Anthracene compound and organic electroluminescent device

Abstract

The invention discloses an anthracene compound and an organic electroluminescent device. The compound has a structure as shown in a formula (1): # imgabs0 #, a ring A is selected from a formula (2) or a formula (3): # imgabs1 #, and the compound can be used as a blue light host material in an OLED luminescent device, has the advantages of low driving voltage, high luminous efficiency, long device life and the like, and has the potential of being applied to the AMOLED industry.

Description

Technical Field

[0001] The invention belongs to the technical field of organic electroluminescence, and particularly relates to an anthracene compound and an organic electroluminescent device. Background Art

[0002] At present, organic electroluminescent devices (OLEDs), as a new generation of display technology, have received more and more attention in both display and lighting technology, and have a wide range of application prospects. However, compared with market application requirements, OLED devices still need to continue to strengthen and improve in terms of luminous efficiency, driving voltage, service life and other performance.

[0003] Generally speaking, the basic structure of an OLED device is a thin film of organic functional materials with various functions sandwiched between metal electrodes, like a sandwich structure. Driven by electric current, holes and electrons are injected from the positive and negative electrodes respectively. After moving a certain distance, the holes and electrons are recombined in the light-emitting layer and released in the form of light or heat, thereby generating the light emission of the OLED. In phosphorescent OLEDs, the device properties are not only determined by the triplet light emitter used, but also significantly affected by other types of materials (such as host materials). The host material plays a vital role in reducing the device driving voltage, improving the luminous efficiency and extending the service life. However, the host materials disclosed in the prior art still have room for optimization in terms of the above-mentioned performance.

[0004] Therefore, it is necessary to continue to develop new host materials to further improve the performance of organic electroluminescent devices. Summary of the invention

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

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

[0007]

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

[0009]

[0010] Among them, X1-X 12 are independently selected from CR0 or N; and X1-X4, X5-X6, X7-X8, X9-X 12There are two adjacent sites in the formula (1) that are fused to the 5-membered ring containing X;

[0011] R0, R1, and 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 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino or C6-C60 arylamine; and adjacent R0s may be connected to form a 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 each independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group;

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

[0017] In the L1, L2, and Ar, the substitutions are each independently substituted by 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 ranges from a single substitution to a maximum number of substitutions;

[0018] The heteroatoms in the heteroarylene group, heteroaryl group, heteroalkyl group or heterocycloalkyl group are independently selected from at least one of O, S, N, Se, Si or Ge.

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

[0020] The anthracene compound of the present invention can be used as the main material of OLED light-emitting devices, and has the advantages of low driving voltage, high luminous efficiency and long 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 THE DRAWINGS

[0021] Figure 1 The compound 7 of the embodiment of the present invention 1 H NMR spectrum;

[0022] Figure 2 FIG. 1 is a schematic structural diagram of an organic electroluminescent device according to an embodiment of the present invention. DETAILED DESCRIPTION

[0023] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.

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

[0025]

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

[0027]

[0028] Among them, X1-X 12 are independently selected from CR0 or N; and X1-X4, X5-X6, X7-X8, X9-X 12 There are two adjacent sites in the formula (1) that are fused to the 5-membered ring containing X;

[0029] R0, R1, and 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 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino or C6-C60 arylamine; and adjacent R0s may be connected to form a 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 each independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group;

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

[0035] In the L1, L2, and Ar, the substitutions are each independently substituted by 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 ranges from a single substitution to a maximum number of substitutions;

[0036] The heteroatoms in the heteroarylene group, heteroaryl group, heteroalkyl group or heterocycloalkyl group are independently selected from at least one of O, S, N, Se, Si or Ge.

[0037] It can be understood that in formula (1), L1 can be connected to ring A or ring E.

[0038] "Adjacent R0" refers to R0 located on adjacent carbon atoms. It can be further understood that "adjacent R0 can be connected to form a ring" means that R0 located on adjacent carbon atoms can be connected to form a ring. For example, when two adjacent R0 are both phenyl groups, they can be connected to form a naphthalene ring.

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

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

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

[0042]

[0043] Among them, the connection structure of ring A and L1 part is:

[0044]

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

[0046] a is an integer of 0-9; if a≥2, each R0 is the same or different, and adjacent R0 can be connected to form a ring.

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

[0048]

[0049] Wherein, c is an integer from 0 to 3; if c is 2 or 3, each R2 is the same or different;

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

[0051]

[0052] Wherein, * represents the site of fusion with the 5-membered ring containing X in formula (1);

[0053] a is an integer of 0-10; if a≥2, each R0 is the same or different, and adjacent R0 can be connected to form a ring. In some embodiments, the ring A is selected from one of the structures shown in the following formula (A-9) to formula (A-16):

[0054]

[0055]

[0056] a is an integer of 0-6; if a≥2, each R0 is the same or different, and adjacent R0 can be connected to form a ring.

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

[0058]

[0059] Here, * represents the site of fusion with the 5-membered ring containing X in formula (1).

[0060] In some embodiments, the R0 is 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 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphino or C6-C30 arylamine; and adjacent R0 may be connected to form a ring.

[0061] In some embodiments, the R0 is independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C20 alkoxy, C6-C20 aryloxy, C3-C20 alkylsilyl, C6-C20 arylsilyl, C1-C20 alkylboryl, C6-C20 arylboryl, C6-C20 arylphosphino or C6-C20 arylamine; and adjacent R0 may be connected to form a ring.

[0062] In some embodiments, the R0 is independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl or C3-C60 heteroaryl; and adjacent R0 may be connected to form a ring.

[0063] In some embodiments, R0, R1, and R2 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C40 alkyl, C1-C40 heteroalkyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, or C3-C60 heteroaryl; and adjacent R0s may be connected to form a ring.

[0064] In some embodiments, R0, R1, and R2 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C30 alkyl, C1-C30 heteroalkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C30 aryl, or C3-C30 heteroaryl; and adjacent R0s may be connected to form a ring.

[0065] In some embodiments, R0, R1, and R2 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C20 alkyl, C1-C20 heteroalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, or C3-C20 heteroaryl.

[0066] In some embodiments, R0, R1, and R2 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C12 alkyl, C1-C12 heteroalkyl, C3-C18 cycloalkyl, C3-C18 heterocycloalkyl, C6-C12 aryl, or C3-C12 heteroaryl.

[0067] In some embodiments, R0, R1, and R2 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C10 alkyl, C1-C10 heteroalkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C12 aryl, or C3-C12 heteroaryl.

[0068] In some embodiments, L1 and L2 are each independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group.

[0069] In some embodiments, L1 and L2 are independently selected from a single bond, a substituted or unsubstituted C6-C24 arylene group, or a substituted or unsubstituted C3-C20 heteroarylene group.

[0070] In some embodiments, L1 and L2 are each independently selected from a single bond, a substituted or unsubstituted C6-C20 arylene group, or a substituted or unsubstituted C3-C20 heteroarylene group.

[0071] In some embodiments, L1 and L2 are independently selected from a single bond, a substituted or unsubstituted C6-C14 arylene group, or a substituted or unsubstituted C3-C12 heteroarylene group.

[0072] In some embodiments, in L1, L2, Ar, the substitutions are each independently substituted by 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-C18 aryl or C1-C6 hydrocarbon substituted or unsubstituted C3-C18 heteroaryl, wherein the number of substitutions is from a single substitution to the maximum number of substitutions. As an example, C3-C16 cycloalkyl may specifically be C3-C12 cycloalkyl or C3-C10 cycloalkyl.

[0073] In some embodiments, in L1, L2, and Ar, the substitutions are each independently substituted by 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-C12 aryl, or C1-C6 hydrocarbon substituted or unsubstituted C3-C12 heteroaryl, wherein the number of substitutions ranges from a single substitution to a maximum number of substitutions.

[0074] In some embodiments, in L1, L2, and Ar, the substitutions are each independently substituted by at least one of deuterium, halogen, cyano, isocyano, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 hydrocarbon substituted or unsubstituted C6-C12 aryl, or C1-C6 hydrocarbon substituted or unsubstituted C3-C12 heteroaryl, wherein the number of substitutions ranges from a single substitution to a maximum number of substitutions.

[0075] In some embodiments, the Ar is selected from a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C2-C30 heteroaryl group.

[0076] In some embodiments, the Ar is selected from a substituted or unsubstituted C6-C25 aryl group or a substituted or unsubstituted C3-C25 heteroaryl group.

[0077] In some embodiments, 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 phenanthrenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted The invention relates to a substituted or unsubstituted carbazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidyl, a substituted or unsubstituted fluoranthene, a substituted or unsubstituted benzoxazolyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted benzotriazolyl, a substituted or unsubstituted triphenylene radical, a substituted or unsubstituted benzocyclohexyl, a substituted or unsubstituted phenanthroxazolyl, an oxaspirofluorene radical or a substituted or unsubstituted benzocarbazolyl, or a combination of at least two of the above; the substitution is substituted by at least one of deuterium, halogen, cyano, isocyano, C1-C6 alkyl or C3-C16 cycloalkyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions. "A combination of at least two of the above" refers to at least two groups as defined above combined to form Ar, for example, a phenyl group and a naphthyl group are combined to form Ar. It should be understood that the combination of the groups is based on the premise of satisfying the carbon number range of Ar defined above.

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

[0079] (1) X1-X 12 are all selected from CR0, R0 is independently selected from hydrogen or deuterium;

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

[0081] (3) R1 is independently selected from hydrogen, deuterium or substituted or unsubstituted phenyl;

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

[0083] (5) L1 and L2 are independently selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted phenanthrylene, a substituted or unsubstituted anthraceneene, a divalent group of dibenzofuran or a divalent group of dibenzothiophene;

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

[0085] Wherein, the substitutions are independently substituted by deuterium or fluorine, wherein the number of substitutions is from a single substitution 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] The subscript "D" followed by a number indicates the number of deuterium substitutions, for example, D26 indicates that the structural formula contains 26 deuterium atoms.

[0107] A second aspect of the present invention 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, a light-emitting layer is disposed 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 includes a dopant material and a host material, and the host material includes at least one of the above anthracene compounds. The mass proportion of the host material in the light-emitting layer can be 90%-99%, or 95%-99%; the mass proportion 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 doping material is a blue light-emitting material.

[0111] A third aspect of the present invention provides an application of the anthracene compounds in the semiconductor field.

[0112] In some embodiments, the anthracene compounds are used to prepare semiconductor devices.

[0113] In some embodiments, the semiconductor device includes an optoelectronic device, such as a lamp, a display (including a car display, a computer display, or a television display, where the display type may be an AMOLED display), or a sensor.

[0114] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0115] The anthracene compound can be used to prepare the main material of OLED light-emitting devices, which can reduce the driving voltage of the device, improve the luminous efficiency, and extend the service life. At the same time, the compound has high optical and electrical stability and may be applied to the AMOLED industry.

[0116] definition

[0117] Unless otherwise specified, the symbols (such as group code Ar, etc.) in all general formulas and their subordinate general formulas involved in the present invention have the same interpretation scope in all embodiments of the present invention. The definition scopes of different symbols can be freely combined, and these combinations all fall within the protection scope of the present invention.

[0118] The term "halogen" refers to one or more of fluorine, chlorine, bromine or iodine, and typically includes fluorine, chlorine or bromine.

[0119] The term "alkyl" refers to a straight or branched saturated hydrocarbon group, and "cycloalkyl" refers to a non-aromatic carbon-based ring consisting of at least 3 carbon atoms, which may include monocyclic, polycyclic and spirane structures.

[0120] The term "heteroalkyl" refers to an alkyl group defined above in which at least one carbon atom is replaced by a non-carbon atom, but does not include a case where a carbon atom as a connection site is replaced by a non-carbon atom (e.g., alkoxy, alkylsilyl). "Heterocycloalkyl" refers to a group formed on the basis of a cycloalkyl group in which at least one carbon atom is replaced by a non-carbon atom. The non-carbon atom may be selected from at least one of O, S, N, Se, Si or Ge.

[0121] The term "aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom, and may be a monocyclic aryl group or a polycyclic aryl group. In a polycyclic aryl group, at least one ring is an aromatic ring system. In a polycyclic aryl group, multiple rings may be connected to each other via a single bond or may be fused to each other. Specific examples of aryl groups include phenyl, naphthyl, anthracenyl, phenanthrenyl, tetraphenylene, pyrenyl, phenyl, benzo[c]phenanthryl, benzo[g]chrysene, fluorenyl, benzofluorenyl, dibenzofluorenyl, biphenyl, terphenyl, quaterphenyl, fluoranthenyl.

[0122] The term "heteroaryl" refers to a monovalent group in which at least one carbon atom based on an aromatic group is replaced by a non-carbon atom, wherein the non-carbon atom can be selected from a heterocyclic aromatic system of O, S, N, Se, Si or Ge, but does not include the case where the aromatic group uses a non-carbon atom as a connection site (for example, an aryloxy group, an arylsilyl group, an arylamine group). Specific examples of the heteroaryl group include pyrrolyl, pyrazinyl, pyridyl, pyrimidinyl, triazine, indolyl, isoindolyl, imidazolyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, azadibenzofuranyl, azadibenzothiophenyl, diazadibenzofuranyl, diazadibenzothiophenyl, quinolyl, isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, oxazolinyl, oxadiazolyl, furazanyl, thienyl, benzothiophenyl, dihydroacridinyl, azacarbazolyl, diazacarbazolyl, and quinazolinyl.

[0123] The terms "arylene" and "heteroarylene" correspond to divalent groups having the same structures as aryl and heteroaryl, respectively.

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

[0125] In the term "alkylsilyl" or "arylsilyl", the number of alkyl or aryl groups may be 1 to 3. "Alkylboryl" includes monoalkylboryl and dialkylboryl, "arylboryl" includes monoarylboryl and diarylboryl, and "arylphosphino" includes monoarylphosphino and diarylphosphino. In the alkylsilyl, arylsilyl, alkylboryl, arylboryl and arylphosphino, the carbon number defined refers to the total carbon number of the corresponding group.

[0126] The term "adjacent" refers to two groups or atoms that are directly bonded to each other, or two groups or atoms that are directly adjacent substituents to each other (ie, the two substituents are directly connected, rather than indirectly connected through other atoms or groups).

[0127] The "carbon number ab" in the expression "a substituted or unsubstituted X group having ab carbon numbers" means the carbon number when the X group is unsubstituted, and does not include the carbon number of a substituent when the X group is substituted.

[0128] The "substituted" in "substituted or unsubstituted" means that one or more hydrogen atoms are replaced by other atoms or functional groups (i.e., substituents), and unless otherwise limited by the definition, it also includes one or more hydrogen atoms being replaced by a group formed by connecting two or more of the above-mentioned substituents to form a group.

[0129] 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.

[0130] 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.

[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), and deionized water (125 ml) were added to a 1000 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. 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 the developing solvent) until the raw material A-1 was consumed.

[0138] The temperature was lowered to 60°C, the solvent was removed by vacuum concentration, ethyl acetate (600 ml) was added, and the mixture was washed three times with deionized water (300 ml × 3). After separation, the sample was mixed with silica gel and dry loaded onto a column, and purified by silica gel column chromatography (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 a white solid A-3 (20.96 g, purity: 99.52%, yield: 72.4%), mass spectrum: 357.81 (M+H).

[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 vacuum nitrogen was replaced three times. Then the system was cooled to 5 ° C, sodium methoxide (5.75 g, 106.50 mmol) was added at once, and the reaction was maintained at 5 ° C for 1 hour. TLC (ethyl acetate: n-hexane = 1:10 as the developing solvent) monitored the reaction until the raw material A-3 was consumed. Deionized water (500 ml) was added thereto, the solvent was removed by vacuum concentration, and ethyl acetate (750 ml) was added for extraction. After separation, the mixture was concentrated under reduced pressure at 70 ° C for 1 hour to obtain a white solid A-5 (19.1 g, yield: 93.6%), mass spectrum: 385.86 (M+H). The obtained compound did not need to be purified and was directly used in the next step.

[0141] Synthesis of Compound A-6

[0142] A-5 (18.5 g, 48.07 mmol) and toluene (200 ml) were added to a 500 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then the system was cooled to 5°C, and methanesulfonic acid (9.24 g, 96.14 mmol) was slowly added dropwise. The addition was completed in 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 the developing solvent) until the raw material A-5 was consumed. Methanol (220 ml) was added thereto to precipitate a large amount of white solid, which was crystallized once with toluene (230 ml) and methanol (200 ml), filtered, and the filter cake was vacuum dried at 80°C for 1 hour to obtain a white solid A-6 (11.65 g, purity: 99.42%, yield: 68.72%), mass spectrum: 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-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (1.32 g, 2.46 mmol), potassium acetate (8.42 g, 61.32 mmol), 1,4-dioxane (200 ml) were added to a 1000 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. 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 the developing solvent) until the raw material A-6 was consumed. The temperature was lowered to 60°C, the solvent was removed by concentrating under reduced pressure, ethyl acetate (300 ml) was added, and the mixture was washed three times with deionized water (150 ml × 3). After separation, the sample was mixed with silica gel and dry-loaded onto a column, and purified by silica gel column chromatography (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 1 hour to obtain a white solid A-8 (11.45 g, purity: 98.6%, yield: 86.55%), mass spectrum: 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), and deionized water (60 ml) were added to a 1000 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then the system was heated to 75 ° C for 3 hours, and the reaction was monitored by TLC (ethyl acetate: n-hexane = 1:10 as the developing solvent) until the raw material A-8 was consumed. Cool to 60 ° C, concentrate under reduced pressure to remove the solvent, and filter to obtain a yellow solid. Add xylene (360 ml), heat to 120 ° C to dissolve the material, cool to room temperature and filter once. Column chromatography silica gel (25 g, 200-300 mesh), the filter cake was rinsed with 150 ml toluene until no product remained, and the organic phase was combined and concentrated at 70°C under reduced pressure for 2 hours to obtain a yellow solid. It was crystallized twice with xylene and methanol, and vacuum dried at 100°C for 8 hours to obtain a yellow solid (crude compound 12, 11.47 g, purity: 99.94%, yield: 80.07%). The obtained 11.47 g crude compound 12 was purified by sublimation to obtain sublimation purified compound 12 (8.53 g, purity: 99.96%, yield: 74.36%), mass spectrum: 579.74 (M+H).

[0147] 1H NMR (400MHz, CDCl3) δ8.27(d,J=8.5Hz,1H),7.95(d,J=8.8Hz,1H),7.91–7.86(m,3H),7.81(d,J=8.4Hz,1H),7. 71–7.64(m,2H),7.64–7.51(m,7H),7.50–7.43(m,1H),7.39(dd,J=7.8,1.2Hz,1H),7.33(tt,J=7.5,1.5Hz,1H).

[0148] 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, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound B-3 (12.46 g, purity: 99.25%, yield: 71.52%), mass spectrum: 357.81 (M+H).

[0152] Synthesis of compound B-5

[0153] Referring to the synthesis and purification method of compound A-5, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound B-5 (10.38 g, purity: 99.63%, yield: 75.26%), mass spectrum: 385.86 (M+H).

[0154] Synthesis of compound B-6

[0155] Referring to the synthesis and purification method of compound A-6, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound B-6 (9.83 g, purity: 99.54%, yield: 68.44%), mass spectrum: 353.82 (M+H).

[0156] Synthesis of compound B-8

[0157] Referring to the synthesis and purification method of compound 12, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound B-8 (8.53 g, purity: 99.93%, yield: 65.68%), mass spectrum: 571.69 (M+H).

[0158] Synthesis of compound 13

[0159] 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-mouth round-bottom flask, and the vacuum nitrogen was replaced 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 to quench the reaction, and stirred at room temperature for 0.5 hours. Ethyl acetate (150 ml) was added, and the mixture was washed three times with deionized water (100 ml × 3). After the organic phases were combined, they were concentrated under reduced pressure at 65 ° C for 1 hour to obtain a white solid. The silica gel was mixed with the sample and dry-coated, and purified by silica gel column chromatography (200-300 mesh silica gel, n-hexane = 100% as eluent). After elution, the mixture was concentrated under reduced pressure at 75°C for 1 hour to obtain a white solid (crude compound 13, 7.52 g, purity: 99.51%, 26 deuterated percentage: 98.57%, yield: 88.73%. The 26 deuterated percentage refers to the proportion of products with a deuterium substitution number of 26, and the test method refers to Example 1 in Chinese patent CN115266981A). The obtained 7.52 g crude compound 13 was purified by sublimation to obtain sublimation-purified compound 13 (6.14 g, purity: 99.95%, yield: 81.64%), mass spectrum: 597.85 (M+H)

[0160] The preparation of other compounds refers to the method of synthesizing B-8 using B-6 and B-7 in compound 13, except that the raw materials used are different, as shown in Table 1. Among them, the preparation of raw material B-6 can refer to the steps disclosed in the embodiments of Chinese patents CN117645592A and CN117924225A. For example, the raw material B-6 of compound 3 can refer to the synthetic route of compound CPD94 in Chinese patent CN117645592A, and adopt the synthetic 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: Fabrication of organic electroluminescent devices

[0166] like Figure 2 As shown, it is a schematic diagram of the structure of an organic electroluminescent device, including a glass substrate 1, an anode 2, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light-emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10 which are stacked in sequence.

[0167] Device manufacturing method:

[0168] A glass substrate 1 having an ITO transparent electrode (anode 2) on its surface is provided, wherein the thickness of the anode 2 is 100 nm;

[0169] The glass substrate 1 was ultrasonically cleaned in ethanol for 10 minutes, then dried at 150° C., and then treated with N2 plasma for 30 minutes;

[0170] Compound HATCN is evaporated on one surface of the anode 2 to form a hole injection layer 3, and the thickness of the hole injection layer 3 is 5 nm;

[0171] Compound HTM1 is evaporated on one surface of the hole injection layer 3 to form a first hole transport layer 4, and the thickness of the first hole transport layer 4 is 60 nm;

[0172] Compound HTM2 is evaporated on one surface of the first hole transport layer 4 to form a second hole transport layer 5, and the thickness of the second hole transport layer 5 is 10 nm;

[0173] A main material and a blue light doping material are co-evaporated on one side of the second hole transport layer 5 to form a light-emitting layer 6, wherein the weight ratio of the main material to the blue light doping material is 97:3 (the types of main materials of each embodiment and comparative example are shown in Table 1), and the thickness of the light-emitting layer 6 is 25 nm;

[0174] The HBL material is evaporated on the surface of one side 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] ETL is evaporated on one side 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 one side 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 was evaporated on one surface of the electron injection layer 9 to form a cathode 10. The thickness of the cathode 10 was 100 nm, and an organic electroluminescent device was obtained.

[0178] Among them, the structural formulas of HATCN, HTM1, HTM2, blue light doping material, HBL, ETL, LiQ and comparative compounds 1-6 are as follows:

[0179]

[0180] Evaluation: Device performance test

[0181] A constant current power supply (Keithley 2400) was used to flow a fixed current density through the light-emitting element, and the luminescence spectrum was measured using a spectroradiometer (CS2000). 2 The IVL (current-voltage-luminance) performance of the device was measured at 50 mA / cm 2 The life of the LT95 device was tested under the following conditions. 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 of 96 means that under the same test conditions, the driving voltage is 96% of that of Comparative Example 1.

[0182] Table 2

[0183]

[0184]

[0185] It can be seen from Table 2 that the current efficiency of the anthracene compounds in the embodiments of the present invention as the blue light host material is significantly better than that of the comparative compounds 1-6, and some compounds show better performance in terms of driving voltage or device life.

[0186] In addition, the anthracene compound has a low melting point and high optical and electrical stability. It can be used as a main material in OLED light-emitting devices and has the potential to be applied in the AMOLED industry.

Claims

1. An anthracene compound, characterized in that: It has the structure shown in formula (1): Wherein, ring A is selected from the following formula (2) or formula (3); Among them, X1-X 12 are independently selected from CR0 or N; and X1-X4, X5-X6, X7-X8, X9-X 12 There are two adjacent sites in the formula (1) that are fused to the 5-membered ring containing X; R0, R1, and 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 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino or C6-C60 arylamine; and adjacent R0s may be connected to form a ring; b is an integer from 0 to 8; if b ≥ 2, each R1 is the same or different; c is an integer from 0 to 4; if c ≥ 2, each R2 is the same or different; X is selected from O or S; L1 and L2 are each independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group; Ar is selected from substituted or unsubstituted C6-C36 aryl or substituted or unsubstituted C2-C36 heteroaryl; In the L1, L2, and Ar, the substitutions are each independently substituted by 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 ranges from a single substitution to a maximum number of substitutions; The heteroatoms in the heteroarylene group, heteroaryl group, heteroalkyl group or heterocycloalkyl group are independently selected from at least one of O, S, N, Se, Si or Ge.

2. The anthracene compound according to claim 1, characterized in that The anthracene compound has a structure as shown in the following formula (4): Among them, the connection structure of ring A and L1 part is: Wherein, * represents the site of fusion with the 5-membered ring containing X in formula (1); a is an integer of 0-9; if a≥2, each R0 is the same or different, and adjacent R0 can be connected to form a ring.

3. The anthracene compound according to claim 1, characterized in that The anthracene compound has a structure as shown in the following formula (6): Wherein, c is an integer from 0 to 3; if c is 2 or 3, each R2 is the same or different; The ring A is selected from one of the structures represented by the following 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 of 0-10; if a≥2, each R0 is the same or different, and adjacent R0 can be connected to form a ring.

4. The anthracene compound according to any one of claims 1 to 3, characterized in that The ring A is selected from one of the structures represented by the following 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 of 0-6; if a≥2, each R0 is the same or different, and adjacent R0 can be connected to form a ring.

5. The anthracene compound according to claim 1, characterized in that The X1-X 12 All selected from CR0; and / or, R0, R1, and R2 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C30 alkyl, C1-C30 heteroalkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C30 aryl, or C3-C30 heteroaryl; and adjacent R0s may be connected to form a ring; and / or, L1 and L2 are independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group; and / or, Ar is selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C2-C30 heteroaryl; And / or, in L1, L2, and Ar, the substitutions are each independently substituted by 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-C18 aryl, or C1-C6 hydrocarbon substituted or unsubstituted C3-C18 heteroaryl, wherein the number of substitutions ranges from a single substitution to a maximum number of substitutions.

6. The anthracene compound according to claim 5, characterized in that Said R0, R1, and R2 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C10 alkyl, C1-C10 heteroalkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C12 aryl or C3-C12 heteroaryl; and / or, L1 and L2 are independently selected from a single bond, a substituted or unsubstituted C6-C14 arylene group or a substituted or unsubstituted C3-C12 heteroarylene group; And / or, in L1, L2, and Ar, the substitutions are each independently substituted by at least one of deuterium, halogen, cyano, isocyano, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 hydrocarbon substituted or unsubstituted C6-C12 aryl, or C1-C6 hydrocarbon substituted or unsubstituted C3-C12 heteroaryl, wherein the number of substitutions ranges from a single substitution to a maximum number of substitutions.

7. The anthracene compound according to claim 1, characterized in that 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 phenanthrenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted The invention relates to a substituted or unsubstituted carbazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidyl, a substituted or unsubstituted fluoranthene, a substituted or unsubstituted benzoxazolyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted benzotriazolyl, a substituted or unsubstituted triphenylene radical, a substituted or unsubstituted benzocyclohexyl, a substituted or unsubstituted phenanthroxazolyl, an oxaspirofluorenyl or a substituted or unsubstituted benzocarbazolyl, or a combination of at least two of the above; the substitution is substitution by at least one of deuterium, halogen, cyano, isocyano, C1-C6 alkyl or C3-C16 cycloalkyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions.

8. The anthracene compound according to claim 1, characterized in that The anthracene compound satisfies at least one of the following conditions: (1) X1-X 12 are all selected from CR0, R0 is independently selected from hydrogen or deuterium; (2) X is selected from O; (3) R1 is independently selected from hydrogen, deuterium or substituted or unsubstituted phenyl; (4) R2 is independently selected from hydrogen or deuterium; (5) L1 and L2 are independently selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted phenanthrylene, a substituted or unsubstituted anthraceneene, a divalent group of dibenzofuran or a divalent group of dibenzothiophene; (6) Ar is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted anthracenyl, dibenzofuranyl, and dibenzothiophenyl; Wherein, the substitutions are independently substituted by deuterium or fluorine, wherein the number of substitutions is from a single substitution to a maximum number of substitutions.

9. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises the anthracene compound according to any one of claims 1 to 8.

10. The organic electroluminescent device according to claim 9, characterized in that: It comprises an anode and a cathode, wherein a light-emitting layer is arranged between the anode and the cathode, and the light-emitting layer comprises the anthracene compound according to any one of claims 1 to 8.

Images