Benzanthracene derivative and application thereof

Abstract

The invention provides a benzanthracene derivative and application thereof. The benzanthracene derivative disclosed by the invention has a structure as shown in a formula I, is used in an organic electroluminescent device, and can remarkably prolong the service life and improve the efficiency of the device as a main body material of a luminescent layer. The invention also provides an organic electroluminescent device and a display or illumination device comprising the benzanthracene derivative.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescence technology, specifically to a benzene anthracene derivative and its application in organic electroluminescent devices. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are current-driven semiconductor light-emitting devices based on organic materials. They generate light by driving the recombination of electrons and holes in the light-emitting layer using voltage. This technology features self-illumination, wide viewing angle, high contrast, and low energy consumption, and has become a core technology for next-generation displays and lighting.

[0003] Blue light source material is a key component of OLEDs, and its performance directly affects luminous efficiency, driving voltage, lifetime, brightness, and chromaticity. Despite significant progress in OLED technology in recent years, the efficiency and stability of blue light source materials remain critical factors limiting its further development. The selection and design of blue light source materials are crucial for improving the overall performance of OLEDs. Existing blue light source materials mainly suffer from low color purity and are not conducive to emitting deep blue light. Furthermore, the luminous efficiency and stability of blue light source materials need further improvement to enhance the display effect and lifespan of the device. Summary of the Invention

[0004] To address one of the aforementioned technical problems in the prior art, this invention provides a benzene-anthracene derivative and its application. The benzene-anthracene derivative exhibits excellent photoelectric properties and, when used in organic electroluminescent devices, enables the devices to have low voltage and higher luminous efficiency and lifetime.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a benzanthracene derivative having a structure as shown in Formula I:

[0007]

[0008] Among them, L 1 L 2 Each is independently selected from any one or a combination of at least two of the single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene;

[0009] Ar 1 Ar 2 Each is independently selected from any one or a combination of at least two of substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C3-C30 heteroaryl groups, and Ar 1 Ar 2At least one of the groups is selected from formula a or formula b:

[0010]

[0011] Among them, X 1 X 2 X 3 Each is independently selected from O, S, or Se;

[0012] Y 1 ~Y 12 Each is independently selected from N, C, or CR. 11 And Y 1 ~Y 12 At least one of them is C and is associated with L. 1 or L 2 connect;

[0013] R 1 ~R 11 Each is independently selected from any one or a combination of at least two of the following: hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl; The R 1 ~R 11 In a ring, any two or more adjacent groups are not connected or are linked by chemical bonds to form a ring;

[0014] L 1 L 2 Ar 1 Ar 2 R 1 ~R 11 The substituents described herein are one or more, and each is independently selected from any one or a combination of at least two of the following: deuterium, halogen, cyano, nitro, hydroxyl, amino, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylsilyl, C2-C30 alkenyl, C3-C30 cycloalkyl, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C30 aryl, and C3-C30 heteroaryl.

[0015] In this invention, L 1 When selected from a single bond, it means Ar 1It is directly linked to the benzenexene group via a single bond. Similarly, L 2 When selected from a single bond, it means Ar 2 It is directly linked to the benzanthracene group via a single bond.

[0016] In this invention, the "substituted or unsubstituted" group may contain no substituent, one substituent, or multiple substituents. When there are multiple substituents (at least two), they may be the same or different substituents. The same expression used below has the same meaning.

[0017] It should be noted that, for ease of explanation, the possible effects of each group / feature have been described separately in this invention, but this does not mean that these groups / features act in isolation. In fact, the essential reason for obtaining good performance is the optimized combination of the entire molecular structure, which is the result of the synergistic effect between various groups, rather than the effect of a single group / feature.

[0018] The following are preferred embodiments of the present invention, but are not intended to limit the embodiments provided by the present invention. The objectives and beneficial effects of the present invention can be better achieved and realized through the following preferred embodiments.

[0019] As a preferred implementation scheme, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10Each is independently selected from any one of hydrogen, deuterium, halogen (e.g., F, Cl, Br, I), cyano, substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) alkyl, substituted or unsubstituted C3-C10 (e.g., C4, C5, C6, C7, C8, or C9, etc.) cycloalkyl, substituted or unsubstituted C6-C15 (e.g., C6, C9, C10, C12, or C14, etc.) aryl, substituted or unsubstituted C3-C15 (e.g., C3, C4, C5, C6, C9, C10, C12, or C14, etc.) heteroaryl. The substituents are one or more, and each is independently selected from deuterium, halogens (e.g., F, Cl, Br, I), C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) alkyl, C3-C10 (e.g., C4, C5, C6, C7, C8, or C9, etc.) cycloalkyl, C6-C15 (e.g., C6, C9, C10, C12, or C14, etc.) aryl, and C3-C15 heteroaryl (e.g., C3, C4, C5, C6, C9, C10, C12, or C14, etc.) combinations of one or at least two.

[0020] As a preferred embodiment, the R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 Each is independently selected from any one or a combination of at least two of the following: hydrogen, deuterium, halogen, cyano, methyl, deuterated methyl, trifluoromethyl, ethyl, isopropyl, isobutyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, deuterated phenyl, tert-butylphenyl, biphenyl, naphthyl, deuterated naphthyl, dibenzofuranyl, dibenzothiopheneyl, fluorenyl, and carbazoleyl.

[0021] As a preferred embodiment, the R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 Each is independently selected from hydrogen or deuterium.

[0022] As a preferred embodiment, the benzanthracene derivative has a structure as shown in Formula I-1:

[0023]

[0024] In Equation I-1, L 1 L 2 Ar 1 Ar 2 The definition is the same as that in formula I.

[0025] As a preferred implementation scheme, Ar 1 Ar 2 Each is independently selected from the structure shown in formula a or formula b.

[0026] As a preferred implementation scheme, Ar 1 and Ar 2 One of them is selected from the structure shown in formula a or formula b, and the other is selected from any one or a combination of at least two of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl.

[0027] As a preferred implementation scheme, Ar 1 and Ar 2 Each is independently selected from any one or a combination of at least two of substituted or unsubstituted C6-C25 (e.g., C6, C9, C10, C12, C14, C15, C16, C18, C20, C22, or C24) aryl groups and substituted or unsubstituted C3-C25 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C15, C16, C18, C20, C22, or C24) heteroaryl groups, and Ar 1 Ar 2 At least one of the structures is selected from either equation a or equation b.

[0028] As a more preferred implementation scheme, Ar 1 and Ar 2 One of them is selected from the structure shown in formula a or formula b, and the other is selected from any of the following groups, substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, binaphthyl, anthracene, phenanthryl, fluoranthyl, triphenylene, benzo[anthracene], pyrene, fluorenyl, spirodifluorenyl, benzo[anthracene], pyridylphenyl, pyridyl, phenylpyridyl, bipyridyl, dibenzofuranyl, benzo[naphthylfuranyl], dibenzothiophene, benzo[naphthiophene].

[0029] In some implementations, the Ar 1 Or Ar 2The substituents described herein are one or more, and each is independently selected from any one or a combination of at least two of the following: deuterium, halogen (e.g., F, Cl, Br, I), cyano, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) alkyl, C3-C10 (e.g., C4, C5, C6, C7, C8, or C9, etc.) cycloalkyl, C6-C15 (e.g., C6, C9, C10, C12, or C14, etc.) aryl, and C3-C15 (e.g., C3, C4, C5, C6, C9, C10, C12, or C14, etc.) heteroaryl.

[0030] In some implementations, the Ar 1 Or Ar 2 The substituents described herein are one or more, and each is independently selected from any one or a combination of at least two of the following: deuterium, halogen, cyano, methyl, ethyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, pyridyl, dibenzofuranyl, and dibenzothiophene.

[0031] In some embodiments, Ar 1 and Ar 2 One of the groups is selected from the group shown in formula a or formula b, and the other is selected from any of the following groups, whether substituted or unsubstituted: phenyl, naphthyl, biphenyl, dibenzofuranyl, terphenyl.

[0032] In some embodiments, Ar 1 and Ar 2 One of the groups is selected from the group shown in formula a or formula b, and the other is selected from any of the following groups: phenyl, deuterated phenyl, naphthyl, biphenyl, dibenzofuranyl, terphenyl.

[0033] In this invention, the group resulting from the combination of two groups may include, for example, partially or completely deuterated alkyl groups formed by combining alkyl and deuterium (e.g., deuterated methyl, deuterated ethyl, deuterated isopropyl, deuterated tert-butyl, etc.); partially or completely haloalkyl groups formed by combining halogen and alkyl groups (e.g., trifluoromethyl, etc.); partially or completely deuterated aryl groups formed by combining aryl and deuterium (e.g., deuterated phenyl, etc.); alkyl-substituted aryl groups formed by combining alkyl and aryl groups (e.g., tert-butylphenyl, dimethylphenyl, etc.) or aryl-substituted alkyl groups (e.g., phenyl-substituted tert-butyl, etc.), etc. When the same description is used below, it has the same meaning and will not be repeated individually.

[0034] As a preferred implementation scheme, X 1 X 2 X 3 Each can be independently selected from O or S.

[0035] In some embodiments, X1 X 2 X 3 All are 0. In some embodiments, X 1 X 2 X 3 All are S. In some embodiments, X 1 Let S and X be the values ​​of S and X. 2 X 3 All are O.

[0036] As a preferred implementation scheme, in formula a, Y 1 ~Y 12 Each is independently selected from N, C, or CR. 11 And Y 1 ~Y 12 Any one or two of them are C and L 1 or L 2 connect.

[0037] As a preferred implementation scheme, in formula a, Y 1 ~Y 12 Each is independently selected from N, C, or CR. 11 And Y 1 ~Y 12 Any one of them is C and L 1 or L 2 connect.

[0038] As a preferred implementation scheme, in formula a, Y 1 Y 2 Y 3 Y 4 Y 5 Y 6 Y 7 Y 8 Y 9 Y 10 Y 11 Y 12 At most one (e.g., 0 or 1) is selected from N.

[0039] As a preferred implementation scheme, in formula a, Y 4 Y 5 Y 9 For N or CR 11 .

[0040] As a preferred implementation scheme, in formula a, Y 4 Or Y 5 Or Y 9 Let N be the number of elements in the array.

[0041] As a preferred implementation scheme, in formula a, Y 1 Y2 Y 3 Y 4 Y 5 Y 6 Y 7 Y 8 Y 9 Y 10 Y 11 Y 12 Any one of them is C and L 1 or L 2 The connection is made, and the rest are selected independently from CR. 11 .

[0042] As a preferred implementation scheme, in formula a, Y 1 ~Y 12 Middle, Y 1 Y 2 Y 3 Y 6 Y 7 Y 8 Y 10 Y 11 Y 12 Any one of them is C and is related to L 1 or L 2 The connections are made, and the rest are independently selected from N or CR. 11 .

[0043] As a preferred implementation scheme, in formula a, Y 1 ~Y 12 Middle, Y 1 Y 2 Y 3 Y 6 Y 7 Y 8 Y 10 Y 11 Y 12 Any one of them is C and L 1 or L 2 The connection is made, and the rest are selected independently from CR. 11 .

[0044] As a preferred implementation scheme, in formula a, Y 1 ~Y 12 Middle, Y 4 Y 5 Y 9 For N or CR 11 Y 1 Y 2 Y 3 Y 6 Y 7 Y 8Y 10 Y 11 Y 12 Any one of them is C and is related to L 1 or L 2 The connection is made, and the rest are selected independently from CR. 11 .

[0045] As a preferred implementation scheme, in formula a, Y 1 ~Y 12 Middle, Y 4 Y 5 Y 9 For N or CR 11 Y 1 Y 2 Y 3 Any one of them is C and is related to L 1 or L 2 The connection is made, and the rest are selected independently from CR. 11 .

[0046] As a preferred implementation scheme, in formula a, Y 1 ~Y 12 Each is independently selected from N, C, or CR. 11 And Y 1 ~Y 12 Any two of them are C and L 1 or L 2 connect.

[0047] As a preferred implementation scheme, in formula a, Y 1 Y 2 Y 3 Y 4 Y 5 Y 6 Y 7 Y 8 Y 9 Y 10 Y 11 Y 12 Any two of them are C and L 1 or L 2 The connection is made, and the rest are selected independently from CR. 11 .

[0048] As a preferred implementation scheme, in formula a, Y 1 ~Y 12 Middle, Y 1 Y 2 Y 3 Y 6 Y 7 Y 8 Y 10 Y11 Y 12 Any two of them are C and L 1 or L 2 The connections are made, and the rest are independently selected from N or CR. 11 .

[0049] As a preferred implementation scheme, in formula a, Y 1 ~Y 12 Middle, Y 1 Y 2 Y 3 Any two of them (e.g., Y) 1 and Y 3 ) is C and is related to L 1 or L 2 The connections are made, and the rest are independently selected from N or CR. 11 The remaining components are preferably selected independently from CR. 11 .

[0050] As a preferred implementation scheme, in formula a, Y 1 ~Y 12 Middle, Y 1 Y 2 Y 3 Any one of them is C and is related to L 1 or L 2 Connection, Y 6 Y 7 Y 8 Any one of them is C and is related to L 1 or L 2 The connections are made, and the rest are independently selected from N or CR. 11 The remaining components are preferably selected independently from CR. 11 .

[0051] As a preferred implementation scheme, in formula b, Y 1 ~Y 12 Each is independently selected from N, C, or CR. 11 And Y 1 ~Y 12 Any one or two of them are C and L 1 or L 2 connect.

[0052] As a preferred implementation scheme, in formula b, Y 1 ~Y 12 Each is independently selected from N, C, or CR. 11 And Y 1 ~Y 12 Any one of them is C and L 1 or L 2 connect.

[0053] As a preferred implementation scheme, in formula b, Y 1 Y 2 Y 3 Y 4 Y 5 Y 6 Y 7 Y 8 Y 9 Y 10 Y 11 Y 12 At most one (e.g., 0 or 1) is selected from N.

[0054] As a preferred implementation scheme, in formula b, Y 4 Y 5 Y 9 For N or CR 11 .

[0055] As a preferred implementation scheme, in formula b, Y 5 Let N be the number of elements in the array.

[0056] As a preferred implementation scheme, in formula b, Y 1 Y 2 Y 3 Y 4 Y 5 Y 6 Y 7 Y 8 Y 9 Y 10 Y 11 Y 12 Any one of them is C and L 1 or L 2 The connection is made, and the rest are selected independently from CR. 11 .

[0057] As a preferred implementation scheme, in formula b, Y 1 ~Y 12 Middle, Y 1 Y 2 Y 3 Y 6 Y 7 Y 8 Y 10 Y 11 Y 12 Any one of them is C and is related to L 1 or L 2 The connections are made, and the rest are independently selected from N or CR. 11 .

[0058] As a preferred implementation scheme, in formula b, Y1 ~Y 12 Middle, Y 1 Y 2 Y 3 Y 6 Y 7 Y 8 Y 10 Y 11 Y 12 Any one of them is C and is related to L 1 or L 2 The connection is made, and the rest are selected independently from CR. 11 .

[0059] As a preferred implementation scheme, in formula b, Y 1 ~Y 12 Middle, Y 4 Y 5 Y 9 For N or CR 11 Y 1 Y 2 Y 3 Y 6 Y 7 Y 8 Y 10 Y 11 Y 12 Any one of them is C and is related to L 1 or L 2 The connection is made, and the rest are selected independently from CR. 11 .

[0060] As a preferred implementation scheme, in formula b, Y 1 ~Y 12 Middle, Y 4 Y 5 Y 9 For N or CR 11 Y 6 Y 7 Y 8 Any one of them is C and is related to L 1 or L 2 The connection is made, and the rest are selected independently from CR. 11 .

[0061] As a preferred implementation scheme, in formula b, Y 1 ~Y 12 Each is independently selected from N, C, or CR. 11 And Y 1 ~Y 12 Any two of them are C and L 1 or L 2 connect.

[0062] As a preferred implementation scheme, in formula b, Y 1 Y 2 Y 3 Y 4 Y 5 Y 6 Y 7 Y 8 Y 9 Y 10 Y 11 Y 12 Any two of them are C and L 1 or L 2 The connection is made, and the rest are selected independently from CR. 11 .

[0063] As a preferred implementation scheme, in formula b, Y 1 ~Y 12 Middle, Y 1 Y 2 Y 3 Y 6 Y 7 Y 8 Y 10 Y 11 Y 12 Any one or two of them are C and are related to L 1 or L 2 The connections are made, and the rest are independently selected from N or CR. 11 .

[0064] As a preferred implementation scheme, in formula b, Y 1 ~Y 12 Middle, Y 6 Y 7 Y 8 Any two of them (e.g., Y) 6 and Y 8 ) is C and is related to L 1 or L 2 The connections are made, and the rest are independently selected from N or CR. 11 The remaining components are preferably selected independently from CR. 11 .

[0065] As a preferred implementation scheme, in formula b, Y 1 ~Y 12 Middle, Y 1 Y 2 Y 3 Any one of them is C and is related to L 1 or L 2 Connection, Y 10 Y 11 Y 12Any one of them is C and is related to L 1 or L 2 The connections are made, and the rest are independently selected from N or CR. 11 The remaining components are preferably selected independently from CR. 11 .

[0066] As a preferred implementation scheme, R 11 Each group is independently selected from hydrogen, deuterium, halogen (e.g., F, Cl, Br, I), cyano, or any of the following substituted or unsubstituted groups: C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) alkyl, C3-C10 (e.g., C4, C5, C6, C7, C8, or C9, etc.) cycloalkyl, C6-C20 (e.g., C6, C9, C10, C12, C14, C15, C16, or C18, etc.) aryl, C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C15, etc.) The substituted substituents are one or more, each independently selected from any one or a combination of at least two of the following: deuterium, halogens (e.g., F, Cl, Br, I), cyano, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) alkyl, C3-C10 (e.g., C4, C5, C6, C7, C8, or C9, etc.) cycloalkyl, C6-C12 (e.g., C6, C9, or C10, etc.) aryl, and C3-C12 (e.g., C3, C4, C5, C6, C9, or C10, etc.) heteroaryl.

[0067] As a preferred implementation scheme, R 11 Each is independently selected from any one or a combination of at least two of the following: hydrogen, deuterium, halogen, cyano, methyl, deuterated methyl, trifluoromethyl, ethyl, isopropyl, isobutyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, deuterated phenyl, tert-butylphenyl, biphenyl, naphthyl, deuterated naphthyl, anthracene, benzoanthracene, dibenzofuranyl, dibenzothiophene, fluorenyl, and carbazole.

[0068] As a more preferred implementation scheme, R 11 Each is independently selected from any one or at least a combination of two of the following: hydrogen, deuterium, halogen, cyano, methyl, deuterated methyl, tert-butyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, anthracene, and benzo[a]anthracene.

[0069] In some embodiments, R 11 Each group is independently selected from the group consisting of hydrogen and the following groups, where * indicates the linking site of the group:

[0070]

[0071] In some embodiments, two adjacent R 11 They can be linked into rings by chemical bonds, such as benzene rings or naphthalene rings, with benzene rings being preferred.

[0072] As a more preferred embodiment, the benzanthracene derivative has a structure as shown in any one of formulas II-1 to II-12:

[0073]

[0074] Among them, R 1 ~R 10 L 1 L 2 Ar 1 Ar 2 The definition is the same as that in Equation I; X 1 ~X 3 The definition is the same as that in equations a and b, Y 1 ~Y 12 Each is independently selected from N or CR 11 R 11 The definition is the same as that in the foregoing definition of this invention.

[0075] As a preferred embodiment, the benzanthracene derivative has a structure as shown in any one of formulas III-1 to III-16:

[0076]

[0077]

[0078] In Equations III-1 to III-16, L 1 L 2 R 11 Ar 1 Ar 2 The definition is the same as that in formula I.

[0079] In some embodiments, in formulas III-1 to III-16, Ar 1 Or Ar 2 Selected from any of the following groups, whether substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, binaphthyl, anthracene, phenanthryl, fluoranthyl, triphenylene, benzo[a]anthrayl, pyrene, fluorenyl, spirodifluorenyl, benzo[a]fluorenyl, pyridylphenyl, pyridyl, phenylpyridyl, bipyridyl, dibenzofuranyl, benzo[a]naphthiofuranyl, dibenzo[a]thiophenyl, benzo[a]naphthiophenyl.

[0080] In some embodiments, in formulas III-1 to III-16, Ar 1 Or Ar 2Selected from any of the following groups, whether substituted or unsubstituted: phenyl, naphthyl, biphenyl, dibenzofuranyl, terphenyl.

[0081] In some embodiments, in formulas III-1 to III-16, Ar 1 Or Ar 2 The substituents described herein are one or more, and each is independently selected from any one or a combination of at least two of the following: deuterium, halogen (e.g., F, Cl, Br, I), cyano, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) alkyl, C3-C10 (e.g., C4, C5, C6, C7, C8, or C9, etc.) cycloalkyl, C6-C15 (e.g., C6, C9, C10, C12, or C14, etc.) aryl, and C3-C15 (e.g., C3, C4, C5, C6, C9, C10, C12, or C14, etc.) heteroaryl.

[0082] In some embodiments, in formulas III-1 to III-16, Ar 1 Or Ar 2 The substituents described herein are one or more, and each is independently selected from any one or a combination of at least two of the following: deuterium, halogen, cyano, methyl, ethyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, pyridyl, dibenzofuranyl, and dibenzothiophene.

[0083] In some embodiments, Ar 1 Or Ar 2 It is selected from any of the following groups: phenyl, deuterated phenyl, naphthyl, biphenyl, dibenzofuranyl, terphenyl.

[0084] As a preferred embodiment, the group represented by formula a is selected from the group consisting of the following structures, where * indicates the linking site of the group:

[0085]

[0086]

[0087] As a preferred embodiment, the group represented by formula b is selected from the group consisting of the following structures, where * indicates the linking site of the group:

[0088]

[0089] As a preferred implementation scheme, L 1 L 2Each is independently selected from any one or a combination of at least two of the following: single-bonded, substituted or unsubstituted C6-C20 (e.g., C6, C9, C10, C12, C14, C15, C16 or C18, etc.) arylene, substituted or unsubstituted C3-C20 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C15, C16 or C18, etc.) heteroarylene.

[0090] In some implementations, L 1 L 2 The substituents described herein are each independently selected from any one or a combination of at least two of the following: deuterium, halogen (e.g., F, Cl, Br, I), cyano, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) alkyl, C3-C10 (e.g., C4, C5, C6, C7, C8, or C9, etc.) cycloalkyl, C6-C15 (e.g., C6, C9, C10, C12, or C14, etc.) aryl, and C3-C15 (e.g., C3, C4, C5, C6, C9, C10, C12, or C14, etc.) heteroaryl.

[0091] As a more preferred implementation scheme, L 1 L 2 Each of the following groups is independently selected from a single bond, or is substituted or unsubstituted: phenylene, biphenylene, naphthylene, fluorene, pyridylene, dibenzofuranyl, dibenzothiophene.

[0092] In some implementations, L 1 L 2 In this context, each of the substituents is independently selected from any one or a combination of at least two of the following: deuterium, halogen, cyano, methyl, ethyl, isopropyl, isobutyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, biphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, and fluorenyl.

[0093] As a preferred implementation scheme, L 1 L 2 In this context, each of the substituents is independently selected from any one or a combination of at least two of the following: deuterium, methyl, ethyl, isopropyl, isobutyl, tert-butyl, and phenyl.

[0094] As a more preferred implementation scheme, L 1 L 2 Each of the following groups, independently selected from single-bonded, deuterated, or unsubstituted groups, is indicated by *, where * represents the linkage site of the group:

[0095]

[0096] In some implementations, L1 L 2 Each group is independently selected from any of the following groups, either single-bonded, substituted, or unsubstituted: phenylene, biphenylene, naphthylene. In some embodiments, the L... 1 L 2 Each is independently selected from single bonds, phenylene, biphenylene, or naphthylene.

[0097] As a preferred embodiment, the benzanthracene derivative is selected from the group consisting of compounds shown in Table 1 below:

[0098] Table 1

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113] Some or all of the hydrogen in the above structure can be replaced by deuterium.

[0114] In a second aspect, the present invention provides the application of benzene-anthracene derivatives as described in the first aspect of the present invention in organic electroluminescent devices.

[0115] In this invention, the benzene anthracene derivative can be used as the main material of the light-emitting layer of an organic electroluminescent device.

[0116] In some implementations, the organic electroluminescent device is a blue organic electroluminescent device.

[0117] In some embodiments, the benzanthracene derivative in the light-emitting layer of the organic electroluminescent device has a mass percentage content of 80% to 99% (e.g., 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96%, 98% or any value between them).

[0118] In some implementations, the light-emitting layer further includes a dopant material (also known as a dopant, luminescent dye, dye, etc.).

[0119] In some embodiments, the doping material is a fluorescent material, a phosphorescent material, or a thermally activated delayed fluorescence material.

[0120] Thirdly, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises at least one benzene-anthracene derivative as described in the first aspect.

[0121] In some embodiments, the organic layer comprises at least one of the compounds A1-A274 described above.

[0122] In some implementations, the organic electroluminescent device is a blue organic electroluminescent device.

[0123] In some embodiments, the organic layer includes a light-emitting layer comprising at least one benzanthracene derivative as described in the first aspect. In some embodiments, the light-emitting layer comprises at least one compound selected from compounds A1-A274 described above.

[0124] In some embodiments, the benzanthracene derivative in the luminescent layer is 80% to 99% by mass (e.g., 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96%, 98% or any value between them).

[0125] In some implementations, the light-emitting layer further includes a dopant material (also known as a dopant, luminescent dye, dye, etc.).

[0126] In some embodiments, the doping material is a fluorescent material, a phosphorescent material, or a thermally activated delayed fluorescence material.

[0127] In some embodiments, the thickness of the light-emitting layer is 10-60 nm, for example, it can be 12 nm, 15 nm, 18 nm, 20 nm, 22 nm, 25 nm, 28 nm, 30 nm, 32 nm, 35 nm, 38 nm, 40 nm, 42 nm, 45 nm, 48 nm, 50 nm, 52 nm, 55 nm, 58 nm, or any value between them. In some embodiments, the thickness of the light-emitting layer is 20-50 nm.

[0128] In some implementations, the organic layer further includes hole transport regions and electron transport regions.

[0129] In some embodiments, the hole transport region includes any one or a combination of at least two of a hole injection layer, a hole transport layer, and an electron blocking layer. In some embodiments, the hole transport region further includes a hole auxiliary layer.

[0130] In some embodiments, the electron transport region includes any one or a combination of at least two of an electron injection layer, an electron transport layer, and a hole blocking layer. In some embodiments, the electron transport region further includes an electron buffer layer.

[0131] In some embodiments, the organic layer includes multiple regions, such as a hole transport region, a light-emitting layer (which may also include a light-emitting auxiliary layer), and an electron transport region; the light-emitting layer includes at least one benzanthracene derivative as described in the first aspect. In some embodiments, the light-emitting layer includes at least one compound selected from compounds A1-A274.

[0132] In a preferred embodiment, the organic electroluminescent device includes a first electrode (anode), an organic layer, and a second electrode (cathode) sequentially disposed. The organic layer includes a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer sequentially disposed, wherein the hole injection layer is in contact with the first electrode. The organic layer (preferably the light-emitting layer) includes at least one benzenexane derivative as described in the first aspect, preferably including at least one compound selected from compounds A1-A274.

[0133] Fourthly, the present invention provides a display device or lighting device, including the organic electroluminescent device as described in the third aspect of the present invention.

[0134] In some implementations, the display device is a display device for smartphones, tablets, laptops, PCs (computers), TVs (television sets), or automobiles.

[0135] In some implementations, the lighting device is an outdoor or indoor lighting device.

[0136] The present invention has the following beneficial technical effects:

[0137] (1) The benzoanthracene derivative provided by the present invention combines a benzoanthracene nucleus with a cyclotriphenylether macrocycle or other structures. As the host material of an organic electroluminescent material, it can effectively promote the injection and transport of carriers, thereby achieving a better carrier balance. Moreover, the macrocyclic ether group increases the molecular steric hindrance and hinders the formation of exciton-exciton complexes between organic molecules, reducing the energy loss channels, and thus significantly improving the internal quantum efficiency of the device.

[0138] (2) The structure of formula a or formula b in the present invention endows the formed benzoanthracene derivative molecular skeleton with high rigidity, enhances the intermolecular force, and can effectively inhibit the crystallization of the material during the operation of the device. The stable molecular structure can withstand the impact of high-energy excitons, slow down the material aging and degradation process, and it has a shorter emission wavelength compared with existing compounds, thereby improving the life and efficiency of the device.

[0139] (3) The benzoanthracene derivative of the present invention is not only applicable to the traditional vacuum evaporation process, but can also be applied to its solution process to prepare the light-emitting layer, reducing costs. Moreover, by flexibly selecting the substituents on the nucleus structure, the charge transfer of the entire molecule can be precisely regulated, thereby obtaining a blue light emission with high color purity. Detailed embodiments

[0140] Hereinafter, the present invention will be described in detail. However, the following description is intended to explain the present invention and does not intend to limit the scope of the present invention in any way.

[0141] In the present invention, the halogen can be fluorine, chlorine, bromine or iodine.

[0142] In the present invention, for the expression of chemical elements, unless otherwise specified, the concept of isotopes with the same chemical properties is included. For example, hydrogen (H) includes 1 H (protium), 2 H (deuterium, D), 3 H (tritium, T), etc.; carbon (C) includes 12 C, 13 C, etc.

[0143] In the present invention, unless otherwise specified, the heteroatoms of heteroaryl are selected from N, O, S, P, B, Si or Se, preferably N, O or S. The heteroatoms of heterocyclic alkyl are selected from N, O, S, P, B, Si or Se, preferably N, O or S.

[0144] In the present invention, the expression of the ring structure with a "-" drawn across it indicates that the connection site is at any position on the ring structure where bonding can occur. <​

[0146] In this invention, "each independently" means that when there are multiple subjects, they can be the same or different from each other.

[0147] In this invention, the expression Ca-Cb represents that the group has ab carbon atoms. Unless otherwise specified, the number of carbon atoms does not include the number of carbon atoms of the substituents.

[0148] In this invention, C1-C30 can all be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C22, C24, C26, C28 or C30, etc.

[0149] In this invention, C3-C30 can all be C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C22, C24, C26, C28 or C30, etc.

[0150] In this invention, C2-C30 can all be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C22, C24, C26, C28 or C30, etc.

[0151] In this invention, C6-C30 can all be C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 or C30, etc.

[0152] In this invention, C3-C30 can all be C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 or C30, etc.

[0153] In this invention, unless otherwise specified, the C6-C30 aryl (preferably C6-C20 aryl) includes monocyclic aryl and fused-ring aryl; the monocyclic aryl means that the group contains at least one phenyl group, and when it contains at least two phenyl groups, the phenyl groups are linked by single bonds, including but not limited to: phenyl, biphenyl, terphenyl, tetraphenyl, etc.; the fused-ring aryl means that the group contains at least two rings (and at least one ring is an aromatic ring), and the rings share two adjacent carbon atoms fused together. Examples include, but are not limited to: naphthyl, anthracene, phenanthryl, indene, fluorenyl and their derivatives (9,9-dimethylfluorenyl, 9,9-diethylfluorenyl, 9,9-dipropylfluorenyl, 9,9-dibutylfluorenyl, 9,9-dipentylfluorenyl, 9,9-dihexylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9,9-dinaphthylfluorenyl, spirodifluorenyl, benzo[a]fluorenyl (benzo[A]fluorenyl, benzo[B]fluorenyl, benzo[C]fluorenyl), fluoranyl, triphenylene, pyrene, perylene, Aryl, tetraphenyl, acenaphthenyl, benzo[a]acenaphthenyl, etc. It should be noted that monocyclic aryl and fused-ring aryl groups linked by single bonds also fall under the category of aryl groups, such as phenylnaphthyl, naphthylphenyl, and binaphthyl.

[0154] In this invention, unless otherwise specified, the C3-C30 heteroaryl (preferably C3-C20 heteroaryl) and C5-C30 heteroaryl include monocyclic heteroaryl or fused-ring heteroaryl. A monocyclic heteroaryl means that the molecule contains at least one heteroaryl group. When the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, etc.), the heteroaryl group and other groups are connected by a single bond, exemplarily including but not limited to: pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furanyl, thiophene, pyrroleyl, bipyridyl, phenylpyridinyl, pyridylphenyl, etc. The term "fused-ring heteroaryl" refers to a molecule containing at least one aromatic heterocycle and one aromatic ring (aromatic heterocycle or aromatic ring), wherein the two share two adjacent atoms fused together in a group. Examples include, but are not limited to: quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, isobenzothiopheneyl, indolyl, dibenzofuranyl, benzonaphthofuranyl (benzo[B]naphtho[2,3-D]furanyl, benzo[B]naphtho[1,2-D) Furanyl, benzo[B]naphtho[2,1-D]furanyl), dibenzothiophene, benzo[B]naphtho[2,3-D]thiophene (benzo[B]naphtho[1,2-D]thiophene, benzo[B]naphtho[2,1-D]thiophene), carbazole and its derivatives (N-phenylcarbazole, N-naphthylcarbazole, benzocarbazole, dibenzocarbazole, indolecarbazole, azacarbazole, etc.), acridineyl, phenothiazinyl, phenotoxazinyl, hydrogenated acridineyl, etc.

[0155] In this invention, a specific example of the C6-C30 arylene group can be the divalent group obtained by removing one hydrogen atom from the above-mentioned aryl group examples.

[0156] In this invention, a specific example of the C3-C30 heteroaryl group can be a divalent group obtained by removing one hydrogen atom from the above-mentioned heteroaryl group examples.

[0157] In this invention, a specific example of the C6-C30 arylamino group is a monovalent group obtained by substituting at least one hydrogen atom in -NH2 with the aforementioned aryl group. A specific example of the C3-C30 heteroarylamino group is a monovalent group obtained by substituting at least one hydrogen atom in -NH2 with the aforementioned heteroaryl group.

[0158] In this invention, the C6-C30 aryloxy group is a monovalent group formed by connecting the above-mentioned aryl group with O, and the C3-C30 heteroaryloxy group is a monovalent group formed by connecting the above-mentioned heteroaryl group with O.

[0159] In this invention, the C6-C30 arylthio group is a monovalent group formed by connecting the aforementioned aryl group with S, and the C3-C30 heteroarylthio group is a monovalent group formed by connecting the aforementioned heteroaryl group with S.

[0160] In this invention, a specific example of the C6-C30 arylsilyl group is a monovalent group obtained by replacing at least one hydrogen in -SiH3 with the above-mentioned aryl group, and a specific example of the C3-C30 heteroarylsilyl group is a monovalent group obtained by replacing at least one hydrogen in -SiH3 with the above-mentioned heteroaryl group.

[0161] In this invention, the C1-C30 alkyl group, preferably C1-C16 alkyl group, and more preferably C1-C10 alkyl group, includes straight-chain alkyl or branched-chain alkyl groups, and exemplary includes, but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, etc.

[0162] In this invention, specific examples of the C1-C30 alkoxy group can be exemplified by the monovalent group obtained by connecting the aforementioned alkyl group to O.

[0163] In this invention, a specific example of the C1-C30 alkylsilyl group is a monovalent group obtained by replacing at least one hydrogen in -SiH3 with the alkyl group described above; a specific example of the C1-C30 alkylamino group is a monovalent group obtained by replacing at least one hydrogen in -NH2 with the alkyl group described above.

[0164] In this invention, the C3-C30 cycloalkyl group, preferably C3-C10 cycloalkyl group, includes monocycloalkyl or polycycloalkyl groups. Monocycloalkyl refers to an alkyl group containing a single ring structure, while polycycloalkyl refers to a structure formed by two or more cycloalkyl groups sharing one or more carbon atoms on a ring. Exemplary examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl.

[0165] In this invention, specific examples of the C2-C30 heterocyclic alkyl group can be exemplified by groups formed by replacing at least one C atom in the aforementioned cycloalkyl group with a heteroatom (e.g., N, O, S, etc.), including but not limited to: epoxy group, oxetane, tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydropyrroleyl, tetrahydropyranyl, piperidinyl, piperazineyl, dioxaneyl, morpholinyl, etc.

[0166] In this invention, the C2-C30 alkenyl group, preferably C2-C10 alkenyl group, contains at least one C=C, and includes, but is not limited to: vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, butadienyl, pentadienyl, etc.

[0167] In this invention, "combination" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that can be conceived by a person skilled in the art from the applicable list. Examples include combinations of alkyl / aryl and deuterium to form partially or fully deuterated alkyl / aryl groups (e.g., deuterated methyl, deuterated ethyl, deuterated tert-butyl, deuterated phenyl, deuterated biphenyl, deuterated naphthyl, etc.); combinations of halogen and alkyl to form partially or fully haloalkyl groups (e.g., trifluoromethyl, etc.); combinations of alkyl and aryl to form alkylaryl groups (methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, isopropylphenyl, diisopropylphenyl, tert-butylphenyl, di-tert-butylphenyl, isobutylphenyl, tert-pentylphenyl, neopentylphenyl, etc.) or arylalkyl groups (e.g., phenyl tert-butyl, etc.); and combinations of halogen, alkyl, and aryl to form haloarylalkyl groups, etc.

[0168] The specific preparation method of the benzene anthracene derivative of the present invention will be described in detail below using several synthetic examples, but the preparation method of the present invention is not limited to these synthetic examples.

[0169] Preparation Example 1

[0170]

[0171] (1-1) Synthesis of intermediate Int.-1:

[0172] Under nitrogen protection, 3,3'-oxydiphenol (20.0 mmol), triphenylphosphine (48.0 mmol), and 1,3-cyclohexanediol (20.0 mmol) were dissolved in dry dichloromethane (200 mL), cooled to 0 °C, and diethyl azodicarbonate (48.0 mmol) was slowly added dropwise. The mixture was stirred for 1 h, then heated to room temperature and stirred for 15 h. Dilute hydrochloric acid (50 mL, 2 M) was added, and the mixture was extracted with dichloromethane. The organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure and dried. The filtrate was purified by silica gel column chromatography to give intermediate Int.-1 (yield 64%).

[0173] (1-2) Synthesis of intermediate Int.-2:

[0174] Intermediate Int.-1 (40.0 mmol) was dissolved in xylene (150 mL), and manganese dioxide (200.0 mmol) was added. The mixture was heated to reflux and stirred under reflux for 24 h. After cooling to room temperature, the mixture was filtered, the filter cake was washed with toluene, and the filtrate was concentrated and dried under reduced pressure. The filtrate was then purified by silica gel column chromatography to obtain intermediate Int.-2 (yield 92%).

[0175] (1-3) Synthesis of intermediate Int.-3:

[0176] Under nitrogen protection, intermediate Int.-2 (20.0 mmol) and p-toluenesulfonic acid (0.2 mmol) were dissolved in dry dichloromethane (120 mL), cooled to -10 °C, and N-bromosuccinimide (NBS, 22.0 mmol) was added in portions. The mixture was stirred for 2 h, and water (50 mL) was added. The organic phase was separated, and the aqueous phase was extracted with dichloromethane. The organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure and dried. The filtrate was purified by silica gel column chromatography to obtain intermediate Int.-3 (yield 85%).

[0177] (1-4) Synthesis of intermediate S1:

[0178] Under nitrogen protection, intermediate Int.-3 (20.0 mmol) was dissolved in dry THF (50 mL), cooled to -78 °C, and a solution of n-butyllithium in n-hexane (24.0 mmol, 2.5 M) was added dropwise. The mixture was stirred for 30 min, followed by the addition of trimethyl borate (30.0 mmol). The mixture was then heated to room temperature and stirred for 1 h. Dilute hydrochloric acid (20 mL, 3 M) was added, and the mixture was stirred for 30 min. The organic phase was separated, and the aqueous phase was extracted with ethyl acetate. The organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure and dried. Petroleum ether (50 mL) was added, stirred, and filtered. The filter cake was washed with petroleum ether to give intermediate S1 (yield 82%). MS (m / e) of intermediate S1: 320.44.

[0179] Following the synthetic method for intermediate S1 described above, the corresponding intermediates S2, S3, S4, S5, S6, S7, S8 (e.g., replacing 3,3'-oxydiphenol with 3,3'-thiodiphenylthiophenol (CAS: 2143958-83-0)), S9, S10, and S11 were prepared:

[0180] Preparation Example 2

[0181]

[0182] (2-1) Synthesis of intermediate Int.-4:

[0183] Under nitrogen protection, 3,3'-oxydiphenol (20.0 mmol), anhydrous cesium carbonate (60.0 mmol), and 3,5-difluorobromobenzene (20.0 mmol, CAS: 461-96-1) were dissolved in dry DMF (100 mL), heated to 120 °C, stirred for 15 h, cooled to room temperature, and the reaction solution was poured into water (500 mL). The mixture was filtered, the filter cake was washed with water, and purified by silica gel column chromatography to give intermediate Int.-4 (yield 48%).

[0184] (2-2) Synthesis of intermediate S12:

[0185] Following the synthesis method described in steps (1-4) of Preparation Example 1 above, intermediate S12 (yield 86%) was obtained by simply replacing intermediate Int.-3 with intermediate Int.-4. The MS (m / e) of intermediate S12 was 320.57.

[0186] Following the synthetic method for intermediate S12 described above, the corresponding intermediates S13, S14, S15, S16, S17, S18 (e.g., replacing 3,5-difluorobromobenzene with 1,5-dibromo-2,4-difluorobenzene (CAS: 28342-75-8)), S19, S20, and S21 were prepared:

[0187]

[0188] Preparation Example 3

[0189]

[0190] (3-1) Synthesis of intermediate Int.-5:

[0191] Following the synthetic method in step (2-1) of Preparation Example 2 above, simply replacing 3,5-difluorobromobenzene with 1,3-difluoronaphthalene (CAS: 319-16-4) yields intermediate Int.-5 (yield 50%).

[0192] (3-2) Synthesis of intermediate Int.-6:

[0193] Following the synthesis method of steps (1-3) in Preparation Example 1 above, intermediate Int.-6 (75% yield) can be obtained by simply replacing intermediate Int.-2 with intermediate Int.-5.

[0194] (3-3) Synthesis of intermediate S22:

[0195] Following the synthesis method described in steps (1-4) of Preparation Example 1 above, intermediate S22 (yield 84%) was obtained by simply replacing intermediate Int.-3 with intermediate Int.-6. The MS (m / e) of intermediate S22 was 370.02.

[0196] Preparation Example 4

[0197]

[0198] (4-1) Preparation of intermediate Int.-7:

[0199] Under nitrogen protection, 2,2'-dihydroxydiphenyl ether (20.0 mmol), anhydrous cesium carbonate (60.0 mmol), and 3,5-difluorobromobenzene (20.0 mmol) were dissolved in dry DMF (100 mL), heated to 120 °C, stirred for 15 h, cooled to room temperature, and the reaction solution was poured into water (500 mL). The mixture was filtered, the filter cake was washed with water, and purified by silica gel column chromatography to give intermediate Int.-7 (yield 48%).

[0200] (4-2) Preparation of intermediate S23:

[0201] Following the synthesis method described in steps (1-4) of Preparation Example 1 above, intermediate S23 (yield 84%) was obtained by simply replacing intermediate Int.-3 with intermediate Int.-7. The MS (m / e) of intermediate S23 was 320.19.

[0202] Following the synthetic method for intermediate S23 described above, the corresponding intermediates S24, S25, S26, S27, S28, S29, S30 (e.g., replacing 2,2'-dihydroxybiphenyl ether with 2,2'-thiobiphenol (CAS: 13693-59-9)), S31, S32, S33, S34, S35, S36, S37 (e.g., replacing 3,5-difluorobromobenzene with 1,5-dibromo-2,4-difluorobenzene), S38, S39, S40, and S41 were prepared:

[0203]

[0204]

[0205] Preparation Example 5

[0206]

[0207] (5-1) Preparation of intermediate Int.-8

[0208] Following the synthetic method in step (2-1) of Preparation Example 2 above, simply replacing 3,5-difluorobromobenzene with 1,3-difluoronaphthalene yields intermediate Int.-8 (yield 55%).

[0209] (5-2) Preparation of intermediate Int.-9

[0210] Following the synthesis method of steps (1-3) in Preparation Example 1 above, intermediate Int.-2 can be replaced with intermediate Int.-8 to obtain intermediate Int.-9 (yield 78%).

[0211] (5-3) Preparation of intermediate S42

[0212] Following the synthesis method described in steps (1-4) of Preparation Example 1 above, intermediate S42 (yield 82%) was obtained by simply replacing intermediate Int.-3 with intermediate Int.-9. The MS (m / e) of intermediate S42 was 370.73.

[0213] Synthesis Example 1: Synthesis of Compound A1

[0214]

[0215] Under nitrogen protection, intermediate S1 (10.0 mmol) and toluene (40 mL) were mixed, and starting material M1-1 (10.0 mmol, CAS: 2580968-64-3), potassium carbonate (20.0 mmol), and Pd(PPh3)4 (0.5 mmol) were added. Then, ethanol (20 mL) and water (20 mL) were added, and the mixture was heated to reflux and stirred for 12 h. After the reaction was complete, the mixture was cooled to room temperature, and the organic phase was separated. The aqueous phase was extracted with toluene, and the organic phase was collected, dried, filtered, and the filtrate was concentrated under reduced pressure and dried. The filtrate was purified by silica gel column chromatography to give a white solid compound A1 (yield 63%). The MS (m / e) value of compound A1 was 578.27.

[0216] Synthesis Example 2: Synthesis of Compound A34

[0217]

[0218]

[0219] (2-1) Synthesis of intermediate SM2-1

[0220] Referring to the synthesis method of the above-described synthesis example 1, only by replacing raw material M1-1 with raw material M2-1 (CAS: 32795-84-9) and intermediate S1 with raw material M2-2 (CAS: 1197180-12-3), intermediate SM2-1 (yield 60%) can be obtained.

[0221] (2-2) Synthesis of intermediate SM2-2

[0222] Following the synthesis method of steps (1-3) in Preparation Example 1 above, simply replacing intermediate Int.-2 with intermediate SM2-1 will yield intermediate SM2-2 (yield 81%).

[0223] (2-3) Synthesis of intermediate SM2-3

[0224] Referring to the synthesis method of Example 1 above, by simply replacing raw material M1-1 with raw material M2-3 (CAS: 63279-58-3), intermediate SM2-3 (yield 66%) can be obtained.

[0225] (2-4) Synthesis of intermediate S2-4

[0226] Following the synthesis method of steps (1-4) in Preparation Example 1 above, simply replacing intermediate Int.-3 with intermediate SM2-3 will yield intermediate SM2-4 (yield 79%).

[0227] (2-5) Synthesis of compound A34

[0228] Following the synthetic method described in Example 1 above, only intermediate S1 was replaced with intermediate SM2-4, and starting material M1-1 was replaced with intermediate SM2-2, to obtain white solid compound A34 (yield 62%). MS (m / e) of compound A34: 785.61.

[0229] Synthesis Example 3: Synthesis of Compound A86

[0230]

[0231] (3-1) Synthesis of intermediate SM3-2

[0232] Following the synthetic methods in steps (2-1) and (2-2) of Example 2 above, simply replacing starting material M2-2 with starting material M3-1 (CAS: 912824-85-2) yields intermediates SM3-1 and SM3-2 (two-step yield 51%). (3-2) Synthesis of compound A86

[0233] Following the synthesis method described in Example 1 above, only intermediate S1 was replaced with intermediate S8, and starting material M1-1 was replaced with intermediate SM3-2, to obtain white solid compound A86 (yield 59%). MS (m / e) of compound A86: 716.44.

[0234] Synthesis Example 4: Synthesis of Compound A92

[0235]

[0236] Following the synthesis method described in Example 1 above, only intermediate S1 was replaced with intermediate S22, and starting material M1-1 was replaced with starting material M4-1 (CAS: 1326240-02-1), to obtain white solid compound A92 (yield 64%). The MS (m / e) of compound A92 was 678.47.

[0237] Synthesis Example 5: Synthesis of Compound A102

[0238]

[0239] Following the synthetic methods in steps (3-1) and (3-2) of Example 3 above, simply replacing starting material M3-1 with intermediate S12 and intermediate S8 with starting material M5-1 (CAS: 2226451-93-8) yields a white solid compound A102 (overall yield 27%). The MS (m / e) of compound A102 is 704.61.

[0240] Synthesis Example 6: Synthesis of Compound A129

[0241]

[0242] (6-1) Synthesis of intermediate SM6-1

[0243] Under nitrogen protection, intermediate S18 (20.0 mmol) was dissolved in dry THF (50 mL), cooled to -78 °C, and a hexane solution of n-butyllithium (48.0 mmol, 2.5 M) was added dropwise. The mixture was stirred for 30 min, and trimethyl borate (60.0 mmol) was added dropwise. The mixture was then heated to room temperature and stirred for 1 h. Dilute hydrochloric acid (30 mL, 3 M) was added, and the mixture was stirred for 30 min. The organic phase was separated, and the aqueous phase was extracted with ethyl acetate. The organic phase was collected, dried, filtered, and the filtrate was concentrated and dried under reduced pressure. Petroleum ether (50 mL) was added, stirred, and filtered. The filter cake was washed with petroleum ether to obtain intermediate SM6-1 (yield 67%).

[0244] (6-2) Synthesis of compound A129

[0245] Under nitrogen protection, intermediate SM6-1 (10.0 mmol) and toluene (40 mL) were mixed, followed by starting material M1-1 (20.0 mmol), potassium carbonate (40.0 mmol), and Pd(PPh3)4 (1 mmol). Ethanol (30 mL) and water (30 mL) were then added, and the mixture was heated to reflux and stirred for 12 h. After the reaction was complete, the mixture was cooled to room temperature, and the organic phase was separated. The aqueous phase was extracted with toluene, the organic phase was dried, filtered, and the filtrate was concentrated under reduced pressure and dried. The filtrate was purified by silica gel column chromatography to give a white solid compound A129 (54% yield). The MS (m / e) value of compound A129 was 880.49.

[0246] Synthesis Example 7: Synthesis of Compound A169

[0247]

[0248] Following the synthetic method described in Example 1 above, only intermediate S1 was replaced with intermediate S23, and starting material M1-1 was replaced with starting material M7-1 (CAS: 1338481-35-8), to obtain white solid compound A169 (yield 60%). The MS (m / e) of compound A169 was 628.01.

[0249] Synthesis Example 8: Synthesis of Compound A199

[0250]

[0251] Following the synthetic methods in steps (3-1) and (3-2) of Example 3 above, simply replacing starting material M3-1 with intermediate S30 and intermediate S8 with starting material M8-1 (CAS: 144432-80-4) yields white solid compound A199 (overall yield 24%). The MS (m / e) of compound A199 is 670.36.

[0252] Synthesis Example 9: Synthesis of Compound A257

[0253]

[0254] Following the synthetic method described in steps (6-1) and (6-2) of Example 6 above, simply replacing intermediate S18 with intermediate S37 yields white solid compound A257 (overall yield 35%). MS (m / e) of compound A257: 880.72.

[0255] Synthesis Example 10: Synthesis of Compound A261

[0256]

[0257] Following the synthetic methods in steps (3-1) and (3-2) of Example 3 above, only replacing starting material M3-1 with starting material M10-1 (CAS: 1036378-83-2) and intermediate S8 with intermediate S42, yielded a white solid compound A261 (overall yield 23%). The MS (m / e) of compound A261 was 780.19.

[0258] This invention provides exemplary methods for synthesizing the above-mentioned compounds. Other compounds for which no specific synthesis method is provided can also be prepared using similar methods, requiring only the replacement of raw materials. These methods will not be elaborated here. Alternatively, those skilled in the art can prepare these compounds using other methods in the prior art.

[0259] Device Example 1:

[0260] A blue organic light-emitting diode (OLED) is fabricated as follows: A glass substrate with a 120 nm thick indium tin oxide (ITO) anode is cleaned and then treated with UV ozone and oxygen plasma. After treatment, the substrate is dried in a nitrogen-filled glove box to remove moisture, and then the substrate is mounted on a substrate holder and placed in a vacuum chamber. The organic layer specified below is applied at a vacuum degree of approximately 10... -8 In the case of Torr, The deposition rate was achieved sequentially on the ITO anode using thermal vacuum. First, compounds HT and HI (97:3, w / w) were co-deposited as a hole injection layer (HIL) with a thickness of [missing information]. Compound HT is used as a hole transport layer (HTL) with a thickness of [missing information]. Compound EB is used as an electron blocking layer (EBL) with a thickness of [missing information]. Then, the host material compound A1 and the dopant material compound BD (98:2, w / w) were co-deposited as the emissive layer (EML) with a thickness of [missing information]. Compound HB is used as a hole blocking layer (HBL) with a thickness of [missing information]. The compound ET and 8-hydroxyquinoline-lithium (Liq) (50:50, w / w) were co-deposited as an electron transport layer (ETL) with a thickness of [missing information]. Finally, vapor deposition Thick 8-hydroxyquinoline-lithium (Liq) was used as the electron injection layer (EIL) and deposited by vapor deposition. A thick layer of aluminum is used as the cathode. The device is then transferred back to the glove box and sealed with a glass cover to complete the device.

[0261] Device Examples 2-10 and Device Comparative Example 1

[0262] A blue organic electroluminescent device is disclosed, which differs from device example 1 only in that the main material compound A1 of the light-emitting layer is replaced with the corresponding compounds in Table 2; the other layers, thicknesses, materials and preparation methods are the same as those in device example 1.

[0263] The molecular structural formulas of the device-related materials are shown below, wherein compound D1 can be obtained commercially or prepared using conventional methods in the prior art:

[0264]

[0265] Performance testing:

[0266] Table 2 lists the values ​​at 10 mA / cm 2 Voltage (V), external quantum efficiency (EQE, %), and lifetime (LT) measured at current density 95 (h). To better illustrate the data comparison, the voltage, external quantum efficiency, and lifetime of Device Comparative Example 1 were set to 1.00, and the voltage, external quantum efficiency, and lifetime of other devices were the ratios of their respective test values ​​to the test values ​​of Device Comparative Example 1.

[0267] Table 2

[0268]

[0269]

[0270] As can be seen from Table 2, compared with organic electroluminescent devices prepared using compound D1 as the host material, the devices using the compound of this invention as the blue light host material have lower voltage, higher luminous efficiency, and longer LT (light emission time). 95 Lifespan is significantly increased.

[0271] The organic electroluminescent device or apparatus of the present invention can be used in planar light sources such as wall-mounted televisions, flat panel displays, and lighting, as well as in backlights of copiers, printers, liquid crystal displays, or light sources of measuring instruments, display panels, and indicator lights.

[0272] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of the claims of this patent application.

Claims

1. A benzanthracene derivative having the structure shown in Formula I: in, L 1 L 2 Each is independently selected from any one or a combination of at least two of the single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene; Ar 1 Ar 2 Each is independently selected from any one or a combination of at least two of substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C3-C30 heteroaryl groups, and Ar 1 Ar 2 At least one of the groups is selected from formula a or formula b: Among them, X 1 X 2 X 3 Each is independently selected from O, S, or Se; Y 1 ~Y 12 Each is independently selected from N, C, or CR. 11 And Y 1 ~Y 12 At least one of them is C and is associated with L. 1 or L 2 connect; R 1 ~R 11 Each is independently selected from any one or a combination of at least two of the following: hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl; The R 1 ~R 11 In a ring, any two or more adjacent groups are not connected or are linked by chemical bonds to form a ring; L 1 L 2 Ar 1 Ar 2 R 1 ~R 11 The substituents described herein are one or more, and each is independently selected from any one or a combination of at least two of the following: deuterium, halogen, cyano, nitro, hydroxyl, amino, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylsilyl, C2-C30 alkenyl, C3-C30 cycloalkyl, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C30 aryl, and C3-C30 heteroaryl.

2. The benzanthracene derivative as described in claim 1, characterized in that, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 Each of the substituents is independently selected from any one or a combination of at least two of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C15 aryl, and substituted or unsubstituted C3-C15 heteroaryl, wherein the substituent is one or more, and each of the substituents is independently selected from any one or a combination of at least two of deuterium, halogen, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C15 aryl, and C3-C15 heteroaryl; preferably, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 Each of the following is independently selected from any one or a combination of at least two of the following: hydrogen, deuterium, halogen, cyano, methyl, deuterated methyl, trifluoromethyl, ethyl, isopropyl, isobutyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, deuterated phenyl, tert-butylphenyl, biphenyl, naphthyl, deuterated naphthyl, dibenzofuranyl, dibenzothiopheneyl, fluorenyl, carbazoleyl, more preferably selected from hydrogen or deuterium; and / or Ar 1 Ar 2 Each is independently selected from the structure shown in equation a or equation b, or, Ar 1 and Ar 2 One of the groups is selected from the structure shown in formula a or formula b, and the other is selected from any of the following groups, substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, binaphthyl, anthracene, phenanthryl, fluoranthyl, triphenylene, benzo[a]anthryl, pyrene, fluorenyl, spirodifluorenyl, benzo[a]fluorenyl, pyridylphenyl, pyridyl, phenylpyridyl, bipyridyl, dibenzofuranyl, benzo[a]naphthofranyl, dibenzothiophene, benzo[a]naphthiophene; the substituted group is one or more substituents. Multiple, each independently selected from any one or at least two combinations of deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C15 aryl, and C3-C15 heteroaryl, preferably selected from any one or at least two combinations of deuterium, halogen, cyano, methyl, ethyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, pyridyl, dibenzofuranyl, and dibenzothiopheneyl.

3. The benzanthracene derivative as described in claim 1 or 2, characterized in that, In equations a and b, X 1 X 2 X 3 Each is independently selected from O or S; and / or In formula a, Y 1 ~Y 12 Middle, Y 1 Y 2 Y 3 Y 6 Y 7 Y 8 Y 10 Y 11 Y 12 Any one or two of them are C and are related to L 1 or L 2 The connections are made, and the rest are independently selected from N or CR. 11 Preferably, Y 4 Y 5 Y 9 For N or CR 11 Y 1 Y 2 Y 3 Y 6 Y 7 Y 8 Y 10 Y 11 Y 12 Any one of them is C and is related to L 1 or L 2 The connection is made, and the rest are selected independently from CR. 11 ; and / or In formula b, Y 1 ~Y 12 Middle, Y 1 Y 2 Y 3 Y 6 Y 7 Y 8 Y 10 Y 11 Y 12 Any one or two of them are C and are related to L 1 or L 2 The connections are made, and the rest are independently selected from N or CR. 11 Preferably, Y 4 Y 5 Y 9 For N or CR 11 Y 1 Y 2 Y 3 Y 6 Y 7 Y 8 Y 10 Y 11 Y 12 Any one of them is C and is related to L 1 or L 2 The connection is made, and the rest are selected independently from CR. 11 ; and / or R 11 Each of the following groups, independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted: C1-C10 alkyl, C3-C10 cycloalkyl, C6-C20 aryl, C3-C20 heteroaryl, wherein the substituted group is one or more, and each is independently selected from any one or a combination of at least two of deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C3-C12 heteroaryl; optionally, two adjacent R groups 11 They are linked together by chemical bonds to form benzene rings or naphthalene rings; Preferably, R 11 Each is independently selected from any one or a combination of at least two of the following: hydrogen, deuterium, halogen, cyano, methyl, deuterated methyl, trifluoromethyl, ethyl, isopropyl, isobutyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, deuterated phenyl, tert-butylphenyl, biphenyl, naphthyl, deuterated naphthyl, anthracene, benzo[a]anthrayl, dibenzofuranyl, dibenzothiophene, fluorenyl, and carbazole. More preferably, R 11 Each is independently selected from any one or a combination of at least two of the following: hydrogen, deuterium, halogen, cyano, methyl, deuterated methyl, tert-butyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, anthracene, and benzo[a]anthracene. More preferably, R 11 Each group is independently selected from the group consisting of hydrogen and the following groups, where * indicates the linking site of the group:

4. The benzanthracene derivative according to any one of claims 1-3, characterized in that, The group represented by formula a is selected from the group consisting of the following structures, where * indicates the linking site of the group: and / or The group shown in formula b is selected from the group consisting of the following structures, where * indicates the linking site of the group:

5. The benzanthracene derivative according to any one of claims 1-4, characterized in that, L 1 L 2 Each group is independently selected from any of the following groups, either single-bonded, substituted, or unsubstituted: phenylene, biphenylene, naphthylene, fluorene, pyridylene, dibenzofuranyl, dibenzothiophene; preferably, L 1 L 2 Each is independently selected from single bonds, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene; L 1 L 2 The substituents described herein are one or more, each independently selected from any one or at least two combinations of deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C15 aryl, and C3-C15 heteroaryl, preferably selected from any one or at least two combinations of deuterium, halogen, cyano, methyl, ethyl, isopropyl, isobutyl, tert-butyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, biphenyl, naphthyl, dibenzofuranyl, dibenzothiophene, and fluorenyl, more preferably selected from any one or at least two combinations of deuterium, methyl, ethyl, isopropyl, isobutyl, tert-butyl, and phenyl. Preferably, L 1 L 2 Each of the following groups, independently selected from single-bonded, deuterated, or unsubstituted groups, is indicated by *, where * represents the linkage site of the group:

6. The benzanthracene derivative according to any one of claims 1-5, characterized in that, The benzanthracene derivative is selected from the group consisting of the following compounds or their deuterated derivatives:

7. The use of the benzanthracene derivative as described in any one of claims 1-6 in organic electroluminescent devices; Preferably, the benzene-anthracene derivative is used as the host material of the light-emitting layer of the organic electroluminescent device; Preferably, in the light-emitting layer of the organic electroluminescent device, the mass percentage of the benzene anthracene derivative is 80% to 99%; Preferably, the light-emitting layer of the organic electroluminescent device further includes a doping material, which is preferably a fluorescent material, a phosphorescent material, or a thermally activated delayed fluorescence material.

8. An organic electroluminescent device, comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises a benzene anthracene derivative as described in any one of claims 1-6; Preferably, the organic layer includes a light-emitting layer, which includes the benzene-anthracene derivative.

9. The organic electroluminescent device as described in claim 8, characterized in that, In the luminescent layer, the mass percentage of benzanthracene derivative is 80%–99%; and / or The luminescent layer also includes doping materials, preferably fluorescent, phosphorescent, or thermally activated delayed fluorescence materials; and / or The organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode arranged sequentially.

10. A display device or lighting device comprising the organic electroluminescent device as described in claim 8 or 9.

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