Organic compound and application thereof

Abstract

The invention relates to an organic compound, belongs to the technical field of organic electroluminescent materials, and also relates to application of the compound and an organic electroluminescent device containing the compound. The compound provided by the invention adopts a benzophenanthrene five-membered ring structure as a parent nucleus structure and has a structure as shown in a formula (1), and at least one of R5 to R12 is a structure as shown in a formula (2). The compound has excellent carrier transport capacity and low triplet state energy level, and when the compound is applied to an OLED device, the efficiency of the device can be improved, the service life of the device can be prolonged, and meanwhile the voltage can be reduced.

Description

Technical Field

[0001] This invention relates to an organic compound, belonging to the field of organic electroluminescent materials technology, and also to the application of this compound and organic electroluminescent devices containing it. Background Technology

[0002] In recent years, optoelectronic devices based on organic materials have developed rapidly and become a research hotspot in the field. Examples of such organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic field-effect transistors, organic photovoltaic cells, and organic sensors. Among them, OLEDs have developed particularly rapidly and have already achieved commercial success in the field of information display. OLEDs can provide highly saturated red, green, and blue colors, and full-color display devices made with them do not require an additional backlight, offering advantages such as vibrant colors, thinness, and flexibility.

[0003] The core of an OLED device is a multilayer thin-film structure containing various organic functional materials. Common functionalized organic materials include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, as well as light-emitting host materials and light-emitting guest materials (dyes). When an electric current is applied, electrons and holes are injected and transported to the light-emitting region, where they recombine, thereby generating excitons and emitting light.

[0004] Common phosphors primarily utilize singlet excitons generated when electrons and holes combine to emit light, and are still widely used in various OLED products. Some metal complexes, such as iridium complexes, can simultaneously utilize both triplet and singlet excitons to emit light; these are called phosphors, and their energy conversion efficiency can be up to four times higher than that of traditional phosphors. Thermally excited delayed fluorescence (TADF) technology promotes the conversion of triplet excitons to singlet excitons, achieving high luminous efficiency without the use of metal complexes, while still effectively utilizing triplet excitons. Thermally excited sensitized fluorescence (TASF) technology uses materials with TADF properties to sensitize the phosphor through energy transfer, also achieving high luminous efficiency.

[0005] Although products using OLED display technology are already commercialized, there is still a need to continuously improve the lifespan, efficiency, and other performance characteristics of these devices to meet people's demands for higher quality. Therefore, there is an urgent need in this field to develop a wider variety of organic materials for use in organic electroluminescent devices, enabling these devices to achieve higher luminous efficiency, lower driving voltage, and longer lifespan. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the present invention aims to provide an organic compound and its application, and an organic electroluminescent device containing the organic compound, wherein the organic compound has excellent charge transport capability; its application in organic electroluminescent devices can improve the luminous efficiency, driving voltage and device lifespan of the device.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] One object of the present invention is to provide an organic compound having the structure shown in formula (1):

[0009]

[0010] In equation (1), X represents O and S;

[0011] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 Each of the following independently represents any one of hydrogen, deuterium, substituted or unsubstituted C1-C30 straight-chain or branched alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C1-C30 arylsilyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 arylamino, and substituted or unsubstituted C3-C60 heteroarylamino; R1 to R 12 Two adjacent elements are not connected or are linked by chemical bonds to form a ring;

[0012] Preferably, in the above general formula (1), adjacent R11 and R12 do not fuse into a ring; adjacent R5 and R6 do not fuse into a ring;

[0013] In equation (1), R5 to R 12 At least one of them is the structure shown in equation (2):

[0014]

[0015] In equation (2), "*" indicates the bonding position with equation (1);

[0016] L, L1, and L2 are each independently one of a single bond, a substituted or unsubstituted C6-C60 arylene, or a substituted or unsubstituted C3-C60 heteroarylene;

[0017] Ar1 and Ar2 are each independently one of substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C3-C60 heteroaryl;

[0018] For the substitution of each of the above-mentioned groups R1 to R 12 12

[0019] In the present invention, for the description 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.

[0020] The hydrogen atoms of the compound described in the above formula (1) can be replaced by deuterium atoms of its isotopes, thereby forming a deuterated compound. The content of deuterium can be 0% to 100%, specifically preferably 10% to 90%, more preferably 20% to 80%, still more preferably 30% to 70%, and most preferably 40% to 60%.

[0021] In the present invention, when the number of hydrogen atoms in the compound is T1 and the number of deuterium atoms replaced after being replaced by deuterium atoms is T2, the deuterium content T% after the compound is deuterated can be defined as T% = T2 / T1 * 100%.

[0022] For example, the number of hydrogen atoms contained in the phenyl substituent is 5 (T1), and the number of deuterium after being replaced by deuterium atoms is 1 (T2), then the deuterium content of this phenyl group is 20%. The phenyl structure with a 20% deuterium content can be represented by the following structural formula:

[0023]

[0024] In the present invention, for the compound with the structure of formula (1), the range of the deuterium atom content is 0% to 100%. 0% means that the hydrogen atoms in the compound are not replaced by deuterium atoms.

[0025] In the present invention, when the hydrogen atoms in the compound with the structure of formula (1) are not all replaced by deuterium atoms, that is, when the deuterium atom content is less than 100%, the number of deuterium atoms in the structure can be represented as Dn, where n represents the number of deuterium atoms.

[0026] In this invention, the "substituted or unsubstituted" group can replace one substituent or multiple substituents. When there are multiple substituents, they can be selected from different substituents. In this invention, when the same expression is used, they all have the same meaning, and the selection range of substituents is as shown above and will not be repeated one by one.

[0027] In this invention, "each of the substituents is independently not connected to the adjacent ring structure" means that the substituent is only connected to the C atom through a single bond; "each of the substituents is independently connected to the adjacent ring structure through chemical bonds to form a ring" means that the substituent, in addition to being connected to the C atom through chemical bonds, is also connected to the adjacent ring through chemical bonds, thereby forming a fused ring structure. The same descriptions will have the same meaning in the following text and will not be repeated.

[0028] In this invention, the expression of Ca to Cb represents that the group has a to b carbon atoms. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms of the substituent.

[0029] In this invention, the "-" line on the group refers to the way the ring structure is drawn, indicating that the bonding site is located at any position on the ring structure where bonding can occur.

[0030] In this invention, "each independently" means that when there are multiple subjects, they can be the same or different from each other.

[0031] In this invention, unless otherwise specified, the description of chemical elements generally includes the concept of their isotopes. For example, the description of "hydrogen (H)" includes its isotopes. 1 H (protium or H), 2 The concept of H (deuterium or D); carbon (C) includes... 12 C 13 C, etc., will not be elaborated further.

[0032] The heteroatoms in the heteroaryl group of this invention generally refer to atoms or groups of atoms selected from N, O, S, P, Si and Se, preferably from N, O and S.

[0033] Examples of halogens in this invention include fluorine, chlorine, bromine, and iodine.

[0034] In this invention, C6-C30 can all be C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.

[0035] C3-C30 can all be C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.

[0036] C1-C30 can all be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C20, C22, C24, C26 or C28, etc.

[0037] C1-C20 can all be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.

[0038] C3-C20 can all be C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.

[0039] C2-C20 can all be C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.

[0040] In this invention, the C6-C60 aryl group, preferably C6-C24 aryl group, includes monocyclic aryl and fused-ring aryl groups; the monocyclic aryl group 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 term "fused-ring aryl" refers to a group containing at least two aromatic rings, wherein the aromatic rings share two adjacent carbon atoms fused together. Exemplary examples include, but are not limited to: naphthyl (1-naphthyl, 2-naphthyl), anthraceneyl (1-anthrayl, 2-anthrayl, 9-anthrayl), 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, 9,9-dinaphthylfluorenyl, phenylmethylfluorenyl, spirodifluorenyl, benzo[a]fluorenyl, etc.), fluoranyl, triphenylene, pyrene (1-pyrene, 2-pyrene, 4-pyrene), peryl, Aryl groups include aryl groups, pheno-tetraphenyl (1-pheno-tetraphenyl, 2-pheno-tetraphenyl, 9-pheno-tetraphenyl), etc. It should be noted that monocyclic aryl groups and fused-ring aryl groups linked by single bonds also fall under the aryl group category, such as phenylnaphthyl, naphthylphenyl, and binaphthyl.

[0041] In this invention, the C3-C60 heteroaryl group, preferably a C3-C20 heteroaryl group, includes monocyclic heteroaryl groups or fused-ring heteroaryl groups. A monocyclic heteroaryl group 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, pyrimidinylphenyl, 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), and the two share two adjacent atoms fused together in a group. Examples include, but are not limited to: quinolinyl, isoquinolinyl, quinoxolinyl, quinazolinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, isobenzothiophenyl, indolyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, naphthobenzothiophenyl, carbazoleyl and its derivatives (N-phenylcarbazoleyl, N-naphthylcarbazoleyl, benzocarbazoleyl, dibenzocarbazoleyl, indolocarbazoleyl, azacarbazoleyl, etc.), acridineyl, phenothiazinyl, phenotoxazinyl, hydrogenated acridineyl, etc. It should be noted that heteroaryl groups connected by single bonds, as well as aryl groups connected by single bonds, also fall under the category of heteroaryl groups, such as phenyldibenzofuranyl, phenyldibenzothiophenyl, dibenzothiophenylphenyl, dibenzofuranylphenyl, etc.

[0042] Specific examples of the C6-C60 arylene group can be exemplified by removing one hydrogen atom from the aryl group examples above, resulting in a divalent group; specific examples of the C3-C60 heteroarylene group can be exemplified by removing one hydrogen atom from the heteroaryl group examples above, resulting in a divalent group.

[0043] The C1-C20 straight-chain or branched alkyl group, preferably C1-C10 straight-chain or branched alkyl group, includes, but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, neohexyl, 2-ethylhexyl, n-octyl, n-heptyl, n-nonyl, n-decyl, etc.

[0044] Specific examples of the C1-C20 alkoxy groups can be exemplified by the monovalent groups obtained by connecting the above-mentioned straight-chain or branched alkyl groups to O.

[0045] The C3-C20 cycloalkyl groups mentioned in this invention are preferably C3-C10 cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, tert-pentyl, cyclohexyl, adamantyl, etc.

[0046] The C2-C20 alkenyl group mentioned in this invention is preferably a C2-C10 alkenyl group, which 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.

[0047] Specific examples of C3-C20 heterocyclic alkyl groups mentioned in this invention 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 group, tetrahydrofuranyl group, tetrahydrothiophenyl group, tetrahydropyrroleyl group, tetrahydropyranyl group, piperidinyl group, piperazineyl group, dioxaneyl group, morpholinyl group, etc.

[0048] Furthermore, the compound of formula (1) of the present invention can be represented as any of the structures shown in formulas (3-1), (3-2), (3-3), (3-4), (3-5), or (3-6):

[0049]

[0050] Among them, X, R1~R 12 The definitions of L, L1, L2, Ar1 and Ar2 are the same as those in equation (1).

[0051] Furthermore, the compound of formula (1) of the present invention is preferably a structure shown in any of formulas (4-1), (4-2), (4-3) or (4-4):

[0052]

[0053] The definitions of X, L, L1, L2, Ar1, and Ar2 are the same as those in equation (1).

[0054] Furthermore, in the above general formula of the present invention, preferably, Ar1 and Ar2 are each independently selected from one of the following groups, substituted or unsubstituted: phenyl, naphthyl, anthraceneyl, phenanthryl, biphenyl, terphenyl, tetraphenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, spirofluorenyl, benzo[a]fluorenyl, benzo[a]furanyl, benzo[a]thiopheneyl, dibenzo[a]furanyl, dibenzo[a]thiopheneyl, carbazoleyl, benzimidazoleyl, benzo[a]indazoleyl, benzo[a] Carbazolyl, benzofuranocarbazolyl, benzothiophenocarbazolyl, indolocarbazolyl, azadibenzothiophenoyl, azadibenzofuranoyl, phenylaminol, naphthylaminol, or biphenylaminol; when Ar1 and Ar2 have substituents, the substituents are selected from deuterium, halogen, cyano, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkoxy, C3-C30 heterocycloalkyl, C6-C30 aryl, or C3-C30 heteroaryl.

[0055] Furthermore, in the above general formula of the present invention, preferably, L, L1, and L2 are each independently selected from one of the following groups, substituted or unsubstituted: single bond, phenylene, naphthylene, anthraceneylene, phenanthrene, biphenylene, 9,9-dimethylfluoreneylene, 9,9-diphenylfluoreneylene, 9-methyl-9-phenylfluoreneylene, spirofluoreneylene, benzo[a]fluoreneylene, benzo[a]furanylene, benzo[a]thiopheneylene, dibenzo[a]furanylene, dibenzo[a]thiopheneylene, carbazoylene, benzimidazolylene, benzo[a]indazolylene, benzo[a]carbazoylene, The following are selected from the following groups: benzofuranocarbazolyl, benzothiocarbazolyl, indolocarbazolyl, azadibenzothiophene, azadibenzofuran, phenylamino, naphthylamino, and biphenylamino; when L, L1, and L2 have substituents, the substituents are selected from the following groups: deuterium, halogen, cyano, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkoxy, C3-C30 heterocycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl.

[0056] The compounds of this invention employ a benzo[pphenanthroline] five-membered ring structure as their core structure. This molecular structure possesses a large spatial plane and a large π-delocalized range, thereby enhancing the π-electron transition capability and thus improving the charge carrier transport capability of the compounds. The introduction of an aromatic amine structure into the core structure of the compounds of this invention can improve the hole mobility of the molecules, thus facilitating hole injection and transport. Furthermore, the excellent planarity of the compounds of this invention allows for more compact molecular stacking, which also facilitates charge transitions, thus reducing device voltage when used in OLED devices. Simultaneously, the benzo[pphenanthroline] five-membered ring structure of this invention has a low triplet energy level, reducing the band gap with the dye when used in OLED devices, thus facilitating energy transfer. When used as the light-emitting host material of the device, the compounds of this invention have lower exciton energies and better stability, potentially effectively preventing non-radiative energy loss, thereby achieving better device efficiency and lifetime. Furthermore, the benzo[a]phenanthrene five-membered ring molecule used in the compound of this invention has high rigidity, which can significantly increase the glass transition temperature of the molecule, avoid molecular aggregation and crystallization during high-temperature evaporation, improve the stability of the material, prevent device degradation, and increase the device lifespan. In summary, the verification results of the application examples of this invention show that when the compound of this invention is applied to OLED devices, it can improve the efficiency and lifespan of the device and reduce the voltage.

[0057] The compounds of the present invention are preferably the following specific compounds, but the present invention is not limited to the specific compounds shown below, wherein in compounds B274 and B551, D indicates that the hydrogen in the structure is replaced by deuterium, and the subscript number of D indicates the number of deuterium:

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089] As another aspect of the invention, the application of the compound described above in an organic electroluminescent device is also provided, wherein the compound is applied to an organic electronic device. Preferably, the organic electronic device includes an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin-film transistor, an organic field-effect transistor, an organic thin-film solar cell, an information tag, an electronic artificial skin sheet, a sheet-type scanner, or electronic paper. More specifically, the application as a light-emitting layer material in an organic electroluminescent device is preferred, and even more preferred is its application in a red-light organic electroluminescent device. More preferably, the compound of the present invention is used as a host material of the organic electroluminescent device, preferably as a red-light host material.

[0090] As another aspect of the present invention, an organic electroluminescent device is also provided, comprising a first electrode, a second electrode and an organic layer inserted between the first electrode and the second electrode, wherein the organic layer contains a compound represented by formula (1) as described above.

[0091] Specifically, one embodiment of the present invention provides an organic electroluminescent device, including a substrate, and a first electrode, a plurality of light-emitting functional layers, and a second electrode sequentially formed on the substrate; the light-emitting functional layers include a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and the light-emitting layer is located between the hole transport layer and the electron transport layer; wherein the light-emitting layer includes a host material and a dopant material, and the host material includes at least one compound represented by formula (1) as described above.

[0092] In this organic electroluminescent device, the light-emitting layer can also employ multiple light-emitting host materials and / or multiple light-emitting dyes. When multiple light-emitting hosts are used, the light-emitting host materials may include a first compound and a second compound. The first compound is at least one compound as shown in formula (1) above, and the second compound can be selected from compounds that match the energy level relationship, carrier transport performance, etc., of the first compound. Specific embodiments of this invention illustrate preferred device implementations.

[0093] The present invention also discloses a display screen or display panel, wherein the display screen or display panel employs the organic electroluminescent device as described above; preferably, the display screen or display panel is an OLED display.

[0094] The present invention also discloses an electronic device having a display screen or display panel, wherein the display screen or display panel employs an organic electroluminescent device as described above.

[0095] Instruction manual illustrations

[0096] Figure 1 The diagram shows the molecular orbitals of the comparative compound R-4 in the examples, where a1 and a2 represent the HOMO and LUMO orbitals of the ground state molecule, respectively, and a3 and a4 represent the HOMO and LUMO orbitals of the excited state molecule, respectively.

[0097] Figure 2 : This is the molecular orbital diagram of compound B160 of the present invention, where b1 and b2 represent the HOMO and LUMO orbitals of the ground state molecule, respectively, and b3 and b4 represent the HOMO and LUMO orbitals of the excited state molecule, respectively. Detailed Implementation

[0098] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention.

[0099] The preferred compounds of this invention can be obtained using common coupling reactions, with representative synthetic routes as follows:

[0100]

[0101] Wherein, Hal represents a halogen or halogen-like group, including but not limited to chlorine, bromine, iodine, methanesulfonyl, trifluoromethanesulfonyl, etc.; Pd2(dba)3 represents tris(dibenzylacetone)dipalladium(0), and Pd(dppf)Cl2 represents (1,1'-bis(diphenylphosphino)di Ferrocene palladium dichloride NaOBu-t represents sodium tert-butoxide, Pd(PPh3)4 represents tetrakis(triphenylphosphine palladium), and SPhos represents 2-biscyclohexylphosphine-2',6'-dimethoxybiphenyl. The preparation method of the compound of formula (1) of the present invention includes, but is not limited to, the above-described method. Compounds of formula (1) synthesized by other methods by those skilled in the art are also within the scope of protection of the present invention.

[0102] More specifically, the present invention provides, through the following exemplary synthetic examples, a specific synthetic method for representative compounds. The chemical reagents or raw materials used can be purchased from the chemical product market or custom-made. Alternatively, those skilled in the art can synthesize the compounds using known methods.

[0103] The mass spectrometry (m / z) characterization data of the intermediates and target products in the following specific embodiments of the present invention were obtained by testing with an Agilent 6530LC / Q-TOF mass spectrometer (APCI ion source).

[0104] Synthesis method of intermediate IM-1:

[0105]

[0106] Synthesis of A-1:

[0107] In a 500 mL three-necked flask, dibenzofuran-3-boric acid (21.0 g), 2-bromo-5-chlorobenzaldehyde (22.0 g), potassium carbonate (17.5 g), toluene (300 mL), ethanol (30 mL), water (30 mL), and Pd(PPh3)4 (1.2 g) were added. The mixture was evacuated to nitrogen three times, then heated to 100 °C and reacted for 8 h. After the reaction was complete, the mixture was extracted with ethyl acetate and water, dried over anhydrous sodium sulfate, and concentrated. The crude product was stirred in methanol to precipitate a solid, which was collected by filtration as a white solid, intermediate A-1. MS (M+H): 307.05.

[0108] Synthesis of intermediate A-2:

[0109] In a 500 mL three-necked flask, (methoxymethyl)triphenylphosphine chloride (20.0 g) and anhydrous tetrahydrofuran (350 mL) were added and stirred until homogeneous. The mixture was then cooled to 0 °C in an ice-water bath. Sodium tert-butoxide (9.6 g) was added, and stirring continued for half an hour. A-1 (15.0 g) was dissolved in 150 mL of anhydrous tetrahydrofuran and slowly added dropwise to the above solution using a constant pressure dropping funnel. After the addition was complete, the mixture was heated to 60 °C and stirred overnight. After the reaction was complete, the mixture was cooled and extracted with ethyl acetate and water. The organic phase was concentrated to obtain a red oily substance. The crude product was purified by silica gel column chromatography (petroleum ether / dichloromethane, 5 / 1) to obtain a yellow oily substance A-2, MS (M+H): 335.08.

[0110] Synthesis of IM-1:

[0111] In a 250 mL three-necked flask, A-2 (15 g) and dichloromethane (200 mL) were added and stirred until homogeneous. Then, methanesulfonic acid (5 g) was added, and a white solid gradually precipitated. After the addition was complete, stirring was continued for 3 hours. The solvent was removed under reduced pressure, and petroleum ether was added and stirred to disperse the solid. The solid was collected by filtration and washed successively with water and ethanol to obtain IM-1. MS (M+H): 303.05.

[0112] Referring to the synthetic method of IM-1, other desired intermediates can be obtained by replacing dibenzofuran-3-boronic acid and 2-bromo-5-chlorobenzaldehyde with the compounds in Table 1.

[0113] Table 1 below is a summary table of intermediate synthesis.

[0114] Table 1:

[0115]

[0116]

[0117] Synthesis Examples

[0118] Synthesis of compound B17:

[0119]

[0120] Synthesis of B17-1

[0121] In a 250 mL three-necked flask, IM-1 (5.0 g), SM-1 (4.1 g), potassium carbonate (3.4 g), Pd2(dba)3 (0.15 g), SPhos (0.15 g), and toluene (100 mL) were added. The reaction system was stirred until homogeneous, and the mixture was purged with nitrogen three times under vacuum. The temperature was then raised to 100 °C and reacted for 7 h. After the reaction was complete, the reaction solution was passed through a silica gel short column and washed with toluene until no product was obtained. The filtrate was concentrated to give a yellow solid. The solid was recrystallized from toluene and ethanol to give a pale yellow solid. MS (M+H): 512.0777.

[0122] B17 Synthesis

[0123] In a 250 mL three-necked flask, add B17-1 (5.0 g), SM-2 (2.5 g), potassium carbonate (2.1 g), Pd2(dba)3 (0.10 g), SPhos (0.10 g), and toluene (80 mL). Stir the reaction mixture thoroughly, purge with nitrogen three times, and then heat to 100 °C for 18 h. After the reaction is complete, pass the reaction solution through a short silica gel column, wash with toluene until no product is obtained, and concentrate the filtrate to give a yellow solid. Recrystallize the solid from toluene and petroleum ether to give a pale yellow solid. MS (M+H): 664.1799.

[0124] Based on the above-described method for synthesizing compound B17, other compounds described in this invention can be obtained by replacing different reaction raw materials IM-1, SM-1, and SM-2, as shown in Table 2 below.

[0125] Table 2:

[0126]

[0127]

[0128]

[0129]

[0130]

[0131] Synthesis of compound B274

[0132]

[0133] In a 250 mL three-necked flask, 5 g of the compound to be deuterated, 3.5 g of trifluoromethanesulfonic acid, and 50 mL of benzene-d6 were added. The reaction mixture was stirred at 40 °C for 4 hours. After the reaction was complete, the reaction was quenched with Na2CO3 in D2O, followed by extraction with dichloromethane. The organic phase was concentrated to give a yellow solid. The solid was recrystallized in toluene and further purified by sublimation to give compound B274, whose molecular weight (M+H) was 623.34 as determined by mass spectrometry.

[0134] Device Examples

[0135] An OLED includes a first electrode and a second electrode, and an organic material layer located between the electrodes. This organic material layer can be further divided into multiple regions. For example, the organic material layer may include a hole transport region, a light-emitting layer, and an electron transport region.

[0136] In specific embodiments, a substrate can be used below the first electrode or above the second electrode. The substrate is typically made of glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. Furthermore, thin-film transistors (TFTs) can also be incorporated into the substrate used for displays.

[0137] The first electrode can be formed by sputtering or depositing the material to be used as the first electrode on a substrate. When the first electrode is used as the anode, it can be a transparent conductive oxide material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof. When the first electrode is used as the cathode, it can be a metal or alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof.

[0138] Organic material layers can be formed on electrodes using methods such as vacuum thermal evaporation, spin coating, and printing. The compounds used as organic material layers can be small organic molecules, large organic molecules, polymers, and combinations thereof.

[0139] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a single-layer hole transport layer (HTL), including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multilayer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0140] The material for the hole transport region can be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers, or polymers containing conductive dopants such as polyphenylene oxide, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate).

[0141] (PEDOT / PSS), polyaniline / camphor sulfonic acid (Pani / CSA), polyaniline / poly(4-styrene sulfonate) (Pani / PSS), aromatic amine derivatives, wherein the aromatic amine derivatives include compounds shown below HT-1 to HT-51; or any combination thereof.

[0142]

[0143]

[0144]

[0145] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can be one or more compounds of HT-1 to HT-51 described above, or one or more compounds of HI-1 to HI-3 described below; it can also be one or more compounds of HT-1 to HT-51 doped with one or more compounds of HI-1 to HI-3 described below.

[0146]

[0147] The emissive layer includes luminescent dyes (i.e., dopants) that can emit different wavelengths of light, and may also include a host material. The emissive layer can be a monochromatic emissive layer emitting a single color such as red, green, or blue. Multiple monochromatic emissive layers of different colors can be arranged in a planar pattern according to pixel design, or they can be stacked together to form a colored emissive layer. When different colored emissive layers are stacked together, they can be separated from each other or connected to each other. The emissive layer can also be a single colored emissive layer that can simultaneously emit different colors such as red, green, and blue.

[0148] Depending on the technology used, the light-emitting layer material can be various, including fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescence materials. An OLED device can employ a single light-emitting technology or a combination of different technologies. These different light-emitting materials, categorized by technology, can emit light of the same color or different colors.

[0149] Specifically, the host material in the luminescent layer may include a single host compound or two host compounds, and the luminescent dye in the luminescent layer may include one type of dye compound or two types of dye compounds. When two host compounds are included, the energy level relationship and carrier transport performance of the two compounds can be matched, designed, and selected according to requirements. When two types of dye compounds are included, the emission wavelengths of the two compounds and their energy level relationship with the host material can be matched, designed, and selected according to requirements.

[0150] The main material in the light-emitting layer adopts a compound with the structure shown in formula (1) of the present invention, or adopts a compound with the structure shown in at least one of the compounds B1 to B720 of the present invention as described above.

[0151] Specifically, in the organic electroluminescent device provided by this invention, the host material of the light-emitting layer can be the organic compound of this invention as a single host material, or the host material treatment of the light-emitting layer can also adopt a technical solution of multiple host materials and / or multiple light-emitting dyes. When multiple host materials are used, the host material may include a first compound and a second compound. The first compound is at least one compound as shown in formula (1) of this invention, or a compound with at least one structure shown in B1 to B720 as described above. The second compound may be selected as a compound that matches the energy level relationship, carrier transport performance, etc. of the first compound, or the second compound may include one or more combinations of PH-1 to PH-89, but is not limited to one or more combinations of PH-1 to PH-89.

[0152]

[0153]

[0154]

[0155]

[0156] In one aspect of the invention, the light-emitting layer employs phosphorescent photoluminescence technology. The phosphorescent dopant of the light-emitting layer may be selected from, but not limited to, one or more combinations of GPD-1 to GPD-47 listed below.

[0157]

[0158]

[0159]

[0160] Where D represents deuterium.

[0161] In one aspect of the invention, the light-emitting layer employs phosphorescent photoluminescence technology. The phosphorescent dopant of the light-emitting layer may be selected from, but not limited to, one or more combinations of RPD-1 to RPD-28 listed below.

[0162]

[0163]

[0164] In one aspect of the invention, the light-emitting layer employs phosphorescent photoluminescence technology. The phosphorescent dopant of the light-emitting layer may be selected from, but not limited to, one or more combinations of YPD-1 to YPD-11 listed below.

[0165]

[0166] The OLED organic material layer may also include an electron transport region between the light-emitting layer and the cathode. The electron transport region can be a single-layer electron transport layer (ETL), including single-layer electron transport layers containing only one compound and single-layer electron transport layers containing multiple compounds. Alternatively, the electron transport region can be a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0167] In one aspect of the present invention, the electron transport layer material may be selected from, but is not limited to, one or more combinations of ET-1 to ET-73 listed below.

[0168]

[0169]

[0170]

[0171]

[0172] The device may also include an electron injection layer located between the electron transport layer and the cathode. The electron injection layer material includes, but is not limited to, one or more combinations of the following: LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Yb, Li or Ca.

[0173] The fabrication process of the organic electroluminescent device in this embodiment is as follows:

[0174] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a acetone:ethanol mixed solvent, baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0175] The glass substrate with the ITO anode was placed in a vacuum chamber and evacuated to a vacuum level of <1×10⁻⁶. -5Pa, on the above anode film, a 10 nm HT-4:HI-3 (97 / 3, w / w) mixture was vacuum thermally deposited as a hole injection layer; a 60 nm compound HT-4 was deposited as a hole transport layer; a 60 nm compound HT-47 was vacuum-deposited on the hole transport layer as an electron blocking layer material; a 40 nm host material PH-86: formula (1) compound: RPD-8 (50:50:3, w / w / w) binary mixture was deposited as a light-emitting layer; a 5 nm ET-17 was vacuum-deposited on the light-emitting layer as a hole blocking layer; a 25 nm compound ET-69:ET-57 (50 / 50, w / w) mixture was deposited as an electron transport layer; a 1 nm LiF was deposited as an electron injection layer; and a 150 nm aluminum was deposited as a cathode. The total deposition rate of all organic layers and LiF was controlled at 0.1 nm / s, and the deposition rate of the metal electrode was controlled at 1 nm / s.

[0176] Device Examples 1 to 12 and Comparative Device Examples 1 to 4 of the present invention were completed according to the above preparation steps and testing methods. The main materials in Device Examples 1 to 12 were the compounds of the present invention, and the main materials in Comparative Device Examples 1 to 4 were compounds R-1, R-2, R-3, and R-4 in the prior art, respectively.

[0177] The structural formulas of compounds R-1 to R-4 are as follows:

[0178] The method described in CN114933577A can be used to obtain it;

[0179] The method described in CN113402508A can be used to obtain it;

[0180] The method described in CN110526825A can be used to obtain it;

[0181] The method described in CN106132944A can be used to obtain...

[0182] The organic electroluminescent devices prepared by the above process were subjected to the following performance measurements:

[0183] Under the same brightness, the driving voltage, current efficiency, and lifetime of the organic electroluminescent devices prepared in the examples and comparative examples were measured. Specifically, the voltage was increased at a rate of 0.1V per second, and the measurement was performed when the brightness of the organic electroluminescent device reached 3000 cd / m². 2The voltage at that time is the driving voltage, and the current density at that time is measured simultaneously; the ratio of brightness to current density is the current efficiency; the life test of LT97 is as follows: using a luminance meter at 10000 cd / m² 2 At a constant current, the brightness of the organic electroluminescent device decreased to 9700 cd / m² under the specified brightness. 2 The time is in hours.

[0184] The performance data of the organic electroluminescent devices prepared in the above-mentioned device embodiments and comparative embodiments are detailed in Table 3 below. In order to better reflect the performance advantages of the present invention, the test data of Comparative Example 1 is set to 1, and the data in the table below are all ratios to it.

[0185] Table 3:

[0186]

[0187]

[0188] As can be seen from Table 1 above, compared with devices prepared using compounds from the prior art, organic electroluminescent devices prepared using the compounds of the present invention as the light-emitting host material have higher luminous efficiency, longer lifetime, and relatively lower voltage.

[0189] Compared with B17 in Example 1, compound R-1 can be connected to phenanthrene-phenyl furan via biphenyl bridging, and the connection site is on the phenyl side, indicating that its device performance is poor. In Example 1, B17 is connected to the phenanthrene side, which is closer to the amine group. The larger delocalization range of π electrons helps stabilize the amine ion radical and has a faster hole mobility, resulting in better device performance than R-1.

[0190] Comparative compound R-3 is structurally similar to B704 in Example 27; comparative compound R-2 is structurally similar to B46 in the example. The fused ring group of R-3 is triphenylene, and that of R-2 is benzophenanthrene. The fused ring groups of B704 and B46 are phenanthrene. However, the compounds of the present invention have better device performance based on the data. This may be because the larger conjugated fused ring disrupts the carrier transport balance and the coating is more easily crystallized.

[0191] In Example 30, B274 is a deuterated compound of B173 in Example 33; in Example 29, B235 is a deuterated compound of B174 in Example 11; and in Example 28, B369 is a deuterated compound of B282 in Example 32. As can be seen from the device data, when the compounds of the present invention are deuterated, the device lifetime is significantly improved by 20% to 30%, but the device voltage and efficiency do not deteriorate. This indicates that the compounds of the present invention have better stability after deuteration and can meet the performance requirements of long-life devices.

[0192] The compound R-4 is similar in structure to B160 in Example 31, but the difference lies in the different ring-closing methods of the phenanthrene group and the furan ring. As can be seen from the device data, the device using the ring-closing method of the present invention has a lower voltage, significantly increased efficiency and lifetime. The compound of the present invention is a better structural choice.

[0193] The molecular orbitals of R-4 and B160 were simulated using Gaussian quantization calculations (see appendix). Figure 1 The triplet energy level (T1) of the molecule in the excited state was calculated using the following method: CAM-B3LYP / 6-31g*opt tda(triplets)||mpw1b95 / 6-31g*tda(triplets). The calculation results are shown in Table 4. The results show that the triplet energy level of compound B160 in the excited state is 2.61 eV, which is lower than the 2.74 eV triplet energy level of R-4. This lower energy level improves the material's stability and extends its lifetime; simultaneously, it avoids losses from non-radiative transitions, increasing efficiency.

[0194] Table 4 shows the triplet quantization calculation results for R-4 and B160:

[0195] Table 4:

[0196] Compound Name Computational model <![CDATA[E HOMO / eV]]> <![CDATA[E LUMO / eV]]> T1 energy level / eV R-4 T1 -6.11 -0.54 2.74 B160 T1 -5.90 -0.34 2.61

[0197] This invention illustrates the compounds of the present invention and their application in OLED devices through the above embodiments. However, the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An organic compound having the structure shown in formula (1): In equation (1), X represents O and S; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 Each of the following independently represents any one of hydrogen, deuterium, substituted or unsubstituted C1-C30 straight-chain or branched alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C1-C30 arylsilyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 arylamino, and substituted or unsubstituted C3-C60 heteroarylamino; R1 to R 12 Two adjacent elements are either not connected or are linked by chemical bonds to form a ring; R5 to R 12 At least one of them is the structure shown in equation (2): In equation (2), "*" indicates the bonding position with equation (1); L, L1, and L2 are each independently one of a single bond, a substituted or unsubstituted C6-C60 arylene, or a substituted or unsubstituted C3-C60 heteroarylene; Ar1 and Ar2 are each independently one of substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C3-C60 heteroaryl; The above R1 to R 12 The substitution of each substituted or unsubstituted group in L, L1, L2, Ar1, and Ar2 refers to the independent substitution by a group selected from one or a combination of two of the following groups: deuterium, halogen, cyano, nitro, hydroxyl, amino, aldehyde, ester, C1-C20 straight-chain or branched alkyl, C2-C20 alkenyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C1-C20 silyl, C6-C60 aryloxy, C6-C60 arylamino, C6-C30 aryl, or C3-C30 heteroaryl.

2. The organic compound according to claim 1, characterized in that, The hydrogen atoms in the compound described in formula (1) may or may not be replaced by deuterium atoms.

3. The organic compound according to claim 1 or 2, characterized in that, The structure is any one of the following formulas (3-1), (3-2), (3-3), (3-4), (3-5), or (3-6): Among them, X, R1~R 12 The definitions of L, L1, L2, Ar1 and Ar2 are the same as those in equation (1).

4. The organic compound according to claim 1 or 2, characterized in that, The structure is any one of equations (4-1), (4-2), (4-3), or (4-4): The definitions of X, L, L1, L2, Ar1, and Ar2 are the same as those in equation (1).

5. The organic compound according to any one of claims 1, 3, or 4, characterized in that, Ar1 and Ar2 are each independently selected from one of the following groups, substituted or unsubstituted: phenyl, naphthyl, anthracene, phenanthrene, biphenyl, terphenyl, tetraphenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, spirofluorenyl, benzo[fluorenyl], benzo[furanyl], benzo[thiophene], dibenzo[furanyl], dibenzo[thiophene], carbazole, benzimidazolyl, benzo[indazole], benzo[carbazole], benzo[furanyl], benzo[thiophene], indole[carbazole], azadibenzo[thiophene], azadibenzofuranyl, phenylamino, naphthylamino, or biphenylamino. When Ar1 and Ar2 have substituents, the substituents are selected from deuterium, halogen, cyano, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkoxy, C3-C30 heterocycloalkyl, C6-C30 aryl or C3-C30 heteroaryl.

6. The organic compound according to claim 1, 3 or 4, characterized in that, The L, L1, and L2 are each independently selected from a single bond or from one of the following groups, substituted or unsubstituted: phenylene, naphthylene, anthracene, phenanthrene, biphenylene, 9,9-dimethylfluorene, 9,9-diphenylfluorene, 9-methyl-9-phenylfluorene, spirofluorene, benzo[a]fluorene, benzo[a]furanyl, benzo[a]thiophene, dibenzo[a]furanyl, dibenzo[a]thiophene, carbazolyl, benzo[a]imidazolyl, benzo[a]indazole, benzo[a]carbazolyl, benzo[a]carbazolyl, benzo[a]furan[a]carbazolyl, benzo[a]thiophene[a]carbazolyl, indole[a]carbazolyl, aza-dibenzo[a]thiophene, aza-dibenzo[a]furanyl, phenylamino, naphthylamino, biphenylamino. When L, L1, and L2 have substituents, the substituents are selected from one of deuterium, halogen, cyano, C1-C30 alkyl, C3-C30 cycloalkyl, C1-C30 alkoxy, C3-C30 heterocycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl.

7. The organic compound according to claim 1 or 2, characterized in that, The compounds B274 and B551 have structures shown in any of the following examples, where D indicates that hydrogen is replaced by deuterium, and the subscript of D indicates the number of deuterium atoms:

8. The use of the organic compound according to any one of claims 1 to 7, wherein the use is as a functional material in an organic electronic device, the organic electronic device including an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin-film transistor, an organic field-effect transistor, an information tag, an electronic artificial skin sheet, a sheet-type scanner, or electronic paper; Preferably, the organic compound is used as a light-emitting layer material in an organic electroluminescent device, and more preferably as a host material in the light-emitting layer.

9. An organic electroluminescent device, comprising a first electrode, a second electrode, and one or more light-emitting functional layers inserted between the first electrode and the second electrode, wherein the light-emitting functional layer comprises a light-emitting layer, and at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron blocking layer, wherein the light-emitting layer comprises a host material and a dopant material, and the host material comprises at least one organic compound as described in any one of claims 1 to 7.

10. An electronic device having a display screen or display panel, the display screen or display panel comprising the organic electroluminescent device of claim 9.

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