Anthracene compound and organic electroluminescent device

Abstract

The application discloses an anthracene compound and an organic electroluminescent device. The compound has a structure shown in formula (1): wherein ring A is selected from formula (2) or formula (3); the compound can be used as a blue light host material in an OLED light-emitting device, has the advantages of low driving voltage, high light-emitting efficiency, long device service life and the like, and has the potential to be applied to the AMOLED industry.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic electroluminescence, and particularly relates to an anthracene compound and an organic electroluminescence device. BACKGROUND

[0002] At present, as a new generation of display technology, the organic electroluminescence device (OLED) has obtained more and more attention in the aspects of display and lighting technology, and has a very wide application prospect. However, compared with the market application requirements, the OLED device still needs to be continuously strengthened and improved in the performance aspects of luminous efficiency, driving voltage, service life and the like.

[0003] Generally, the basic structure of the OLED device is a sandwich structure in which various different functional organic functional material thin films are interposed in the middle of the metal electrode, and under the driving of the current, holes and electrons are injected from the cathode and anode respectively, the holes and electrons are combined in the light-emitting layer after moving a distance, and are released in the form of light or heat, thereby generating the light emission of the OLED. In the phosphorescent OLED, the device properties are not only determined by the used triplet light emitter, but also significantly affected by other types of materials (such as the host material). The host material plays a crucial role in reducing the driving voltage of the device, improving the luminous efficiency, and prolonging the service life and the like. However, the host materials disclosed in the prior art still have optimization space in the above performance aspects.

[0004] Therefore, it is necessary to continue to develop new host materials in order to further improve the performance of the organic electroluminescence device. SUMMARY

[0005] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, the present application provides an anthracene compound which can be used as a host material of an OLED light-emitting device, can significantly reduce the driving voltage of the device, improve the luminous efficiency, and prolong the service life of the device. The present application also provides an organic electroluminescence device comprising the compound.

[0006] Specifically, the first aspect of the present application relates to an anthracene compound having the structure shown in formula (1):

[0007]

[0008] wherein ring A is selected from the following formula (2) or formula (3);

[0009]

[0010] wherein X1-X 12 are independently selected from CR0or N; and X1-X4, X5-X6, X7-X8, X9-X 12Two adjacent positions are fused with the 5-membered ring containing X in formula (1);

[0011] R0, R1, R2 are independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboron, C6-C60 arylboron, C6-C60 arylphosphine or C6-C60 arylamine; and adjacent R0 can be connected to form a fused ring;

[0012] b is an integer from 0 to 8; if b≥2, each R1 is the same or different;

[0013] c is an integer from 0 to 4; if c≥2, each R2 is the same or different;

[0014] X is selected from O or S;

[0015] L1 and L2 are independently selected from a single bond, substituted or unsubstituted C6-C60 arylene or substituted or unsubstituted C3-C60 heteroarylene;

[0016] Ar is selected from substituted or unsubstituted C6-C36 aryl or substituted or unsubstituted C2-C36 heteroaryl;

[0017] In the L1, L2, Ar, the substitution is each independently at least one of deuterium, halogen, cyano, isocyano, phosphine, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl-substituted amine, C1-C6 hydrocarbon-substituted or unsubstituted C6-C30 aryl or C1-C6 hydrocarbon-substituted or unsubstituted C3-C30 heteroaryl, wherein the number of substitutions is mono-substitution to the maximum number of substitutions;

[0018] wherein the heteroatom in the heteroarylene, heteroaryl, heteroalkyl or heterocycloalkyl is independently selected from at least one of O, S, N, Se, Si or Ge.

[0019] The beneficial effects of the present application are as follows:

[0020] The anthracene compound described in the present application can be used as a host material in an OLED light-emitting device, has the advantages of low driving voltage, high luminous efficiency and long service life, and is particularly suitable for blue light-emitting devices. In addition, the compound has high optical and electrical stability, and has the possibility of being applied to the AMOLED (active matrix organic light-emitting diode) industry. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 For the compound 7 of the embodiment of the present application 1 H NMR spectrum;

[0022] Figure 2 The structural schematic diagram of the organic electroluminescent device of an embodiment of the present application. DETAILED DESCRIPTION

[0023] In order to make the skilled in the art more clearly understand the technical solutions described in the present application, the following examples are listed for illustration. It should be pointed out that the following examples do not constitute a limitation on the scope of protection required by the present application.

[0024] The first aspect of the embodiment of the present application provides an anthracene compound having the structure shown in formula (1):

[0025]

[0026] Wherein, ring A is selected from the following formula (2) or formula (3):

[0027]

[0028] Wherein, X1-X 12 are independently selected from CR0 or N; and X1-X4, X5-X6, X7-X8, X9-X 12 Two adjacent sites in the above formula (1) are fused with the 5-membered ring containing X;

[0029] R0, R1, R2 are independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboron, C6-C60 arylboron, C6-C60 arylphosphine or C6-C60 arylamine; and adjacent R0 can be connected to form a fused ring;

[0030] b is an integer from 0 to 8; if b≥2, each R1 is the same or different;

[0031] c is an integer from 0 to 4; if c≥2, each R2 is the same or different;

[0032] X is selected from O or S;

[0033] L1 and L2 are independently selected from a single bond, substituted or unsubstituted C6-C60 arylene or substituted or unsubstituted C3-C60 heteroarylene;

[0034] Ar is selected from substituted or unsubstituted C6-C36 aryl or substituted or unsubstituted C2-C36 heteroaryl;

[0035] each of the L1, L2, Ar is independently substituted with at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbon substituted or unsubstituted C6-C30 aryl, or C1-C6 hydrocarbon substituted or unsubstituted C3-C30 heteroaryl, wherein the number of substitutions is mono-substitution to the maximum number of substitutions;

[0036] wherein the heteroatom in the heteroarylene, heteroaryl, heteroalkyl or heterocycloalkyl is independently selected from at least one of O, S, N, Se, Si or Ge.

[0037] It can be understood that in formula (1), L1may be connected to ring A or ring E.

[0038] "Adjacent R0" refers to R0on adjacent carbon atoms, and further it can be understood that "adjacent R0may be connected to form a fused ring" refers to R0on adjacent carbon atoms can be connected to form a fused ring, for example, when the two adjacent R0are both phenyl, they can be connected to form a naphthalene ring.

[0039] In some embodiments, the X1-X 12 are all selected from CR0.

[0040] In some embodiments, the X1-X 12 contain at least one N.

[0041] In some embodiments, the anthracene compound has the following structure shown in formula (4):

[0042]

[0043] wherein the connection structure of ring A and L1part is:

[0044]

[0045] wherein * represents the site of fusion with the X-containing 5-membered ring in formula (1);

[0046] a is an integer from 0 to 9; if a≥2, each R0is the same or different, and adjacent R0may be connected to form a fused ring.

[0047] In some embodiments, the anthracene compound has the following structure shown in formula (6):

[0048] In some embodiments, the anthracene compound has the following structure shown in formula (6):

[0049] wherein c is an integer from 0 to 3; if c is 2 or 3, each R2is the same or different;

[0050] said ring A is selected from one of the following structures of formula (A-1) to (A-8):

[0051]

[0052] wherein * indicates the site of fusion to the 5-membered ring containing X in formula (1);

[0053] a is an integer from 0 to 10; if a is 2 or greater, each R0is the same or different, and adjacent R0s can be connected to form a fused ring. In some embodiments, said ring A is selected from one of the following structures of formula (A-9) to (A-16):

[0054]

[0055]

[0056] a is an integer from 0 to 6; if a is 2 or greater, each R0is the same or different, and adjacent R0s can be connected to form a fused ring.

[0057] In some embodiments, said anthracene compound has the following structure:

[0058]

[0059] wherein * indicates the site of fusion to the 5-membered ring containing X in formula (1).

[0060] In some embodiments, said R0is independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C30 alkenyl, C2-C30 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C30 alkoxy, C6-C30 aryloxy, C3-C30 alkylsilyl, C6-C30 arylsilyl, C1-C30 alkylboron, C6-C30 arylboron, C6-C30 arylphosphine, or C6-C30 arylamine; and adjacent R0s can be connected to form a fused ring.

[0061] In some embodiments, each R0is independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40alkyl, C1-C40heteroalkyl, C2-C10alkenyl, C2-C10alkynyl, C3-C40cycloalkyl, C3-C40heterocycloalkyl, C6-C60aryl, or C3-C60heteroaryl; and adjacent R0may be joined to form a fused ring.

[0062] In some embodiments, each R0is independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40alkyl, C1-C40heteroalkyl, C2-C10alkenyl, C2-C10alkynyl, C3-C40cycloalkyl, C3-C40heterocycloalkyl, C6-C60aryl, or C3-C60heteroaryl; and adjacent R0may be joined to form a fused ring.

[0063] In some embodiments, each R0, R1, R2is independently selected from hydrogen, deuterium, halogen, cyano, C1-C40alkyl, C1-C40heteroalkyl, C3-C40cycloalkyl, C3-C40heterocycloalkyl, C6-C60aryl, or C3-C60heteroaryl; and adjacent R0may be joined to form a fused ring.

[0064] In some embodiments, each R0, R1, R2is independently selected from hydrogen, deuterium, halogen, cyano, C1-C30alkyl, C1-C30heteroalkyl, C3-C30cycloalkyl, C3-C30heterocycloalkyl, C6-C30aryl, or C3-C30heteroaryl; and adjacent R0may be joined to form a fused ring.

[0065] In some embodiments, each R0, R1, R2is independently selected from hydrogen, deuterium, halogen, cyano, C1-C20alkyl, C1-C20heteroalkyl, C3-C20cycloalkyl, C3-C20heterocycloalkyl, C6-C20aryl, or C3-C20heteroaryl.

[0066] In some embodiments, each R0, R1, R2is independently selected from hydrogen, deuterium, halogen, cyano, C1-C12alkyl, C1-C12heteroalkyl, C3-C18cycloalkyl, C3-C18heterocycloalkyl, C6-C12aryl, or C3-C12heteroaryl.

[0067] In some embodiments, each of R0, R1, R2is independently selected from hydrogen, deuterium, halogen, cyano, C1-C10alkyl, C1-C10heteroalkyl, C3-C10cycloalkyl, C3-C10heterocycloalkyl, C6-C12aryl, or C3-C12heteroaryl.

[0068] In some embodiments, each of L1and L2is independently selected from a single bond, substituted or unsubstituted C6-C30arylene, or substituted or unsubstituted C3-C30heteroarylene.

[0069] In some embodiments, each of L1and L2is independently selected from a single bond, substituted or unsubstituted C6-C24arylene, or substituted or unsubstituted C3-C20heteroarylene.

[0070] In some embodiments, each of L1and L2is independently selected from a single bond, substituted or unsubstituted C6-C20arylene, or substituted or unsubstituted C3-C20heteroarylene.

[0071] In some embodiments, each of L1and L2is independently selected from a single bond, substituted or unsubstituted C6-C14arylene, or substituted or unsubstituted C3-C12heteroarylene.

[0072] In some embodiments, each of L1, L2, Ar, the substitution is independently at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6alkyl, C3-C16cycloalkyl, C1-C6alkyl substituted amine, C1-C6hydrocarbyl substituted or unsubstituted C6-C18aryl, or C1-C6hydrocarbyl substituted or unsubstituted C3-C18heteroaryl, wherein the number of substitutions is from mono-substitution to the maximum number of substitutions. As an example, wherein the C3-C16cycloalkyl, specifically can be C3-C12cycloalkyl or C3-C10cycloalkyl.

[0073] In some embodiments, each of L1, L2, Ar, the substitution is independently at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6alkyl, C3-C16cycloalkyl, C1-C6alkyl substituted amine, C1-C6hydrocarbyl substituted or unsubstituted C6-C12aryl, or C1-C6hydrocarbyl substituted or unsubstituted C3-C12heteroaryl, wherein the number of substitutions is from mono-substitution to the maximum number of substitutions.

[0074] In some embodiments, each of the L1, L2, Ar is independently substituted with at least one of deuterium, halogen, cyano, isocyano, C1-C6alkyl, C3-C16cycloalkyl, C1-C6alkyl-substituted or unsubstituted C6-C12aryl, or C1-C6alkyl-substituted or unsubstituted C3-C12heteroaryl, wherein the number of substitutions ranges from monosubstitution up to the maximum number of substitutions.

[0075] In some embodiments, the Ar is selected from substituted or unsubstituted C6-C30aryl or substituted or unsubstituted C2-C30heteroaryl.

[0076] In some embodiments, the Ar is selected from substituted or unsubstituted C6-C25aryl or substituted or unsubstituted C3-C25heteroaryl.

[0077] In some embodiments, the Ar is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted unsubstituted benzoxazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzotriazolyl, substituted or unsubstituted benzophenanthryl, substituted or unsubstituted benzocyclohexyl, substituted or unsubstituted phenoxazinyl, oxaspirofluorenyl, or substituted or unsubstituted benzocarbazolyl, or a combination of at least two of the above; the substitution is with at least one of deuterium, halogen, cyano, isocyano, C1-C6alkyl, or C3-C16cycloalkyl, wherein the number of substitutions ranges from monosubstitution up to the maximum number of substitutions. The "combination of at least two of the above" means that at least two groups as defined above are combined to form Ar, for example, phenyl and naphthyl are combined to form Ar, it should be understood that the combination of groups is subject to the carbon number range of Ar as defined above.

[0078] In some embodiments, the anthracene compound satisfies at least one of the following conditions:

[0079] (1) the X1-X 12 are each selected from CR0, R0is independently selected from hydrogen or deuterium;

[0080] (2) the X is selected from O;

[0081] (3) the R1is independently selected from hydrogen, deuterium, or substituted or unsubstituted phenyl;

[0082] (4) The R2 is independently selected from hydrogen or deuterium;

[0083] (5) The L1 and L2 are independently selected from single bonds, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted phenanthrene, substituted or unsubstituted anthracene, divalent groups of dibenzofuran or dibenzothiophene;

[0084] (6) The Ar is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthrayl, dibenzofuranyl, and dibenzothiophenyl;

[0085] The substitutions are independently either deuterium or fluorine, and the number of substitutions ranges from monosubstituted to a maximum number of substitutions.

[0086] In some embodiments, the compound is one of the following structural formulas, or a structure in which hydrogen is partially or completely replaced by deuterium or fluorine:

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106] wherein subscript "D" followed by a number represents the number of deuterium substitutions, for example, D26 means that there are 26 deuterium atoms in the structural formula.

[0107] The second aspect embodiment of the present application provides an organic electroluminescent device comprising the anthracene compound described above.

[0108] In some embodiments, the organic electroluminescent device comprises an anode and a cathode, and a light-emitting layer is arranged between the anode and the cathode, and the light-emitting layer comprises the anthracene compound described above. The anthracene compound can be used alone or after being doped to prepare the light-emitting layer.

[0109] In some embodiments, the light-emitting layer comprises a dopant material and a host material, and the host material comprises at least one anthracene compound described above. The mass fraction of the host material in the light-emitting layer can be 90%-99%, or 95%-99%; the mass fraction of the dopant material can be 1%-10%, or 1%-5%.

[0110] In some embodiments, the light-emitting layer is a blue light-emitting layer, and the dopant material is a blue light-emitting material.

[0111] The third aspect embodiment of the present application provides the use of the anthracene compound described above in the field of semiconductors.

[0112] In some embodiments, the anthracene compound described above is used to prepare a semiconductor device.

[0113] In some embodiments, the semiconductor device comprises an optoelectronic device, such as a lamp, a display (including a vehicle display, a computer display, or a television display, wherein the display type can be an AMOLED display), or a sensor, etc.

[0114] Compared with the prior art, the present application has the following advantages:

[0115] The anthracene compound can be used to prepare a host material for an OLED light-emitting device, which can reduce the driving voltage of the device, improve the light-emitting efficiency, and prolong the service life. At the same time, the compound has high optical and electrical stability, and has the potential to be applied in the AMOLED industry.

[0116] Definitions

[0117] Unless otherwise specified, all symbols (e.g., the group symbol Ar, etc.) in the general formulae and sub-formulae related to the present application have the same interpretation range in all embodiments of the present application. The definition range of different symbols can be freely combined, and these combinations fall within the scope of the present application.

[0118] The term "halogen" means one or more of fluorine, chlorine, bromine, or iodine, typically including fluorine, chlorine, or bromine.

[0119] The term "alkyl" means a straight chain or branched saturated hydrocarbon group, and "cycloalkyl" means a non-aromatic carbon-based ring consisting of at least 3 carbon atoms, which can include monocyclic, polycyclic, and spiro-alkane structures.

[0120] The term "heteroalkyl" means that at least one carbon atom in the alkyl group defined above is replaced with a non-carbon atom, except for the case where the carbon atom at the bonding site is replaced with a non-carbon atom (e.g., alkoxy, alkylsilyl). "Heterocycloalkyl" means a group formed by replacing at least one carbon atom in a cycloalkyl group with a non-carbon atom. The non-carbon atom can be selected from at least one of O, S, N, Se, Si, or Ge.

[0121] The term "aryl" means an aromatic hydrocarbon group derived by removing a hydrogen atom from an aromatic ring compound, which can be a monocyclic aryl group or a polycyclic aryl group. At least one ring in the polycyclic aryl group is an aromatic ring system. The multiple rings in the polycyclic aryl group can be connected to each other via a single bond or can be fused to each other. As specific examples of aryl groups, for example, phenyl, naphthyl, anthryl, phenanthryl, tetracenyl, pyrenyl,

[0122] The term "heteroaryl" means a monovalent group of a heterocyclic aromatic system in which at least one carbon atom is replaced with a non-carbon atom on the basis of an aryl group, the non-carbon atom can be selected from O, S, N, Se, Si, or Ge, but does not include the case where the aryl group is connected to the non-carbon atom as the bonding site (e.g., aryloxy, arylsilyl, arylamine). As specific examples of heteroaryl groups, for example, pyrrolyl, pyrazinyl, pyridyl, pyrimidinyl, triazinyl, indolyl, isoindolyl, imidazolyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, azadibenzofuranyl, azadibenzothiophenyl, diazadibenzofuranyl, diazadibenzothiophenyl, quinolyl, isoquinolyl, quinoxalyl, carbazolyl, phenanthridyl, acridyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, oxazolinyl, oxadiazolyl, furazanyl, thiophenyl, benzothiophenyl, dihydroacridyl, azacarbazolyl, diazacarbazolyl, quinazolinyl.

[0123] ​The term "arylene" and "heteroarylene" respectively corresponds to a divalent group of the same structure as aryl and heteroaryl.

[0124] The term "hydrocarbyl" refers to a group consisting of only carbon and hydrogen atoms, including saturated hydrocarbyl groups (e.g., alkyl, cycloalkyl), unsaturated non-aromatic hydrocarbyl groups (e.g., alkenyl, alkynyl), and aromatic hydrocarbyl groups (e.g., phenyl).

[0125] In the term "alkylsilyl" or "arylsilyl", the number of alkyl or aryl groups can be 1 to 3. "Alkylboronyl" includes monoalkylboronyl and dialkylboronyl, "arylboryl" includes monoarylboryl and diarylboryl, and "arylphosphino" includes monoarylphosphino and diarylphosphino. In alkylsilyl, arylsilyl, alkylboronyl, arylboronyl, and arylphosphino, the defined number of carbons refers to the total number of carbons of the corresponding group.

[0126] The term "adjacent" refers to two groups or atoms being directly bonded, or two groups or atoms being directly adjacent substituents of each other (i.e., two substitution sites are directly connected, not indirectly connected through other atoms or groups).

[0127] In the expression "substituted or unsubstituted X group of carbon number a-b", "carbon number a-b" refers to the number of carbons in the case where X group is unsubstituted, excluding the number of carbons of substituents when X group is substituted.

[0128] "Substituted" in "substituted or unsubstituted" means that one or more hydrogen atoms are replaced with other atoms or functional groups (i.e., substituents), and unless otherwise limited by definition, also includes that one or more hydrogen atoms are replaced with a group formed by linking two or more of the above substituents.

[0129] The following examples are merely for the purpose of facilitating the understanding of the technical invention, and should not be regarded as specific limitations of the present invention.

[0130] The raw materials and solvents involved in the synthesis of the compounds in the present application are purchased from suppliers well known to those skilled in the art, such as Alfa, Acros, etc.

[0131] Synthesis of compounds 1 to 23

[0132] The structures of compounds 1 to 23 are as follows:

[0133]

[0134] The specific synthesis method of compound 12 is as follows:

[0135]

[0136] Synthesis of compound A-3

[0137] A-1 (20.00 g, 81.15 mmol), A-2 (19.08 g, 81.15 mmol), tetrakis(triphenylphosphine)palladium (1.88 g, 1.62 mmol), potassium carbonate (22.43 g, 162.3 mmol), tetrahydrofuran (400 ml), deionized water (125 ml) were added to a 1000 ml three-necked round bottom flask, and the system was replaced with nitrogen three times under vacuum. Then the system was heated to 70°C for 4 hours, and the reaction was monitored by TLC (ethyl acetate: n-hexane = 1:10 as developing agent) until the starting material A-1 was consumed.

[0138] The temperature was lowered to 60°C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (600 ml) was added, and the mixture was washed with deionized water three times (300 ml x 3). After the mixture was separated, the silica gel was mixed and dried, and column chromatography was performed using silica gel (200-300 mesh silica gel, ethyl acetate:n-hexane = 1:15 as eluent). After elution, the mixture was concentrated under reduced pressure at 70°C for 2 hours to obtain white solid A-3 (20.96 g, purity: 99.52%, yield: 72.4%).

[0139] Synthesis of compound A-5

[0140] A-3 (19.00 g, 53.45 mmol), A-4 (21.9 g, 63.9 mmol), tetrahydrofuran (280 ml) were added to a 1000 ml three-necked round bottom flask, and the system was replaced with nitrogen three times under vacuum. Then the system was cooled to 5°C, and sodium methoxide (5.75 g, 106.50 mmol) was added at once. The reaction was maintained at 5°C for 1 hour, and the reaction was monitored by TLC (ethyl acetate:n-hexane = 1:10 as developing agent) until the starting material A-3 was consumed. Deionized water (500 ml) was added, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (750 ml) was added to extract the mixture, and the mixture was separated. The mixture was concentrated under reduced pressure at 70°C for 1 hour to obtain white solid A-5 (19.1 g, yield: 93.6%). The mass of the resulting compound was 385.86 (M+H). The compound was used directly in the next reaction without purification.

[0141] Synthesis of compound A-6

[0142] A-5 (18.5 g, 48.07 mmol), toluene (200 ml) were charged into a 500 ml three-necked round-bottom flask, and the system was replaced with nitrogen three times under vacuum, then the system was cooled to 5°C, and methylsulfonic acid (9.24 g, 96.14 mmol) was slowly added dropwise over 3 minutes, and the reaction was maintained at 5°C for 1 hour. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:15 as a developing agent), and the starting material A-5 was consumed. Methanol (220 ml) was added thereto, and a large amount of white solid was precipitated. The solid was crystallized once using toluene (230 ml) and methanol (200 ml), and filtered under suction, and the filter cake was dried at 80°C under vacuum for 1 hour to obtain white solid A-6 (11.65 g, purity: 99.42%, yield: 68.72%), mass: 353.82 (M+H).

[0143] Synthesis of compound A-8

[0144] A-6 (10.5 g, 29.76 mmol), A-7 (9.07 g, 35.71 mmol), tris(dibenzylideneacetone)dipalladium (1.12 g, 1.23 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropyl biphenyl (1.32 g, 2.46 mmol), potassium acetate (8.42 g, 61.32 mmol), 1,4-dioxane (200 ml) were charged into a 1000 ml three-necked round-bottom flask, and the system was replaced with nitrogen three times under vacuum. Then the system was heated to 100°C for 2 hours, and the reaction was monitored by TLC (ethyl acetate: n-hexane = 1:10 as a developing agent), and the starting material A-6 was consumed. The system was cooled to 60°C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (300 ml) was added, and the mixture was washed with deionized water three times (150 ml x 3). After the mixture was separated, the solid was column-chromatographed using silica gel (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:15 as an eluent). After elution, the product was concentrated under reduced pressure at 70°C for 1 hour to obtain white solid A-8 (11.45 g, purity: 98.6%, yield: 86.55%), mass: 445.21 (M+H).

[0145] Synthesis of compound 12

[0146] A-8 (11.00 g, 24.76 mmol), A-9 (9.29 g, 27.23 mmol), tetrakis(triphenylphosphine)palladium (0.76 g, 0.88 mmol), potassium carbonate (6.13 g, 49.52 mmol), tetrahydrofuran (220 ml), deionized water (60 ml) were charged into a 1000 ml three-necked round bottom flask and purged with vacuum-nitrogen three times. Then the system was heated to 75 °C for 3 hours, the reaction was monitored by TLC (ethyl acetate: n-hexane = 1:10 as developing agent) until the starting material A-8 was consumed. The temperature was decreased to 60 °C and the solvent was removed by concentration under reduced pressure, and the yellow solid was filtered. Xylene (360 ml) was added and the material was dissolved by heating to 120 °C, and then the temperature was decreased to room temperature and filtered once. Column chromatography on silica gel (25 g, 200-300 mesh) was performed, and the filter cake was washed with 150 ml of xylene until no product was left, and the organic phase was combined and concentrated under reduced pressure at 70 °C for 2 hours to obtain a yellow solid. The yellow solid was crystallized twice using xylene and methanol, and dried at 100 °C under vacuum for 8 hours to obtain a yellow solid (compound 12 crude, 11.47 g, purity: 99.94%, yield: 80.07%). The obtained 11.47 g of compound 12 crude was purified by sublimation to obtain sublimed compound 12 (8.53 g, purity: 99.96%, yield: 74.36%), mass: 579.74 (M+H).

[0147] 1H NMR (400 MHz, CDCl3) δ 8.27 (d, J = 8.5 Hz, 1H), 7.95 (d, J = 8.8 Hz, 1H), 7.91 - 7.86 (m, 3H), 7.81 (d, J = 8.4 Hz, 1H), 7.71 - 7.64 (m, 2H), 7.64 - 7.51 (m, 7H), 7.50 - 7.43 (m, 1H), 7.39 (dd, J = 7.8, 1.2 Hz, 1H), 7.33 (tt, J = 7.5, 1.5 Hz, 1H).

[0148] wherein the specific synthesis method of compound 13 is as follows:

[0149]

[0150] Synthesis of compound B-3

[0151] Referring to the synthesis and purification method of compound A-3, only the corresponding starting material was changed to obtain the target compound B-3 (12.46 g, purity: 99.25%, yield: 71.52%) as a white solid, mass: 357.81 (M+H).

[0152] Synthesis of compound B-5

[0153] The compound A-5 was obtained as a white solid by the same method as described in the synthesis and purification of the compound A-5, except that the corresponding starting materials were changed (10.38 g, purity: 99.63%, yield: 75.26%).

[0154] Synthesis of the compound B-6

[0155] The compound B-6 was obtained as a white solid by the same method as described in the synthesis and purification of the compound A-6, except that the corresponding starting materials were changed (9.83 g, purity: 99.54%, yield: 68.44%).

[0156] Synthesis of the compound B-8

[0157] The compound B-8 was obtained as a white solid by the same method as described in the synthesis and purification of the compound 12, except that the corresponding starting materials were changed (8.53 g, purity: 99.93%, yield: 65.68%).

[0158] Synthesis of the compound 13

[0159] The compound B-8 (8.1 g, 14.19 mmol), deuterated benzene-D6 (80 mL), trifluoroacetic acid (1.39 g, 14.19 mmol) were added to a 250 mL single-necked round-bottomed flask, and the system was replaced with vacuum nitrogen three times. Then the system was heated to 50°C and stirred for 24 hours. The system was cooled to room temperature, and heavy water (30 mL) was added dropwise to quench the reaction, and stirred at room temperature for 0.5 hours. Ethyl acetate (150 mL) was added, and deionized water was washed three times (100 mL x 3), and the organic phase was combined and concentrated under reduced pressure at 65°C for 1 hour to obtain a white solid. The silica gel was mixed and dried, and column chromatography was performed (200-300 mesh silica gel, n-hexane = 100% as eluent). After elution, the white solid was obtained by concentrating under reduced pressure at 75°C for 1 hour (compound 13 crude product, 7.52 g, purity: 99.51%, 26 deuterium substitution ratio: 98.57%, yield: 88.73%). The 26 deuterium substitution ratio refers to the proportion of the product in which the number of deuterium substitutions is 26, and the test method is described in Example 1 of Chinese patent CN115266981A. After sublimation purification of the obtained 7.52 g of the compound 13 crude product, the sublimation purified compound 13 was obtained (6.14 g, purity: 99.95%, yield: 81.64%), mass spectrum: 597.85 (M+H)

[0160] The other compounds were prepared according to the method for synthesizing B-8 in compound 13 using B-6 and B-7, except that the raw materials used were different, as shown in Table 1. Among them, the preparation of raw material B-6 can refer to the steps disclosed in the examples of Chinese patents CN117645592A and CN117924225A. For example, the raw material B-6 of compound 3 can refer to the synthesis route of compound CPD94 in Chinese patent CN117645592A, and adopt the synthesis method of CPD94-5. The preparation methods of other compounds are not listed one by one.

[0161] Table 1

[0162]

[0163]

[0164]

[0165] Application example: preparation of an organic electroluminescent device

[0166] As shown in the structure schematic diagram of an organic electroluminescent device, it includes glass substrate 1, anode 2, hole injection layer 3, first hole transport layer 4, second hole transport layer 5, light-emitting layer 6, hole blocking layer 7, electron transport layer 8, electron injection layer 9, cathode 10 arranged in turn. Figure 2 Device preparation method:

[0167] A glass substrate 1 with an ITO transparent electrode (anode 2) on the surface was provided, and the thickness of the anode 2 was 100 nm;

[0168] The glass substrate 1 was ultrasonically cleaned in ethanol for 10 minutes, then dried at 150°C, and then treated with N2 Plasma (plasma) for 30 minutes;

[0169] Compound HATCN was evaporated on the surface of the anode 2 side to form a hole injection layer 3, and the thickness of the hole injection layer 3 was 5 nm;

[0170] Compound HTM1 was evaporated on the surface of the hole injection layer 3 side to form a first hole transport layer 4, and the thickness of the first hole transport layer 4 was 60 nm;

[0171] Compound HTM2 was evaporated on the surface of the first hole transport layer 4 side to form a second hole transport layer 5, and the thickness of the second hole transport layer 5 was 10 nm;

[0172]

[0173] ​A host material and a blue light dopant material are co-evaporated on the surface of the second hole transport layer 5 to form a light emitting layer 6, wherein the weight ratio of the host material to the blue light dopant material is 97:3 (see Table 1 for the type of host material in each example and comparative example), and the thickness of the light emitting layer 6 is 25 nm;

[0174] An HBL material is evaporated on the surface of the light emitting layer to form a hole blocking layer 7, and the thickness of the hole blocking layer 7 is 5 nm;

[0175] An ETL is evaporated on the surface of the hole blocking layer 7 to form an electron transport layer 8, and the thickness of the electron transport layer 8 is 30 nm;

[0176] LiQ is evaporated on the surface of the electron transport layer 8 to form an electron injection layer 9, and the thickness of the electron injection layer 9 is 1 nm;

[0177] Al is evaporated on the surface of the electron injection layer 9 to form a cathode 10, and the thickness of the cathode 10 is 100 nm, thereby obtaining an organic electroluminescent device.

[0178] The structural formulae of HATCN, HTM1, HTM2, the blue light dopant material, the HBL, the ETL, the LiQ, and the comparative compounds 1-6 are as follows:

[0179]

[0180] Evaluation: Device performance test

[0181] A constant current power supply (Keithley 2400) is used to flow a fixed current density through the light emitting element, and a spectroradiometric luminance meter (CS2000) is used to test the light emitting spectrum. At the same time, the IVL (current-voltage-luminance) performance of the device is determined at 10 mA / cm 2 The LT95 device lifetime is tested at 50 mA / cm 2 The results are shown in Table 2, and all data are based on the index value of Comparative Example 1 (set as 100). For example, the driving voltage 96 indicates that the driving voltage is 96% of Comparative Example 1 under the same test conditions.

[0182] Table 2

[0183]

[0184]

[0185] As can be seen from Table 2, the current efficiency is significantly better than that of Comparative Compounds 1-6 when anthracene compounds in the examples of the present application are used as blue light host materials, and some of the compounds show better performance in driving voltage or device lifetime.

[0186] In addition, the anthracene compound has low melting point and high light and electrical stability, can be used as a host material in an OLED light-emitting device, and has potential for application in an AMOLED industry.

Claims

1. An anthracene compound, characterized by, having a structure represented by formula (1): wherein ring A is selected from the following formula (2) or formula (3); Among them, X1-X 12 Each is independently selected as CR0 or N; and X1-X4, X5-X6, X7-X8, X9-X 12 Two adjacent sites are fused with the 5-membered ring containing X in equation (1); R0, R1, R2are each independently selected from hydrogen, deuterium, halogen, cyano, C1-C12alkyl or C3-C18cycloalkyl; b is an integer from 0 to 8; if b≥2, each R1is the same or different; c is an integer from 0 to 4; if c≥2, each R2is the same or different; X is selected from O or S; L1and L2are each independently selected from a single bond, substituted or unsubstituted C6-C60arylene or substituted or unsubstituted C3-C60heteroarylene; Ar is selected from substituted or unsubstituted C6-C36aryl or substituted or unsubstituted C2-C36heteroaryl; each of the L1, L2, Ar is independently substituted with at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6alkyl, C3-C16cycloalkyl, C1-C6alkyl substituted amine, C1-C6hydrocarbyl substituted or unsubstituted C6-C30aryl or C1-C6hydrocarbyl substituted or unsubstituted C3-C30heteroaryl, wherein the number of substitutions is mono-substitution to the maximum number of substitutions; wherein the heteroatoms in the heteroarylene, heteroaryl, heteroalkyl or heterocycloalkyl are independently selected from at least one of O, S, N, Se, Si or Ge.

2. The anthracene compound according to claim 1, characterized by the anthracene compound has a structure represented by formula (4) as follows: wherein the connection structure of ring A and L1moiety is: wherein * represents the site of fusion with the 5-membered ring containing X in formula (1); a is an integer from 0 to 9; if a≥2, each R0is the same or different.

3. The anthracene compound according to claim 1, characterized by the anthracene compound has a structure represented by formula (6) as follows: wherein c is an integer from 0 to 3; if c is 2 or 3, each R2is the same or different; the ring A is selected from one of the following structures represented by formula (A-1) to formula (A-8): wherein * represents the site of fusion with the 5-membered ring containing X in formula (1); a is an integer from 0 to 10; if a≥2, each R0is the same or different.

4. The anthracene compound according to any one of claims 1 to 3, characterized by the ring A is selected from one of the following structures represented by formula (A-9) to formula (A-16): wherein * represents the site of fusion with the 5-membered ring containing X in formula (1); a is an integer from 0 to 6; if a≥2, each R0is the same or different.

5. The anthracene compound according to claim 1, characterized by The X1-X 12 All are selected from CR0; and / or, R0, R1, R2are each independently selected from hydrogen, deuterium, halogen, cyano, C1-C10alkyl or C3-C10cycloalkyl; and / or, L1and L2are each independently selected from a single bond, substituted or unsubstituted C6-C30arylene or substituted or unsubstituted C3-C30heteroarylene; and / or, Ar is selected from substituted or unsubstituted C6-C30aryl or substituted or unsubstituted C2-C30heteroaryl; and / or, in said L1, L2, Ar, said substitution is each independently at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbyl unsubstituted C6-C18 aryl, or C1-C6 hydrocarbyl unsubstituted C3-C18 heteroaryl, wherein the number of substitutions is from monosubstitution to the maximum number of substitutions.

6. The anthracene compound according to claim 5, characterized by said R0, R1, R2 are each independently selected from hydrogen, deuterium, halogen, or cyano; and / or, said L1and L2are each independently selected from a single bond, substituted or unsubstituted C6-C14 arylene, or substituted or unsubstituted C3-C12 heteroarylene; and / or, in said L1, L2, Ar, said substitution is each independently at least one of deuterium, halogen, cyano, isocyano, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 hydrocarbyl unsubstituted C6-C12 aryl, or C1-C6 hydrocarbyl unsubstituted C3-C12 heteroaryl, wherein the number of substitutions is from monosubstitution to the maximum number of substitutions.

7. The anthracene compound according to claim 1, characterized by Ar is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzotriazolyl, substituted or unsubstituted benzophenanthryl, substituted or unsubstituted benzocyclohexyl, substituted or unsubstituted phenoxazinyl, oxaspirofluorenyl, or substituted or unsubstituted benzocarbazolyl, or a combination of at least two of the foregoing; the substitution is by at least one of deuterium, halogen, cyano, isocyano, C1-C6 alkyl, or C3-C16 cycloalkyl, wherein the number of substitutions ranges from mono-substitution to the maximum number of substitutions.

8. The anthracene compound according to claim 1, characterized by said anthracene compound satisfies at least one of the following conditions: (1) said X1-X 12 are each selected from CR0, R0being independently selected from hydrogen or deuterium; (2) said X is selected from O; (3) said R1is independently selected from hydrogen or deuterium; (4) said R2is independently selected from hydrogen or deuterium; (5) said L1and L2are each independently selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted anthrylene, a bivalent radical of dibenzofuran, or a bivalent radical of dibenzothiophene; (6) said Ar is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl, dibenzofuranyl, dibenzothiophenyl; wherein said substitution is each independently substituted with deuterium or fluorine, wherein the number of substitutions is from monosubstitution to the maximum number of substitutions.

9. An anthracene compound, characterized by, said anthracene compound is one of the following structural formulae: wherein the subscript "D" followed by a number indicates the number of deuterium substitutions.

10. An organic electroluminescent device, characterized by said organic electroluminescent device comprises the anthracene compound according to any one of claims 1-9.

11. The organic electroluminescent device according to claim 10, characterized in that said organic electroluminescent device comprises the anthracene compound according to any one of claims 1-9. said organic electroluminescent device comprises the anthracene compound according to any one of claims 1-9.

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