 in Example 19: H195, H213, H222, H234, H245, H263, H276, with the difference being that the starting materials ix, vx, viiii-x and xi-x were used in equivalent amounts to replace compounds i-H203, v-H203, viiii-H203 and xi-H203, respectively. The main starting materials used, the intermediates synthesized, the yields and mass spectrometry characterization data are shown in Table 4.

[0126] Table 4

[0127]

[0128] Example 27

[0129] Synthesis of compound H283

[0130]

[0131] First, following the preparation method of compound ii-H3, compound i-H283 was synthesized by equimolarly replacing compound i-H3 with compound i-H283. Next, following the synthetic route of compound H3, starting with compound iv-H3 and proceeding through compound vi-H3 to finally obtain compound H3, compound iii-H283 was synthesized. The difference was that 9-fluorenone was used, and compounds v-H283 and vii-H283 were equimolarly replacing compounds iv-H3, v-H3, and vii-H3, respectively. The resulting compounds ii-H283 and iii-H283 underwent a one-step Suzuki coupling reaction to finally obtain the target compound H283. The overall reaction yield was 34.5%. Mass spectrometry (m / z) = 818.37 [M+H] +

[0132] Examples 28-32: The following compounds (x) were synthesized according to the preparation method of compound H203 in Example 27: H292, H300, H305, H314, H324. The difference was that the starting materials ix, vx and vii-x were used to replace compounds i-H203, v-H203 and vii-H203 in equivalent amounts. The main starting materials used, the intermediates synthesized, the yields and mass spectrometry characterization data are shown in Table 5.

[0133] Table 5

[0134]

[0135] The NMR characterization data of the representative compounds involved in Examples 1-32 are shown in Table 6.

[0136] Table 6

[0137]

[0138] The anthracene compounds used in the following device examples have all been purified by sublimation, and their purity is greater than 99.98%.

[0139] Device Example 1: Fabrication of a Blue Organic Electroluminescent Device

[0140] According to such Figure 1The structure shown is used to fabricate a blue top-emitting organic light-emitting device. The fabrication process is as follows: A transparent ITO film with a thickness of 150 nm is formed on a glass substrate 101 to obtain the first electrode 102 as the anode. Then, a mixture of compound 1 and compound 1-1 is deposited as a hole injection layer 103 with a mixing ratio of 3:97 (mass ratio) and a thickness of 10 nm. Then, compound 1-1 with a thickness of 100 nm is deposited to obtain the first hole transport layer 104. Then, compound 1-2 with a thickness of 20 nm is deposited to obtain the second hole transport layer 105. Then, compound H3 and compound 1-4 of the present invention (thickness of 30 nm) are deposited at a deposition rate of 95:5 to fabricate the blue light-emitting unit 106. Then, compound 5 with a thickness of 10 nm is deposited sequentially to form a hole blocking layer 107, and compound 6 and LiQ with a mixing ratio of 4:6 (mass ratio) are deposited to form an electron transport layer 108 (thickness of 30 nm). Subsequently, ytterbium (Yb) with a thickness of 3 nm, magnesium (Mg) and silver (Ag) with a thickness of 10 nm were vacuum-deposited onto the electron injection layer at a deposition rate of 1:9 to serve as the second electrode 109. Then, compound 7 with a thickness of 70 nm was deposited as a capping layer material, completing the fabrication of the organic light-emitting device.

[0141] Table 7

[0142]

[0143] Device Examples 2-32

[0144] Except that when forming the hole injection layer and the hole transport layer, compound H3 was replaced with the compounds in Table 8, the organic electroluminescent device was fabricated using the same method as in Example 1 of the blue light device.

[0145] Comparative Examples 1-4

[0146] Except that compounds C1-C4 were used to replace compound H3 when forming the hole injection layer and the hole transport layer, the organic electroluminescent device was fabricated using the same method as in Example 1 of the blue light device.

[0147] The chemical structures of compounds 1, 1-1, 1-2, 1-3, 1-4, 5, 6, 7 and LiQ are shown in Table 7.

[0148] The compounds C1-C4 are shown below:

[0149]

[0150] The operating voltage and efficiency of the organic electroluminescent devices prepared above were calculated using a computer-controlled Keithley 2400 testing system. The device lifetime under dark conditions was obtained using a Polaronix (McScience Co.) lifetime measurement system equipped with a power supply and photodiodes as detection units. Each set of embodiment devices was produced and tested in the same batch as the device of Comparative Example 1. The operating voltage, efficiency, and lifetime of the device of Comparative Example 1 were each denoted as 1, and the ratios of the corresponding indicators of the devices of Embodiments 1-32 and Comparative Examples 2-4 to those of Comparative Example 1 were calculated, as shown in Table 9.

[0151] Table 9

[0152] Hole transport layer relative operating voltage relative efficiency Relative lifespan Comparative Example 1 C1 1 1 1 Comparative Example 2 C2 0.980 0.866 1.350 Comparative Example 3 C3 1.080 1.180 0.925 Comparative Example 4 C4 1.250 1.132 0.888 Blue light device example 1 H3 0.900 1.073 1.980 Blue light device example 2 H12 0.906 1.058 1.933 Blue light device example 3 H24 0.930 1.108 1.705 Blue light device example 4 H36 0.944 1.200 1.667 Blue light device example 5 H51 0.880 1.137 1.696 Blue light device example 6 H54 0.939 1.085 1.955 Blue light device example 7 H71 0.928 1.167 1.550 Blue light device example 8 H87 0.889 1.150 1.635 Blue light device example 9 H97 0.927 1.079 1.560 Blue light device example 10 H102 0.936 1.062 1.838 Blue light device example 11 H116 0.898 1.111 1.711 Blue light device example 12 H129 0.960 1.098 1.884 Blue light device example 13 H136 0.922 1.105 1.676 Blue light device example 14 H144 0.948 1.186 1.451 Blue light device example 15 H155 0.895 1.140 1.575 Blue light device example 16 H164 0.918 1.125 1.630 Blue light device example 17 H173 0.932 1.095 1.654 Blue light device example 18 H183 0.946 1.100 1.539 Blue light device example 19 H195 0.914 1.148 1.488 Blue light device example 20 H203 0.890 1.090 1.581 Blue light device example 21 H213 0.912 1.156 1.640 Blue light device example 22 H222 0.891 1.117 1.562 Blue light device example 23 H234 0.925 1.083 1.690 Blue light device example 24 H245 0.885 1.054 1.846 Blue light device embodiment 25 H262 0.942 1.128 1.678 Blue light device example 26 H276 0.910 1.109 1.875 Blue light device example 27 H283 0.908 1.087 1.422 Blue light device example 28 H292 0.952 1.142 1.547 Blue light device example 29 H300 0.921 1.133 1.493 Blue light device example 30 H305 0.940 1.121 1.530 Blue light device example 31 H314 0.927 1.115 1.486 Blue light device example 32 H323 0.934 1.164 1.450

[0153] In summary, compared with the devices prepared from the compounds in Examples 1-32 used as the main light-emitting materials for blue light devices, the devices prepared from the compounds in Comparative Examples 1-4 have a lower device voltage by at least 4%, a higher luminous efficiency by at least 5%, and a longer lifetime by at least 42.2%, demonstrating better performance.

[0154] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. Anthracene compounds, characterized in that, Selected from the following chemical structures: 。 2. An organic electroluminescent device comprising one or more of the anthracene compounds of claim 1.

3. The organic electroluminescent device according to claim 2, characterized in that, It includes a substrate, a first electrode, an organic functional layer, and a second electrode, wherein the organic functional layer is selected from at least one of a light-emitting layer, an electron transport layer, or a hole transport layer, and the light-emitting layer material includes one or more of the anthracene compounds described in claim 1.

4. A display or lighting device, characterized in that, Includes the organic electroluminescent device as described in claim 2 or 3.

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