Bis-dibenzofuran compound and organic electroluminescent device thereof

Abstract

The invention relates to a bis-dibenzofuran compound and a luminescent device thereof. The compound provided by the invention has a structure as shown in a formula (I). The compound has a bis-dibenzofuran mother nucleus and a structure similar to bridged biphenyl, has high thermal stability, high chemical stability and high carrier transport property, and also has proper singlet state, triplet state and molecular orbital energy level and high light-emitting quantum efficiency, and when the compound is used as a main body material, a light-emitting device generally has more excellent performance, and the application prospect is wide. The driving voltage, the luminous efficiency and the service life are obviously improved. Therefore, the compound is an organic electroluminescent device material with good performance.

Description

Technical Field

[0001] The present invention relates to the field of organic electroluminescent materials, and in particular to a bisdibenzofuran compound and an organic electroluminescent device thereof. Background Art

[0002] Organic Light-Emitting Diode (OLED) technology is a display and lighting technology based on organic materials. Its core lies in leveraging the luminescence properties of organic semiconductor materials when stimulated by an electric field. The following background information is provided, including its technical principles, development history, advantages, and challenges: Emissive Layer (EML): Contains luminescent materials (such as small molecules or polymers), where electrons and holes recombine, releasing energy and emitting light. Electron Transport Layer (ETL) and Hole Transport Layer (HTL): These layers are responsible for transporting electrons and holes, respectively, to the OLED, improving efficiency. Substrate: Typically glass or flexible plastic (such as polyimide), supporting the entire structure.

[0003] The blue host material is the core matrix in the OLED light-emitting layer, used to support the luminescent guest (such as fluorescent, phosphorescent, or TADF materials). It must simultaneously fulfill the following functions: energy transfer: efficiently transferring exciton energy to the luminescent guest; carrier transport: balancing the injection and transport of electrons and holes; and exciton confinement: preventing excitons from diffusing into non-luminescent areas (such as adjacent layers or electrodes). However, existing blue light-emitting materials have the following problems: 1) Efficiency: Low quantum efficiency: The external quantum efficiency (EQE) of blue light-emitting materials is generally lower than that of green and red light (e.g., blue light EQE is approximately 10%, while green light can reach over 30%); exciton quenching: High-energy blue light is prone to exciton annihilation (such as triplet-triplet quenching), which is particularly pronounced at high temperatures or high brightness. 2) Lifespan: Material degradation: The short wavelength of blue light (~450nm) and high photon energy easily trigger chemical bond breakage in organic molecules; and driving voltage: High driving voltage accelerates material aging, leading to brightness decay (e.g., the lifespan of blue light devices is only 1 / 3 to 1 / 5 that of green light). 3) Color Purity and Spectral Stability: Spectral Broadening: Blue light materials are susceptible to molecular vibration and stacking, resulting in broadened emission spectra (full width at half maximum > 50nm); Color shift: After long-term use, the luminescence peak shifts, affecting display consistency. 4) Cost and Process Complexity: Dependence on precious metals: Phosphorescent blue light requires rare metals such as iridium (Ir) and platinum (Pt), resulting in high material costs; Synthesis Difficulty: The synthesis steps of high-performance host materials (such as TADF) are complex and have low yields.

[0004] Therefore, it is urgent to develop more high-performance blue light materials, especially blue light host materials, to meet market demand. Summary of the Invention

[0005] In response to the problems existing in the prior art, the present invention provides a bis(dibenzofuran) compound, which can be used as a main material for an organic electroluminescent device and can improve the driving voltage, luminous efficiency and life of the device.

[0006] The present invention provides a bisdibenzofuran compound having a structure shown in formula (I):

[0007]

[0008] in,

[0009] Ar1 and Ar2 are the same or different and are independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;

[0010] R1-R2 are the same or different and are independently selected from hydrogen, deuterium, tritium, fluorine, bromine, iodine, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; or two adjacent R1s are linked together to form a substituted or unsubstituted ring, or two adjacent R2s are linked together to form a substituted or unsubstituted ring;

[0011] R3 are the same or different and are independently selected from hydrogen, deuterium, tritium, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;

[0012] L1-L3 are the same or different and are independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C2-C30 heteroarylene group;

[0013] n is the same or different and is independently selected from 0, 1, 2, 3 or 4;

[0014] m is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0015] The present invention also provides an organic electroluminescent device comprising a first electrode, a second electrode opposite to the first electrode, and at least one organic layer sandwiched between the first electrode and the second electrode, wherein the at least one organic layer comprises the bisdibenzofuran compound of the present invention.

[0016] The present invention provides a series of novel bis(dibenzofuran) compounds and light-emitting devices thereof. These compounds possess a bis(dibenzofuran) core structure and a structure similar to that of a bridged biphenyl. They exhibit high thermal and chemical stability, high carrier transport properties, suitable singlet and triplet states, and molecular orbital energy levels, and high luminescence quantum efficiency. When used as blue light-emitting host materials, these compounds generally exhibit superior performance in light-emitting devices, including significantly improved driving voltage, luminous efficiency, and lifetime. Therefore, the bis(dibenzofuran) compounds of the present invention are excellent materials for organic electroluminescent devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 Schematic diagram of the structure of an organic electroluminescent device.

[0018] Explanation of the reference numerals: 1 substrate; 2 anode; 3 hole injection layer; 4 hole transport layer; 5 electron blocking layer; 6 light-emitting layer; 7 hole blocking layer; 8 electron transport layer; 9 electron injection layer; 10 cathode.

[0019] Figure 2 Fluorescence emission spectrum of Example device 1. DETAILED DESCRIPTION

[0020] The following will be a clear and complete description of the technical solutions of the specific embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making any creative efforts shall fall within the scope of protection of the present invention.

[0021] In the compounds of the present invention, any atom not designated as a specific isotope is included as any stable isotope of that atom, and includes the atom at both its natural isotopic abundance and unnatural abundance.

[0022] Unless otherwise specified, the term "alkyl" refers to a monovalent saturated aliphatic hydrocarbon group, a straight or branched chain group containing 1 to 30 carbon atoms, preferably containing 1 to 15 carbon atoms, 1 to 10 carbon atoms, or 1 to 6 carbon atoms. Examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and the like.

[0023] Unless otherwise specified, the term "cycloalkyl" refers to a monocyclic saturated aliphatic hydrocarbon group having a specific number of carbon atoms, preferably containing 3-30 carbon atoms, preferably containing 3-15 carbon atoms or 3-10 carbon atoms or 3-8 carbon atoms, examples of which include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, etc.

[0024] Unless otherwise specified, the term "aryl" or "aromatic ring group" refers to a monocyclic, polycyclic, or fused aromatic carbocyclic ring system containing 6 to 30 carbon atoms, or 6 to 25 carbon atoms, or 6 to 14 carbon atoms, or 6 to 10 carbon atoms. The term "aryl" can be used interchangeably with the term "aromatic ring." Examples of aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, quaterphenyl, 1-phenylnaphthyl, 2-phenylnaphthyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, pyrenyl, perylenyl, fluoranthenyl, fluorenyl, benzofluorenyl, spirofluorenyl, spirobifluorenyl, and the like.

[0025] Unless otherwise specified, the term "arylene" refers to a radical derived from an aryl radical by removing a hydrogen atom. The arylene radical contains 6 to 30 carbon atoms, or 6 to 25 carbon atoms, or 6 to 14 carbon atoms, or 6 to 10 carbon atoms; examples of arylene radicals include, but are not limited to, phenylene, biphenylene, terphenylene, quaterphenylene, phenylnaphthylene, naphthylene, anthrylene, phenanthrenylene, triphenylene, pyrenylene, perylene, fluoranthenylene, fluorenylene, benzofluorenylene, spirofluorenylene, spirobifluorenylene, and the like.

[0026] Unless otherwise specified, the term "heteroaryl" or "heteroaryl ring group" means a monocyclic, polycyclic or fused ring system containing 2-30 carbon atoms, 2-25 carbon atoms, or 2-14 carbon atoms, or 3-10 carbon atoms, in which 1, 2, 3 or more of the ring atoms are heteroatoms independently selected from oxygen, sulfur, nitrogen, silicon, selenium or phosphorus atoms and the remaining atoms are carbon. Examples of heteroaryl groups include, but are not limited to, pyrrolyl, furanyl, thienyl, oxazolyl, thiazolyl, imidazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, bipyridyl, bipyrimidinyl, phenylpyridyl, phenylpyrimidinyl, spiroxanthenyl, spiroxanthenyl, acridinyl, 9,10-dihydroacridinyl, naphthyridinyl, indolyl, phenoxazinyl, phenothiazinyl, phenoxathiyl, quinolinyl, isoquinolinyl, , benzoquinolinyl, benzoisoquinolinyl, quinazoline, benzoquinazolinyl, quinoxalinyl, benzoquinoxalinyl, o-phenanthroline, benzofuranyl, dibenzofuranyl, naphthiobenzofuranyl, benzothienyl, benzothiazolyl, dibenzothienyl, naphthiobenzothienyl, benzoxazolyl, naphthioxazolyl, benzimidazolyl, naphthiazolyl, benzothiazolyl, naphthiozolyl, carbazolyl, benzocarbazolyl, and the like.

[0027] Unless otherwise specified, the term "heteroarylene" refers to a radical derived from a heteroaryl radical by removing a hydrogen atom. A heteroarylene radical contains 2-30 carbon atoms, 2-25 carbon atoms, or 2-14 carbon atoms, or 3-10 carbon atoms, wherein one, two, three or more ring atoms are heteroatoms and the remaining atoms are carbon, the heteroatoms being independently selected from oxygen, sulfur, nitrogen, silicon, selenium, or phosphorus atoms. Examples of heteroarylene radicals include, but are not limited to, pyridylene, pyrimidylene, triazinylene, dibenzofuranylene, dibenzothiophenylene, carbazolylene, and the like.

[0028] Unless otherwise specified, the term "halogen" or "halo" refers to F, Cl, Br, and I.

[0029] Unless otherwise indicated, the structural formulas described herein include all isomeric forms (e.g., enantiomers, diastereomers, and geometric isomers (or conformers)): for example, R and S configurations containing asymmetric centers, (Z) and (E) isomers of double bonds, and (Z) and (E) conformers. Therefore, single stereochemical isomers of the compounds of the present invention or mixtures of their enantiomers, diastereomers, or geometric isomers (or conformers) are within the scope of the present invention.

[0030] Unless otherwise specified, the term "substituted" means that a hydrogen atom in certain functional groups is replaced by another atom or functional group (i.e., a substituent), and the position of the substitution is not limited as long as the position is the position where the hydrogen atom is replaced, and when two or more substituents are substituted, the two or more substituents may be the same as or different from each other.

[0031] Unless otherwise specified, the term "substituted or unsubstituted" means not substituted or substituted with one or more substituents selected from the group consisting of deuterium, tritium, halogen, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C25 heteroaryl, amino substituted with substituted or unsubstituted C6-C25 aryl and / or substituted or unsubstituted C2-C25 heteroaryl, and substituted or unsubstituted silyl. Preferably, the "substituted or unsubstituted" means not substituted or substituted by one or more substituents selected from the group consisting of: deuterium, tritium, halogen, cyano, C1-C10 alkyl, halogen-substituted alkyl, C3-C10 cycloalkyl, C6-C14 aryl, C2-C14 heteroaryl, substituted or unsubstituted C6-C14 aryl and / or substituted or unsubstituted C2-C14 heteroaryl substituted amino, substituted or unsubstituted silyl. In the case of being substituted by multiple substituents, the multiple substituents are the same or different from each other. Most preferably, the term "substituted or unsubstituted" means not substituted or substituted with one or more substituents selected from the group consisting of deuterium, tritium, fluorine, chlorine, bromine, iodine, cyano, methyl, trifluoromethyl, deuterated methyl, ethyl, deuterated ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, deuterated phenyl, naphthyl, deuterated naphthyl, Anthracenyl, deuterated anthracenyl, phenanthryl, deuterated phenanthryl, triphenylene, pyrenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirobifluorenyl, pyridyl, pyrimidinyl, triazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, N-phenylcarbazolyl, N-biphenylcarbazolyl, dibenzofuranyl, dibenzothiophenyl, trimethylsilyl, triphenylsilyl; when substituted with multiple substituents, the multiple substituents may be the same or different.

[0032] Unless otherwise specified, when a substituent on a ring is not indicated as fixed, it represents that the substituent is attached to any of the corresponding optional positions of the ring.

[0033] Unless otherwise specified, when a substituent or a bond at a site of attachment runs through two or more rings, it indicates that it can be attached to any of the two or more rings, specifically any of the corresponding optional sites of the rings.

[0034] Unless otherwise specified, "adjacent groups connected to form a substituted or unsubstituted ring" means that adjacent groups are bonded and optionally aromatized to form a substituted or unsubstituted aromatic ring, heteroaromatic ring, aliphatic ring, or aliphatic heterocycle. Furthermore, the ring formed by the connection includes, but is not limited to, benzene, naphthalene, indene, cyclopentane, cyclohexane, pyridine, and pyrimidine. The term "adjacent groups" includes groups substituted on the same atom, groups substituted on adjacent atoms, and groups adjacent in space.

[0035] It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features described in detail below (such as in the embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they are not listed here one by one.

[0036] In a first aspect, the present invention provides a bisdibenzofuran compound having a structure shown in formula (I):

[0037]

[0038] in,

[0039] Ar1 and Ar2 are the same or different and are independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;

[0040] R1-R2 are the same or different and are independently selected from hydrogen, deuterium, tritium, fluorine, bromine, iodine, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; or two adjacent R1s are linked together to form a substituted or unsubstituted ring, or two adjacent R2s are linked together to form a substituted or unsubstituted ring;

[0041] R3 are the same or different and are independently selected from hydrogen, deuterium, tritium, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;

[0042] L1-L3 are the same or different and are independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C2-C30 heteroarylene group;

[0043] n is the same or different and is independently selected from 0, 1, 2, 3 or 4;

[0044] m is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0045] Preferably, Ar1 and Ar2 are the same or different and are independently selected from one of the following structures:

[0046]

[0047] Among them, R 11 、R 12 are the same or different and are independently selected from hydrogen, deuterium, tritium, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C18 heteroaryl; or two adjacent R 11 linked together to form substituted or unsubstituted rings;

[0048] M is selected from O, S, CR 13 R 14 or NR 15 , the R 13 、R 14 、R 15 the same or different, independently selected from substituted or unsubstituted C-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C18 heteroaryl;

[0049] a1 is the same or different and is independently selected from 0, 1, 2, 3, 4 or 5; a2 is the same or different and is independently selected from 0, 1, 2, 3 or 4; a3 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5, 6 or 7; a4 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; a0 is the same or different and is independently selected from 0, 1 or 2.

[0050] Preferably, Ar1 and Ar2 are the same or different and are independently selected from one of the following structures:

[0051]

[0052] Among them, R 11 、R 12 、R 21 the same or different, independently selected from hydrogen, deuterium, tritium, fluorine, chlorine, bromine, iodine, substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, pyrenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenylcarbazolyl, 9-biphenylcarbazolyl, 9-naphthylcarbazolyl;

[0053] a1 is the same or different and is independently selected from 0, 1, 2, 3, 4 or 5; a2 is the same or different and is independently selected from 0, 1, 2, 3 or 4; a3 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5, 6 or 7; a4 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; a0 is the same or different and is independently selected from 0, 1 or 2; a5 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5 or 6; a is the same or different and is independently selected from 0, 1, 2, 3, 4 or 5.

[0054] Preferably, R 11 、R 12 、R 21 The substituents in the "substituted or unsubstituted" are selected from the group consisting of deuterium, tritium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted phenyl, and substituted or unsubstituted pyridyl.

[0055] Preferably, Ar1 and Ar2 are the same or different and are independently selected from one of the following structures:

[0056]

[0057] Preferably, L1-L3 are the same or different and are independently selected from a single bond, or substituted or unsubstituted: phenylene, biphenylene, naphthylene, pyridylene, pyrimidylene.

[0058] Preferably, L1-L3 are the same or different and are independently selected from a single bond, or one of the following groups:

[0059]

[0060] Among them, R a is selected from hydrogen, deuterium, tritium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C14 aryl, substituted or unsubstituted C2-C12 heteroaryl; or two adjacent R a linked together to form a substituted or unsubstituted C6-C10 aromatic ring;

[0061] b1 is the same or different and is independently selected from 0, 1, 2, 3 or 4; b2 is the same or different and is independently selected from 0, 1, 2 or 3; b3 is the same or different and is independently selected from 0, 1 or 2; b4 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5 or 6.

[0062] Preferably, R aSelected from hydrogen, deuterium, tritium, fluorine, chlorine, bromine, iodine, cyano, trifluoromethyl, substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl.

[0063] Preferably, R a The substituents in the "substituted or unsubstituted" are selected from the group consisting of deuterium, tritium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted phenyl, and substituted or unsubstituted pyridyl.

[0064] Preferably, the R1-R2 are the same or different and are independently selected from hydrogen, deuterium, tritium, fluorine, bromine, iodine, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C14 aryl, substituted or unsubstituted C2-C12 heteroaryl; or two adjacent R1s are connected together to form a substituted or unsubstituted C6-C10 aromatic ring, or two adjacent R2s are connected together to form a substituted or unsubstituted C6-C10 aromatic ring.

[0065] Preferably, the R3 are the same or different and are independently selected from hydrogen, deuterium, tritium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C14 aryl, substituted or unsubstituted C2-C12 heteroaryl.

[0066] Preferably, R1-R2 are the same or different and are independently selected from hydrogen, deuterium, tritium, fluorine, bromine, iodine, substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, pyrenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenylcarbazolyl, 9-biphenylcarbazolyl, 9-naphthylcarbazolyl.

[0067] Preferably, the R3 are the same or different and are independently selected from hydrogen, deuterium, tritium, fluorine, chlorine, bromine, iodine, substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, pyrenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenylcarbazolyl, 9-biphenylcarbazolyl, 9-naphthylcarbazolyl.

[0068] Preferably, the substituents in "substituted or unsubstituted" in R1-R3 are selected from: deuterium, tritium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl.

[0069] In one embodiment, the bisdibenzofuran compound has a structure shown in formula (I-1) to formula (I-3):

[0070]

[0071] wherein, Ring A is selected from a C6-C10 aromatic ring substituted or unsubstituted by one or more R1; Ring B is selected from a C6-C10 aromatic ring substituted or unsubstituted by one or more R2;

[0072] n1 is the same or different and is independently selected from 0, 1 or 2; n2 is the same or different and is independently selected from 0, 1 or 2.

[0073] Ar1-Ar2, R1-R3, L1-L3, n, and m are as defined herein.

[0074] Preferably, R1-R2 are the same or different and are independently selected from hydrogen, deuterium, tritium, fluorine, bromine, iodine, substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, phenyl, biphenyl, terphenyl, naphthyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl.

[0075] Preferably, the ring A is selected from the group consisting of a benzene ring and a naphthalene ring, which are substituted or unsubstituted with one or more R3.

[0076] Preferably, the ring B is selected from the group consisting of a benzene ring and a naphthalene ring, which are substituted or unsubstituted with one or more R4.

[0077] In the present invention, Ring A and Ring B may be fused at any appropriate position of the benzene ring to be fused therewith.

[0078] In one embodiment, the bisdibenzofuran compound has a structure shown in formula (I-4) to formula (I-6):

[0079]

[0080] wherein n3 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5 or 6; and n4 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5 or 6.

[0081] Ar1-Ar2, R1-R3, L1-L3, n, and m are as defined herein.

[0082] Preferably, R1-R2 are the same or different and are independently selected from hydrogen, deuterium, tritium, fluorine, bromine, iodine, substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, phenyl, biphenyl, terphenyl, naphthyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl.

[0083] In one embodiment, the deuteration rate of the bis-dibenzofuran compound is 1-99%, preferably, the deuteration rate is 10-90%, and more preferably, the deuteration rate of the bis-dibenzofuran compound is 60-90%.

[0084] In one embodiment, the bisdibenzofuran compound is selected from:

[0085]

[0086]

[0087] The above lists only some specific structural forms of the bis(dibenzofuran) compounds represented by formula (I), but the present invention is not limited to these chemical structures listed. All chemical structures based on formula (I) and with substituents as defined in the present invention are included.

[0088] The bisdibenzofuran compound represented by formula (I) of the present invention can be prepared by one of the following synthetic routes:

[0089]

[0090] wherein X1, X2, X3, and X4 are the same or different and are independently selected from chlorine, bromine, or iodine;

[0091] M1, M2 are the same or different, and are independently selected from -B(OH)2 or

[0092] In a second aspect, the present invention further provides a light-emitting device comprising a first electrode, a second electrode opposite to the first electrode, and at least one organic layer sandwiched between the first electrode and the second electrode, wherein the at least one organic layer comprises the bis(dibenzofuran) compound of the present invention.

[0093] In one embodiment, the light-emitting device is an organic electroluminescent device; preferably, the light-emitting device is a blue organic electroluminescent device.

[0094] In one embodiment, the organic layer includes a light-emitting layer, and the light-emitting layer contains the bisdibenzofuran compound of the present invention.

[0095] In one embodiment, the organic layer includes a light-emitting layer, the light-emitting layer includes a host material, and the host material includes the bis(dibenzofuran) compound of the present invention.

[0096] In one embodiment, Figure 1 As shown, the organic electroluminescent device of the present invention is obtained by sequentially arranging various layers (for example, an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking 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) on a substrate 1.

[0097] The organic electroluminescent device of the present invention is not limited to such a structure. For example, in the multilayer structure, one or some of the organic layers can be omitted. For example, the hole blocking layer 7 between the light-emitting layer 6 and the electron transport layer 8 can be omitted, and the anode 2, the hole injection layer 3, the hole transport layer 4, the electron blocking layer 5, the light-emitting layer 6, the electron transport layer 8, the electron injection layer 9 and the cathode 10 are sequentially arranged on the substrate 1. Alternatively, the hole injection layer 3 between the anode 2 and the hole transport layer 4, the hole blocking layer 7 between the light-emitting layer 6 and the electron transport layer 8, and the electron injection layer 9 between the electron transport layer 8 and the cathode 10 can be omitted at the same time, and the anode 2, the hole transport layer 4, the electron blocking layer 5, the light-emitting layer 6, the electron transport layer 8 and the cathode 10 are sequentially arranged on the substrate 1 to finally obtain the corresponding organic electroluminescent device.

[0098] The organic electroluminescent device of the present invention is not limited to such a structure. For example, in the multilayer structure, one or some of the organic layers can be omitted. For example, the hole blocking layer 7 between the light-emitting layer 6 and the electron transport layer 8 can be omitted, and the anode 2, the hole injection layer 3, the hole transport layer 4, the electron blocking layer 5, the light-emitting layer 6, the electron transport layer 8, the electron injection layer 9 and the cathode 10 are sequentially arranged on the substrate 1. Alternatively, the hole injection layer 3 between the anode 2 and the hole transport layer 4, the hole blocking layer 7 between the light-emitting layer 6 and the electron transport layer 8, and the electron injection layer 9 between the electron transport layer 8 and the cathode 10 can be omitted at the same time, and the anode 2, the hole transport layer 4, the electron blocking layer 5, the light-emitting layer 6, the electron transport layer 8 and the cathode 10 are sequentially arranged on the substrate 1 to finally obtain the corresponding organic electroluminescent device.

[0099] The anode of the organic electroluminescent device of the present invention can be composed of known electrode materials. For example, electrode materials with a large work function can be used, such as metals such as vanadium, chromium, copper, zinc, and gold, or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline. Among these, ITO is preferred.

[0100] As the hole injection layer of the organic electroluminescent device of the present invention, known materials with hole injection properties can be used. For example, porphyrin compounds represented by copper phthalocyanine, naphthalenediamine compounds, star-shaped triphenylamine compounds, aromatic amine compounds having a structure in which three or more triphenylamine structures are connected by a single bond or a divalent group containing no heteroatoms, triphenylamine trimers and tetramers, acceptor-type dibenzofuran compounds such as hexacyanoazatriphenylene, and coating-type polymer materials. These materials can be formed into thin films by known methods such as vapor deposition, spin coating, and inkjet methods.

[0101] As the hole transport layer of the organic electroluminescent device of the present invention, a well-known material with hole transport properties can be used. In addition, other well-known materials with hole transport properties can also be used. For example, compounds containing m-carbazolylphenyl; such as N,N'-diphenyl-N,N'-di(m-tolyl)benzidine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), N,N,N',N'-tetraphenylbenzidine and other benzidine derivatives; 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC); various triphenylamine trimers and tetramers; 9,9',9"-triphenyl -9H,9'H,9"H-3,3':6',3"-tricarbazole (Tris-PCz), etc. These can be formed into films alone or as a single layer formed by mixing with other materials. They can also be formed into a stacked structure of layers formed from individual films, a stacked structure of layers formed from mixed films, or a stacked structure of layers formed from individual films and layers formed from mixed films. These materials can be formed into thin films by known methods such as vapor deposition, spin coating, and inkjet methods.

[0102] In addition, materials commonly used in the hole injection layer or hole transport layer may be further P-doped with tribromoaniline antimony hexachloride, a radialene derivative, or a polymer compound partially having a structure of a benzidine derivative such as TPD.

[0103] As the electron blocking layer of the organic electroluminescent device of the present invention, a well-known material with electron blocking properties can be used. In addition, other well-known compounds with electron blocking effects can also be used to form it. For example, carbazole derivatives such as 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA), 9,9-bis[4-(carbazol-9-yl)phenyl]fluorene, 1,3-bis(carbazol-9-yl)benzene (mCP), 2,2-bis(4-carbazol-9-ylphenyl)adamantane (Ad-Cz); compounds with triphenylsilyl and triarylamine structures represented by 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluorene Compounds with electron-blocking properties, such as monoamine compounds with high electron-blocking properties and various triphenylamine dimers, can be used alone or in a single layer by mixing with other materials. They can also be used in a laminated structure of layers formed from individual films, a laminated structure of layers formed from mixed films, or a laminated structure of layers formed from individual films and mixed films. These materials can be formed into thin films using known methods such as vapor deposition, spin coating, and inkjet methods.

[0104] The light-emitting layer of the organic electroluminescent device of the present invention preferably comprises a fluorene dibenzofuran compound represented by formula (I) of the present invention. In addition, various metal complexes such as metal complexes of hydroxyquinoline derivatives headed by Alq3, compounds having a pyrimidine ring structure, anthracene derivatives, bis(vinylbenzene) derivatives, pyrene derivatives, oxazole derivatives, and poly(p-phenylene vinylene) derivatives can also be used.

[0105] The light-emitting layer can be composed of a host material and a dopant material. As the host material, it is preferred to include a fluorene dibenzofuran compound represented by formula (I) of the present invention. In addition, mCBP, mCP, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, dibenzofuran compounds having an indole ring as a partial structure of the fused ring, etc. can also be used. As the dopant material, it is preferred to include a dibenzofuran derivative of the present invention. In addition, aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, etc. can also be used. For example, pyrene derivatives, anthracene derivatives, quinacridone, coumarin, rubrene, perylene and their derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, spirocyclic bisfluorene derivatives, etc. can be listed. These materials can be formed into films alone or mixed with other materials to form a single layer. They can also be used in the form of a laminated structure of layers formed alone, a laminated structure of layers formed as a mixture, or a laminated structure of layers formed alone and layers formed as a mixture. These materials can be formed into thin films by known methods such as vapor deposition, spin coating, and inkjet.

[0106] Preferably, the mass ratio of the host material to the doping material in the light-emitting layer may be 50-99:1-50, and preferably, the mass ratio may be 80-99:1-20.

[0107] As the hole blocking layer of the organic electroluminescent device of the present invention, a known material with hole blocking properties can be used. In addition, other compounds with hole blocking properties can also be used to form. For example, phenanthroline derivatives such as 2,4,6-tris (3-phenyl) -1,3,5-triazine (T2T), 1,3,5-tris (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBi), bathocuproine (BCP), metal complexes of quinolinol derivatives such as aluminum (III) bis (2-methyl-8-hydroxyquinoline) -4-phenylphenolate (BAlq), and various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, etc. have hole blocking effects. They can be formed into a film alone, or used in the form of a single layer formed by mixing a film with other materials, or can be made into a stacked structure of layers formed by separate film formation, a stacked structure of layers formed by mixed film formation, or a stacked structure of layers formed by separate film formation and a layer formed by mixed film formation. These materials can be formed into thin films by known methods such as vapor deposition, spin coating, and inkjet.

[0108] The above-mentioned hole-blocking material can also be used to form the electron transport layer described below. That is, by using the above-mentioned known hole-blocking material, a layer serving as both a hole-blocking layer and an electron transport layer can be formed.

[0109] As the electron transport layer of the organic electroluminescent device of the present invention, a well-known material with electron transport properties can be used. In addition, other compounds with electron transport properties can also be used. For example, metal complexes of hydroxyquinoline derivatives headed by Alq3 and BAlq; various metal complexes; triazole derivatives; triazine derivatives; oxadiazole derivatives; pyridine derivatives; bis(10-hydroxybenzo[H]quinoline)beryllium (Be(bq)2); benzimidazole derivatives such as 2-[4-(9,10-dinaphthyl-2-anthracen-2-yl)phenyl]-1-phenyl-1H-benzimidazole (ETL); thiadiazole derivatives; anthracene derivatives; carbodiimide derivatives; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives; thiole derivatives, etc. These materials can be formed into films alone, or used as a single layer formed by mixing with other materials, or can be formed into a laminated structure of layers formed alone, a laminated structure of layers formed as a mixture, or a laminated structure of layers formed alone and layers formed as a mixture. These materials can be formed into thin films by known methods such as vapor deposition, spin coating, and inkjet.

[0110] As the electron injection layer of the organic electroluminescent device of the present application, a material known per se can be used. For example, alkali metal salts such as lithium fluoride, cesium fluoride; alkaline earth metal salts such as magnesium fluoride; metal complexes of hydroxyquinoline derivatives such as lithium quinolate; metal oxides such as aluminum oxide; and the like.

[0111] In the electron transport layer or the electron injection layer, a material further doped with a metal such as cesium, a triarylphosphine oxide derivative, or the like can be used for the material usually used in the layer.

[0112] As the cathode of the organic electroluminescent device of the present application, an electrode material having a low work function (such as aluminum, magnesium) or an alloy having a low work function (such as a magnesium-silver alloy, a magnesium-indium alloy, an aluminum-magnesium alloy) is preferably used as the electrode material.

[0113] As the substrate of the present application, a substrate used in conventional organic light-emitting devices, such as glass or plastic, can be used. In the present application, a glass substrate is selected.

[0114] The present application will be further described below with reference to specific examples. It should be understood that these examples are intended to illustrate the present application and are not intended to limit the scope of the present application. The experimental methods in the following examples, for which specific conditions are not mentioned, are generally carried out under conventional conditions or under conditions recommended by the manufacturers. Unless otherwise defined, all the professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any method and material similar or equivalent to those described can be used in the present application. The preferred methods and materials shown herein are only for demonstration.

[0115] Example 1: Synthesis of BH1

[0116]

[0117] Step 1: The reactant 2,5-dibromo-1,4-benzenediol (60 g, 223.96 mmol) was dissolved in 400 ml of tetrahydrofuran, cooled to 0°C, and 60% sodium hydride (26.87 g, 671.88 mmol) was added portionwise slowly. After the addition was completed, the mixture was stirred for 20 min, and bromomethyl methyl ether (83.96 g, 671.88 mmol) was added dropwise. After the dropwise addition was completed, the mixture was stirred for 30 min, and then the temperature was raised to room temperature and stirring was continued for 4 h. After the reaction was completed, the organic phase was quenched with 300 ml of water, and then 200 ml of ethyl acetate was added for extraction. This process was repeated three times, and the combined organic phase was washed with 300 ml of water three times. The organic phase was concentrated under reduced pressure at low temperature to obtain a residue, which was purified by silica gel column chromatography (petroleum ether: ethyl acetate = 0-100%) to obtain the product of step 1: 75 g, yield: 94.06%. MS-ESI calculated value [M+H] + 357.01, found 357.01.

[0118] Step 2: The product of step 1 (75 g, 210.67 mmol), reactant 1, i.e., 2-fluorophenylboronic acid (64.85 g, 463.47 mmol), potassium carbonate (116.46 g, 842.67 mmol), 400 ml of 1,4-dioxane, and 200 ml of water were stirred and dissolved, and the atmosphere was replaced with nitrogen three times. Then, catalyst Pd(PPh3)4 (1.95 g, 1.69 mmol) was added, and the atmosphere was replaced with nitrogen three times. The temperature was raised to 85°C and refluxed for 5 h. The reaction system was cooled and concentrated under reduced pressure to obtain a residue. The residue was dissolved and extracted with water and dichloromethane, and the organic phase was separated. The organic phase was concentrated and loaded and purified by silica gel column chromatography (petroleum ether: ethyl acetate = 0-100%) to obtain step 2 product: 70 g, yield

[0119] Efficiency: 85.99%. MS-ESI calculated value [M+H] + 387.39, the actual measured value is 387.39.

[0120] Step 3: Dissolve the product from Step 2 (70 g, 181.16 mmol) in tetrahydrofuran and ethanol (200 ml:100 ml). Cool to below 0°C and slowly add concentrated hydrochloric acid (54.82 g, 1500 mmol) dropwise to the reaction mixture. Stir for 0.5 h. Return to room temperature and stir for 5 h. After TLC confirmation of the complete reaction, quench the organic phase with 300 ml of water and extract with 200 ml of ethyl acetate three times. Repeat this process three times. Combine the organic phases, wash three times with 300 ml of water, and concentrate under reduced pressure at low temperature to obtain a residue. The residue is purified by silica gel column chromatography (petroleum ether:ethyl acetate = 0-100%) to obtain 50 g of the product from Step 3, in a yield of 92.53%. MS-ESI calculated value [M+H] + 299.26, the measured value is 299.26.

[0121] Step 4: The product from Step 3 (50 g, 167.62 mmol) was dissolved in DMF (250 ml). Powdered potassium carbonate (92.66 g, 670.49 mmol) was added, and the mixture was heated to 150°C and refluxed. After stirring for 5 h, the mixture was concentrated under reduced pressure to obtain a residue. The residue was extracted with water and dichloromethane, and the organic phase was separated. The organic phase was concentrated and purified by silica gel column chromatography (petroleum ether:ethyl acetate = 0-100%) to obtain 37 g of the product from Step 4, in a yield of 85.46%. MS-ESI calculated [M+H] value was 259.28, and the measured value was 259.28.

[0122] Step 5: Dissolve the product from Step 4 (37 g, 143.26 mmol) in 300 ml of anhydrous THF, cool to -78°C, and add 116.4 ml of n-butyllithium (1.6 M in THF) dropwise to the reaction mixture. After complete addition, incubate for 1 hour. Add dibromotetrachloroethane (69.97 g, 214.89 mmol) dropwise to the reaction mixture. After 2 hours, return the mixture to room temperature and continue the reaction. Samples were taken to monitor the complete reaction. After addition, saturated aqueous ammonium chloride was added to quench the reaction. Extraction was performed with 200 ml of ethyl acetate three times. The organic phases were combined and washed three times with 300 ml of water. The organic phases were then concentrated under reduced pressure at low temperature to obtain a residue. The residue was purified by silica gel column chromatography (petroleum ether:ethyl acetate = 0-100%) to obtain 35 g of the product from Step 5, in a yield of 72.46%. MS-ESI calculated value [M+H] + 338.17, the measured value is 338.17.

[0123] Step 6: The product from Step 5 (35 g, 103.80 mmol), reactant 2 (phenylboronic acid (15.19 g, 124.57 mmol), potassium carbonate (43.04 g, 311.41 mmol), 300 mL of 1,4-dioxane, and 150 mL of water were stirred and dissolved. The atmosphere was purged with nitrogen three times, and then the catalyst, Pd(PPh3)4 (0.6 g, 0.519 mmol), was added. After purging with nitrogen three times, the temperature was raised to 85°C and refluxed for 5 h. The reaction system was cooled and concentrated under reduced pressure to obtain a residue. The residue was dissolved and extracted with water and dichloromethane. The organic phase was separated and concentrated, and the organic phase was purified by silica gel column chromatography (petroleum ether:ethyl acetate = 0-100%) to obtain 30 g of the product from Step 6, in a yield of 86.43%. MS-ESI calculated value [M+H] + 335.37, the measured value is 335.37.

[0124] Step 7: Dissolve the product from Step 6 (30 g, 89.72 mmol) in 300 ml of anhydrous THF, cool to -78°C, and add 72.90 ml of n-butyllithium (1.6 M in THF) dropwise to the reaction mixture. After complete addition, incubate for 1 hour. Add dibromotetrachloroethane (43.82 g, 134.58 mmol) dropwise to the reaction mixture. After 2 hours, return the mixture to room temperature and continue the reaction. Samples were taken to monitor the complete reaction. After addition, saturated aqueous ammonium chloride was added to quench the reaction. Extraction was performed with 200 ml of ethyl acetate three times. The organic phases were combined and washed three times with 300 ml of water. The organic phases were then concentrated under reduced pressure at low temperature to obtain a residue. The residue was purified by silica gel column chromatography (petroleum ether:ethyl acetate = 0-100%) to obtain 26 g of the product from Step 7, in a yield of 70.12%. MS-ESI calculated value [M+H] +413.27, the measured value is 413.27.

[0125] Step 8: The product from Step 7 (26 g, 62.91 mmol), reactant 3 (phenylanthraceneboronic acid (24.38 g, 81.79 mmol), potassium carbonate (26.08 g, 188.74 mmol), 300 mL of 1,4-dioxane, and 150 mL of water were stirred and dissolved. The atmosphere was purged with nitrogen three times, and then the catalyst, Pd(PPh3)4 (0.363 g, 0.315 mmol), was added. After purging with nitrogen three times, the temperature was raised to 85°C and refluxed for 5 h. The reaction system was cooled and concentrated under reduced pressure to obtain a residue. The residue was dissolved and extracted with water and dichloromethane. The organic phase was separated and concentrated, and the organic phase was purified by silica gel column chromatography (petroleum ether:ethyl acetate = 0-100%) to obtain 30 g of the product from Step 6. White crystals were crystallized from toluene and dried to obtain 28 g, with a yield of 75.65%. MS-ESI calculated value [M+H] + 587.19, the actual measured value is 587.19.

[0126] Example 2-12

[0127] With reference to the synthetic route in Example 1, and selecting the corresponding reactant 1, reactant 2 and reactant 3, a series of specific compounds of the present invention were prepared respectively (see Table 1).

[0128] Table 1

[0129]

[0130]

[0131]

[0132]

[0133] The yield and mass spectrum of the target product are shown in Table 2 below:

[0134] Table 2

[0135]

[0136]

[0137]

[0138]

[0139] Example 13: Synthesis of BH13

[0140] Compound BH1 (5 g, 8.522 mmol), 10% palladium on carbon (0.2 g), and deuterated water (150 mL) were added to a 300 mL autoclave and heated to 240°C for 12 h. The reaction system was cooled to room temperature, the organic phase was concentrated, the deuterated water was recovered, and the concentrated solid was purified by silica gel column chromatography (petroleum ether:ethyl acetate = 0-100%) to obtain 4.5 g of the product, with a yield of 90%. MS-ESI analysis value [M+H] + The molecular weight of BH1 is 609.19, compared with 586.25 of BH1, with 22 deuterium substitutions and a deuteration rate of 84.6%.

[0141] Example 14: Synthesis of BH14

[0142] Compound BH10 (5 g, 7.86 mmol), 10% palladium on carbon (0.2 g), and deuterated water (150 mL) were added to a 300 mL autoclave and heated to 240°C for 12 h. The reaction system was cooled to room temperature, the organic phase was concentrated, the deuterated water was recovered, and the concentrated solid was purified by silica gel column chromatography (petroleum ether:ethyl acetate = 0-100%) to give 4.5 g of the product, in a 90% yield. MS-ESI analysis value [M+H] + The molecular weight of BH10 is 661.21, compared with 636.21, there are 24 deuterium substitutions and the deuteration rate is 85.7%.

[0143] Example 15: Preparation of organic electroluminescent device 1 (organic EL device 1)

[0144] A hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, an electron transport layer 8, an electron injection layer 9 and a cathode 10 are sequentially formed on a transparent anode 2 pre-formed on a glass substrate 1 to prepare a Figure 1 The organic electroluminescent device shown (but without the hole blocking layer 7).

[0145] Specifically, a glass substrate with a 100 nm thick ITO film was ultrasonically treated in Decon 90 alkaline cleaning solution, rinsed in deionized water, cleaned three times in acetone and ethanol, baked in a clean environment until the water was completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam. The glass substrate with the ITO electrode was placed in a vacuum chamber and evacuated to 4×10 -4 -2×10 -5Pa. Then, 97wt% HIL / 3wt% HTL was evaporated on the above-mentioned glass substrate with an ITO electrode at a evaporation rate of 0.2nm / s to form a layer with a thickness of 10nm, which served as a hole injection layer. On the hole injection layer, HTL was evaporated at a evaporation rate of 0.2nm / s to form a layer with a thickness of 40nm, which served as a hole transport layer. On the hole transport layer, EBL was evaporated at a evaporation rate of 0.2nm / s to form a layer with a thickness of 10nm, which served as an electron blocking layer. On the electron blocking layer, the compound (BH1) in Example 1 as the main material was evaporated at a rate of 0.19nm / s and the BD1 as the dopant material was evaporated at a rate of 0.01nm / s to form a layer with a thickness of 20nm, which served as a light-emitting layer. The doping weight ratio of BD1 was 5wt%. On the light-emitting layer, ZADN was deposited at a rate of 0.2 nm / s to form a 40 nm thick layer, serving as an electron-transporting layer. On the electron-transporting layer, Liq was deposited at a rate of 0.02 nm / s to form a 2 nm thick layer, serving as an electron-injection layer. Finally, aluminum was deposited at a rate of at least 0.5 nm / s on the electron-injection layer to form a 100 nm thick cathode.

[0146] Examples 16-28: Preparation of Organic EL Devices 2-14

[0147] Referring to the preparation conditions of the organic EL device 1 in Example 15, organic EL devices 2 to 14 were prepared respectively using compounds corresponding to the structures of each layer.

[0148] Comparative Examples 1-6: Preparation of Single-layer Organic EL Devices Comparative Examples 1-6

[0149] Referring to the preparation conditions of the organic EL device 1 in Example 15, and using the compounds corresponding to the layer structures in Table 3, organic EL device Comparative Examples 1-6 were prepared respectively.

[0150] Table 3

[0151]

[0152]

[0153] The organic EL devices in Table 3 use the dibenzofuran compounds of the present invention as the blue light host material of the light-emitting layer, and are matched with the blue light guest material BD1, while the comparative examples of the organic EL devices use the naphthofuran anthracene-containing DBH1, DBH2, naphthoanthracene mono-substituted dibenzofuran DBH3, and anthracene mono-substituted dibenzofuran compound DBH4, fluorene furan structure DBH5, and anthracene substituted fluorene DBH6 used in the existing market as the blue light host material of the light-emitting layer, and the same blue light guest.

[0154] The structures of the compounds involved in the organic EL device and the comparative example of the organic EL device are as follows:

[0155]

[0156] The luminescence characteristics of the organic EL devices 1-14 prepared in Examples 15-28 and the organic EL devices Comparative Examples 1-6 prepared in Comparative Examples 1-6 were measured under a DC voltage applied at room temperature in air. The current-luminance-voltage characteristics of the devices were measured using a Keithley source-measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) equipped with a calibrated silicon photodiode. The electroluminescence spectra were measured using a Photo Research PR655 spectrometer. The external quantum efficiency of the devices was calculated using the method described in Adv. Mater., 2003, 15, 1043-1048. The measurement results are shown in Table 4.

[0157] Table 4

[0158]

[0159]

[0160] As shown in Table 4, single-layer organic EL devices made with the compounds of the present invention exhibit lower voltage, higher efficiency, and longer lifespan compared to devices composed of existing commercial materials DBH1-DBH4, demonstrating that devices using the compounds of the present invention as blue light-emitting host materials generally exhibit superior performance. This is primarily due to the fact that the bis(dibenzofuran) structure extends the electron cloud conjugation length compared to a simple dibenzofuran structure. When the molecule accepts electrons and transforms into an anionic state, the negative charge is effectively and evenly dispersed across the bis(dibenzofuran) fragments, avoiding uneven charge distribution that would otherwise lead to excessive energy, further improving the compound's thermal stability. Furthermore, compared to devices composed of the similarly structured DBH5 and DBH6, the compounds exhibit superior performance. This is primarily due to the fact that the phenyl and anthracene groups are introduced at different sites, making the molecule of the present invention equivalent to a bridged biphenyl structure while simultaneously taking into account the properties of bis(dibenzofuran), resulting in high thermal stability, high chemical stability, and high carrier transport. More importantly, they possess suitable singlet and triplet states, molecular orbital energy levels, and high luminescence quantum efficiency. In addition, compared with DBH6, the introduction of aromatic groups not only plays a bridging structural role and provides molecular stability, but the additional aromatic groups increase conjugation and improve luminous efficiency. At the same time, the device performance results of BH1-BH9 and BH13 show that the device corresponding to the bis-dibenzofuran compounds of the present invention containing deuterium atoms will have improved efficiency and longer device life than the device corresponding to the compound without deuterium atoms. The reason is that the CD bond is more stable than the C-H bond. It is also found that the effects of non-positional deuteration and full deuteration are similar. The reason is that the process of deuteration is to replace the C-H bond with small bond energy, and the more stable C-H bond is not easily deuterated. Secondly, the effect of deuteration at different sites is different. The main reason is that the charge is distributed in different areas in the molecule, the C-H bond energy is different, and the stability is different.

[0161] In addition, from Figure 2 The results shown in FIG2 show that when the bis(dibenzofuran) compounds of the present invention are used as the main material of the light-emitting layer in the device, the luminescence pattern of the device is not affected, indicating that energy can be completely transferred to the light-emitting material in the device.

[0162] As can be seen from the above, the bis(dibenzofuran) compounds of the present invention can effectively reduce the operating voltage compared to the commonly used blue light host materials in the prior art, while improving the external quantum efficiency and extending the device life.

[0163] The above describes the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A bisdibenzofuran compound having a structure shown in formula (I): in, Ar1 and Ar2 are the same or different and are independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; R1-R2 are the same or different and are independently selected from hydrogen, deuterium, tritium, fluorine, bromine, iodine, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; or two adjacent R1s are linked together to form a substituted or unsubstituted ring, or two adjacent R2s are linked together to form a substituted or unsubstituted ring; R3 are the same or different and are independently selected from hydrogen, deuterium, tritium, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; L1-L3 are the same or different and are independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C2-C30 heteroarylene group; n is the same or different and is independently selected from 0, 1, 2, 3 or 4; m is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

2. The compound according to claim 1, characterized in that The Ar1 and Ar2 are the same or different and are independently selected from one of the following structures: Among them, R 11 、R 12 are the same or different and are independently selected from hydrogen, deuterium, tritium, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C18 heteroaryl; or two adjacent R 11 linked together to form substituted or unsubstituted rings; M is selected from O, S, CR 13 R 14 or NR 15 , the R 13 、R 14 、R 15 the same or different, independently selected from substituted or unsubstituted C-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C18 heteroaryl; a1 is the same or different and is independently selected from 0, 1, 2, 3, 4 or 5; a2 is the same or different and is independently selected from 0, 1, 2, 3 or 4; a3 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5, 6 or 7; a4 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; a0 is the same or different and is independently selected from 0, 1 or 2.

3. The compound according to claim 1, characterized in that The Ar1 and Ar2 are the same or different and are independently selected from one of the following structures: Among them, R 11 、R 12 、R 21 the same or different, independently selected from hydrogen, deuterium, tritium, fluorine, chlorine, bromine, iodine, substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, pyrenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenylcarbazolyl, 9-biphenylcarbazolyl, 9-naphthylcarbazolyl; a1 is the same or different and is independently selected from 0, 1, 2, 3, 4 or 5; a2 is the same or different and is independently selected from 0, 1, 2, 3 or 4; a3 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5, 6 or 7; a4 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; a0 is the same or different and is independently selected from 0, 1 or 2; a5 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5 or 6; a is the same or different and is independently selected from 0, 1, 2, 3, 4 or 5.

4. The compound according to claim 1, characterized in that The L1-L3 are the same or different and are independently selected from a single bond, or substituted or unsubstituted: phenylene, biphenylene, naphthylene, pyridylene, pyrimidylene; Preferably, L1-L3 are the same or different and are independently selected from a single bond, or one of the following groups: Among them, R a is selected from hydrogen, deuterium, tritium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C14 aryl, substituted or unsubstituted C2-C12 heteroaryl; or two adjacent R a linked together to form a substituted or unsubstituted C6-C10 aromatic ring; b1 is the same or different and is independently selected from 0, 1, 2, 3 or 4; b2 is the same or different and is independently selected from 0, 1, 2 or 3; b3 is the same or different and is independently selected from 0, 1 or 2; b4 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5 or 6.

5. The compound according to claim 1, characterized in that The R1-R2 are the same or different and are independently selected from hydrogen, deuterium, tritium, fluorine, bromine, iodine, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C14 aryl, substituted or unsubstituted C2-C12 heteroaryl; or two adjacent R1s are linked together to form a substituted or unsubstituted C6-C10 aromatic ring, or two adjacent R2s are linked together to form a substituted or unsubstituted C6-C10 aromatic ring; the R3 are the same or different and are independently selected from hydrogen, deuterium, tritium, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C14 aryl, substituted or unsubstituted C2-C12 heteroaryl; Preferably, R1-R2 are the same or different and are independently selected from hydrogen, deuterium, tritium, fluorine, bromine, iodine, substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, pyrenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenylcarbazolyl, 9-biphenylcarbazolyl, 9-naphthylcarbazolyl R3 is the same or different and is independently selected from hydrogen, deuterium, tritium, fluorine, chlorine, bromine, iodine, substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, pyrenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenylcarbazolyl, 9-biphenylcarbazolyl, 9-naphthylcarbazolyl.

6. The compound according to claim 1, characterized in that The bisdibenzofuran compounds have structures shown in formula (I-1) to formula (I-3): wherein, Ring A is selected from a C6-C10 aromatic ring substituted or unsubstituted by one or more R1; Ring B is selected from a C6-C10 aromatic ring substituted or unsubstituted by one or more R2; n1 is the same or different and is independently selected from 0, 1 or 2; n2 is the same or different and is independently selected from 0, 1 or 2. Preferably, the bisdibenzofuran compound has a structure shown in formula (I-4) to formula (I-6): wherein n3 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5 or 6; and n4 is the same or different and is independently selected from 0, 1, 2, 3, 4, 5 or 6.

7. The compound according to claim 1, characterized in that The deuteration rate of the bis(dibenzofuran) compound is 1-99%, preferably, the deuteration rate is 10-90%.

8. The compound according to claim 1, characterized in that The compound is selected from: 9 . A light-emitting device comprising a first electrode, a second electrode opposite to the first electrode, and at least one organic layer sandwiched between the first electrode and the second electrode, wherein the at least one organic layer comprises the bisdibenzofuran compound according to claim 1 .

10. The light emitting device according to claim 9, characterized in that The organic layer includes a light-emitting layer, and the light-emitting layer contains the bisdibenzofuran compound according to any one of claims 1 to 8.

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