A boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure and an organic electroluminescent device thereof

Abstract

The present invention relates to a boron-containing organic compound containing a diphenyl-substituted naphthoxypyrrole structure and an organic electroluminescent device thereof, belonging to the field of semiconductor technology. The present invention provides a compound having a structure as shown in general formula (1): the compound of the present invention has a narrow half-peak width and a high fluorescence quantum yield. When used as a green light doping material in a light-emitting layer of an organic electroluminescent device, the current efficiency of the device is significantly improved, and the luminescent color purity and device life are also greatly improved.

Description

Technical Field

[0001] The invention relates to the field of semiconductor technology, and in particular to a boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure and an organic electroluminescent device thereof. Background Art

[0002] Traditional fluorescent doped materials are limited by early technologies and can only use 25% of singlet excitons formed by electrical excitation to emit light. The internal quantum efficiency of the device is low (up to 25%), and the external quantum efficiency is generally less than 5%, which is far behind the efficiency of phosphorescent devices. Phosphorescent materials can effectively use singlet and triplet excitons formed by electrical excitation to emit light, due to the strong spin-orbit coupling of the heavy atom center, which enhances intersystem crossing, so that the internal quantum efficiency of the device can reach 100%.

[0003] With the advent of the 5G era, higher requirements are placed on color rendering standards. In addition to being efficient and stable, luminescent materials also require a narrower half-width to improve the purity of the device's luminescent color. Fluorescent doped materials can achieve high fluorescence quantum and narrow half-width through molecular engineering. Blue fluorescent doped materials have achieved a phased breakthrough, and the half-width of boron materials can be reduced to below 30nm. In the green light region, which is more sensitive to the human eye, research is mainly focused on phosphorescent doped materials, but their luminescent peak shape is difficult to narrow by simple methods. Therefore, in order to meet higher color rendering standards, it is of great significance to study efficient green fluorescent doped materials with narrow half-width.

[0004] In addition, the sensitization technology combines triplet exciton-sensitizing materials with fluorescent doping materials, uses triplet exciton-sensitizing materials as exciton-sensitizing media, makes full use of triplet excitons, and transfers energy to fluorescent doping materials through energy transfer, which can also achieve 100% device quantum efficiency. This technology can make up for the shortcomings of insufficient exciton utilization of fluorescent doping materials, and effectively give play to the characteristics of high fluorescence quantum yield, high device stability, high color purity and low price of fluorescent doping materials, and has broad prospects in OLEDs applications.

[0005] Boron compounds with a resonant structure are more likely to achieve narrow half-width luminescence. Such materials are used in sensitized fluorescence technology to achieve the preparation of devices with high efficiency and narrow half-width emission. For example, CN 107507921 A and CN 110492006 A disclose a luminescent layer combination technology with a TADF material having a difference between the lowest singlet and the lowest triplet energy level of less than or equal to 0.2eV as the main body and a boron-containing material as the doping; CN 110492005 A and CN 110492009 A disclose a luminescent layer combination scheme with an exciplex as the main body and a boron-containing material as the doping; both can achieve efficiency comparable to phosphorescence and a relatively narrow half-width. Therefore, the development of sensitization technology based on narrow half-width boron-based luminescent materials has unique advantages and strong potential in terms of BT.2020 display indicators.

[0006] The DABNA-1 structure reported in the paper (CAS: 1689552-89-3, 10.1002 / adma.201505491) is a good resonant framework structure for light-emitting layer doping materials. JP2022032943A discloses a resonant organic compound with a carbazole-indole fused ring introduced on the basis of the DABNA-1 structure, which can be used as a doping material for the light-emitting layer to achieve the effect of blue narrow half-width emission. Summary of the invention

[0007] In view of the above problems existing in the prior art, the applicant of the present invention provides a boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure and an organic electroluminescent device thereof. The present invention forms a resonant organic compound by introducing a diphenyl-substituted naphthopyrrole structure at a specific position of a boron-nitrogen skeleton, and the resonant organic compound is used as a green light doping material of a light-emitting layer, which has the effects of significantly adjusting light color, improving quantum yield and improving device life.

[0008] The technical solution of the present invention is as follows: a boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure, wherein the structure of the boron-containing organic compound is shown in the general formula (1):

[0009]

[0010] In the general formula (1), Z is C-R1; R1, which is the same or different each time, is H, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C 10 Alkyl or silyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted amino, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0011] Z1, Z2, Z3, Z4, and Z5 are independently represented by CH or CR;

[0012] R, which is the same or different each time it appears, represents a deuterium atom, a tritium atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-C 10 Alkyl or silyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted amino, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0013] M1 represents a substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0014] X represents one of N-R2, O, S, C(R3)(R4);

[0015] R2 is independently represented by C1-C 10 Alkyl or silyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0016] R3 and R4 appear the same or different each time and represent H, deuterium atom, tritium atom, cyano group, C1-C 10 alkyl or silyl, substituted amino, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0017] The substituents for the substituent groups are selected from halogen atoms, deuterium atoms, cyano groups, C1-C 10 Alkyl, C5-C 10 Cycloalkenyl, C1-C 10 Alkoxy, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C3-C 30 one or more of heteroaryl groups;

[0018] The heteroatom in the heteroaryl group is selected from one of O, S, N and Si.

[0019] In a preferred embodiment, the structure of the boron-containing organic compound is shown in any one of general formulas (2) to (4):

[0020]

[0021] In general formula (2) to general formula (4), the definitions of Z, Z1, Z2, Z3, Z4, Z5, and X are the same as those defined above;

[0022] Y1 and Y2 are independently O or S.

[0023] In a preferred embodiment, the structure of the boron-containing organic compound is as shown in general formula (5) to general formula (13):

[0024]

[0025] In general formula (5) to general formula (13), the definitions of Z, Z1, Z2, Z3, Z4, and Z5 are the same as those defined above;

[0026] Ar1-Ar5 are independently represented by C1-C 10 Alkyl or silyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0027] The substituents for the substituent groups are selected from halogen atoms, deuterium atoms, cyano groups, C1-C 10 Alkyl, C5-C 10 Cycloalkenyl, C1-C 10 Alkoxy, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C3-C 30 one or more of heteroaryl groups;

[0028] The heteroatom in the heteroaryl group is selected from one of O, S, N and Si.

[0029] In a preferred embodiment, the structure of the boron-containing organic compound is as shown in general formula (14) to general formula (32):

[0030]

[0031]

[0032] In general formula (15) to general formula (32), the definitions of Z, Z1, Z2, Z3, Z4, and Z5 are the same as those defined above;

[0033] Ar6—Ar 15 They are independently represented as C1-C 10 Alkyl or silyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0034] The substituents for the substituent groups are selected from halogen atoms, deuterium atoms, cyano groups, C1-C 10 Alkyl, C5-C 10 Cycloalkenyl, C1-C 10 Alkoxy, C3-C 20 Cycloalkyl, C6-C 30 Aryl, C3-C 30 one or more of heteroaryl groups;

[0035] The heteroatom in the heteroaryl group is selected from one of O, S, N and Si.

[0036] In a preferred embodiment, the structure of the boron-containing organic compound is shown in any one of the general formulas (33) to (37):

[0037]

[0038] In general formula (33) to general formula (37), the definition of Z is the same as defined above;

[0039] Ar 16 -Ar 19 They are independently represented as C1-C 10 Alkyl or silyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C3-C 30 heteroaryl;

[0040] R a , R b , R c , R d , R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , R o , R p , R q Each occurrence is the same or different and represents a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3~C 10 Cycloalkyl, substituted or unsubstituted C1~C 10 Alkoxy, substituted or unsubstituted C6~C10 Aryloxy, substituted or unsubstituted arylamine, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C2~C 30 One of the heteroaryl groups;

[0041] The substituents for the substituent groups are selected from deuterium atoms, halogen atoms, cyano groups, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 30 Aryl, C2-C 30 One or more of heteroaryl and amine;

[0042] The heteroatom in the heteroaryl group is selected from one of O, S, N and Si.

[0043] Preferably, R, R1, R2, R3, R4, R a , R b , R c , R d , R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , R o , R p , R q It is represented by the following structure:

[0044]

[0045] The M1 is represented by any of the following ring structures:

[0046]

[0047]

[0048] The definition of Z is the same as above;

[0049] Ar1-Ar 19 They are independently represented as follows:

[0050]

[0051] Preferably, R, R1, R2, R3, R4, R a , R b , R c , R d, R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , R o , R p , R q Each occurrence, which is the same or different, of hydrogen, deuterium, tritium, methyl, deuterated methyl, tritiated methyl, ethyl, deuterated ethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, deuterated cyclopentyl, tritiated cyclopentyl, cyclopentyl, phenyl, deuterated phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl, deuterated tert-butyl Phenyl, tritiated terphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, pyridyl, quinolyl, furanyl, thienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, methyl substituted phenyl, ethyl substituted phenyl, isopropyl substituted phenyl, tert-butyl substituted phenyl, methyl substituted diphenyl biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, tritiated methyl-substituted phenyl, tritiated ethyl-substituted phenyl, tritiated isopropyl-substituted phenyl, tritiated tert-butyl-substituted phenyl, adamantyl-substituted phenyl, tritiated methyl-substituted biphenyl, tritiated ethyl-substituted biphenyl, tritiated isopropyl-substituted biphenyl or tritiated tert-butyl-substituted biphenyl, diphenyl-substituted amino, diphenyl-substituted amino, diphenyl-substituted triazinyl;

[0052] The M1 is represented by phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, phenyl-substituted amino, tert-butyl-substituted dibenzofuranyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, and xanthone;

[0053] Ar1-Ar 19 Phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracenyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolyl, furanyl, thienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, tert-butyl-substituted dibenzothienyl, carbazolyl, tert-butyl-substituted carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, phenyl-substituted amino, tert-butyl One of substituted dibenzofuranyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, adamantyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, xanthone, adamantyl, methyl-substituted adamantyl, phenyl-substituted adamantyl, cyclohexyl, methyl-substituted cyclohexyl, and diphenyl-substituted amine;

[0054] The substituent for the substituent group is optionally selected from one or more of a deuterium atom, a chlorine atom, a fluorine atom, a trifluoromethyl group, an adamantyl group, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-amyl group, a tert-butyl group, a butyl group, a methoxy group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyridyl group, a pyrimidyl group, a pyrazinyl group, a pyridazinyl group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalinyl group, a quinolyl group, an isoquinolyl group, a furanyl group, a thienyl group, an indolyl group, a pyrrolyl group, a dibenzofuranyl group, a dibenzothienyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a carbazolinyl group, and an azaphenanthryl group.

[0055] In a preferred embodiment, the specific structural formula of the boron-containing organic compound is any one of the following structures:

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067] The present invention also provides an organic light-emitting device, comprising a cathode, an anode and a functional layer, wherein the functional layer is located between the cathode and the anode, and the functional layer of the organic light-emitting device comprises the boron-containing organic compound.

[0068] Preferably, the functional layer comprises a light-emitting layer, and the light-emitting layer is the boron-containing organic compound;

[0069] Preferably, the functional layer comprises a light-emitting layer, the light-emitting layer comprises a main material and a doping material, and the doping material of the light-emitting layer is the boron-containing organic compound.

[0070] In a preferred embodiment, the light-emitting layer comprises a first main material, a second main material and a doping material, at least one of the first main material and the second main material is a TADF material, and the doping material is the boron-containing organic compound.

[0071] In a preferred embodiment, the light-emitting layer comprises a main material, an exciton-sensitizing material and a doping material, wherein the exciton-sensitizing material is a complex containing a metal element, and the doping material is the boron-containing organic compound.

[0072] Compared with the prior art, the beneficial technical effects of the present invention are:

[0073] (1) The compounds of the present invention are applied to OLED devices and can be used as green light doping materials for light-emitting layer materials. They can emit green fluorescence under the action of an electric field and can be applied to OLED lighting or OLED display fields;

[0074] (2) The compound of the present invention has a high fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of the material is close to 100%;

[0075] (3) The spectral FWHM of the compound of the present invention is relatively narrow, which can effectively improve the color gamut of the device and the luminous efficiency of the device;

[0076] (4) Introducing a diphenyl-substituted naphthopyrrole structure at a specific position of the boron-nitrogen fused ring is beneficial to further enhance the resonance effect of the molecule, thereby further narrowing the emission spectrum of the material;

[0077] (5) The introduction of a diphenyl-substituted naphthopyrrole structure at a specific position of the boron-nitrogen fused ring can increase the degree of delocalization of the electron cloud, enhance the oscillator strength of the excited state, and reduce the reorganization energy of the molecule, thereby reducing the Stokes shift and narrowing the half-peak width.

[0078] The compound of the invention has a narrow half-peak width and a high fluorescence quantum yield, and can be used as a green light doping material of a light-emitting layer of an organic electroluminescent device, thereby improving the light-emitting color purity and life of the device.

[0079] The present invention can adjust the emission peak to within the range of 510-550nm by changing the naphthopyrrole structure substituted with diphenyl, effectively adjust the light color, improve the efficiency, and achieve the effect of green light narrow half-width emission. BRIEF DESCRIPTION OF THE DRAWINGS

[0080] Figure 1 This is a schematic diagram of the structure of an OLED device in which the materials listed in the present invention are applied;

[0081] Among them, 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer. DETAILED DESCRIPTION

[0082] The present invention is described in detail below in conjunction with the accompanying drawings and embodiments.

[0083] In the present invention, when describing electrodes and organic electroluminescent devices, as well as other structures, the words "upper", "lower", "top" and "bottom" used to indicate orientation only indicate the orientation in a certain state, and do not mean that the related structure can only exist in the orientation described; on the contrary, if the structure can change its position, such as inverted, the orientation of the structure will be changed accordingly. Specifically, in the present invention, the "bottom" or "lower" side of the electrode refers to the side of the electrode close to the substrate during the preparation process, and the opposite side away from the substrate is the "top" or "upper" side.

[0084] In the present invention, the substituted or unsubstituted C6-C 30 Aryl refers to substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted p-terphenyl, substituted or unsubstituted m-terphenyl, substituted or unsubstituted The invention may include, but is not limited to, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylenyl group, and a substituted or unsubstituted indenyl group.

[0085] In the present invention, substituted or unsubstituted C2-C 30The heteroaryl group refers to a substituted or unsubstituted furanyl, a substituted or unsubstituted thienyl, a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted triazolyl, a substituted or unsubstituted oxazolyl, a substituted or unsubstituted thiazolyl, a substituted or unsubstituted oxadiazolyl, a substituted or unsubstituted thiadiazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted benzothienyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted The invention also includes substituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenathiazinyl, substituted or unsubstituted phenathiazinyl, substituted or unsubstituted phenathiazinyl, substituted or unsubstituted phenathiazinyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, combinations thereof, or fused rings of combinations of the foregoing groups, but is not limited thereto.

[0086] The C1-C 10 Alkyl (including straight-chain alkyl and branched alkyl) refers to methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, sec-butyl, neopentyl, n-pentyl, isopentyl, octyl, heptyl, n-decyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-butylpentyl and the like, but is not limited thereto.

[0087] The C3-C 10 Cycloalkyl refers to a monovalent monocyclic saturated hydrocarbon group including 3 to 10 carbon atoms as ring atoms. In this article, C4-C9 cycloalkyl is preferably used, C5-C8 cycloalkyl is more preferably used, and C5-C7 cycloalkyl is particularly preferably used. Non-limiting examples thereof may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, adamantyl and cycloheptyl, but are not limited thereto.

[0088] As the substrate of the organic electroluminescent device of the present invention, any substrate commonly used in organic electroluminescent devices can be used. Examples are transparent substrates such as glass or transparent plastic substrates; opaque substrates such as silicon substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance. Depending on the properties of the substrate, its use direction is different. In the present invention, a transparent PI film substrate is preferably used. The thickness of the substrate is not particularly limited.

[0089] A first electrode is formed on a substrate, and the first electrode and the second electrode may be opposite to each other. The first electrode may be an anode. The first electrode may be a transmissive electrode, a semi-transmissive electrode or a reflective electrode. When the first electrode is a transmissive electrode, it may be formed using a transparent metal oxide, such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO) or indium tin zinc oxide (ITZO). When the first electrode is a semi-transmissive electrode or a reflective electrode, it may include Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr or a metal mixture. The thickness of the first electrode layer depends on the material used, and is typically 50-500nm, preferably 70-300nm and more preferably 100-200nm.

[0090] The organic functional material layer disposed between the first electrode and the second electrode includes, from bottom to top, a hole transport region, a light emitting layer and an electron transport region.

[0091] Herein, the hole transport region constituting the organic electroluminescent device can be exemplified by a hole injection layer, a hole transport layer, an electron blocking layer, and the like.

[0092] As the material for the hole injection layer, the hole transport layer, and the electron blocking layer, any material can be selected from known related materials used for OLED devices.

[0093] Examples of the above materials include phthalocyanine derivatives, triazole derivatives, triarylmethane derivatives, triarylamine derivatives, oxazole derivatives, oxadiazole derivatives, hydrazone derivatives, stilbene derivatives, pyridoline derivatives, polysilane derivatives, imidazole derivatives, phenylenediamine derivatives, amino-substituted quilone derivatives, styryl anthracene derivatives, styrylamine derivatives and the like, fluorene derivatives, spirofluorene derivatives, silazane derivatives, aniline copolymers, porphyrin compounds, carbazole derivatives, polyarylalkane derivatives, polyphenylene vinyl and its derivatives, polythiophene and its derivatives, poly-N-vinylcarbazole derivatives, thiophene oligomers and the like, conductive polymer oligomers, aromatic tertiary amine compounds, styrene amination compounds, compounds, triamines, tetraamines, benzidines, propargyl diamine derivatives, p-phenylenediamine derivatives, m-phenylenediamine derivatives, 1,1'-bis(4-diarylaminophenyl)cyclohexane, 4,4'-bis(diarylamino)biphenyls, bis[4-(diarylamino)phenyl]methanes, 4,4'-bis(diarylamino)terphenyls, 4,4'-bis(diarylamino)quaterphenyls, 4,4'-bis(diarylamino)diphenyl ethers, 4,4'-bis(diarylamino)diphenylsulfanes, bis[4-(diarylamino)phenyl]dimethylmethanes, bis[4-(diarylamino)phenyl]-bis(trifluoromethyl)methanes, or 2,2-diphenylethylene compounds.

[0094] Furthermore, according to the device matching requirements, the hole transport film layer between the electron blocking layer and the hole injection layer of the organic electroluminescent device can be a single film layer or a superposition structure of multiple hole transport materials. In this article, for the above-mentioned hole carrier conduction film layers with different functions, their film thickness is not particularly limited.

[0095] The hole injection layer contains a main organic material that can conduct holes, and also contains a P-type dopant material with a deep HOMO energy level (the corresponding LUMO energy level will also be very deep). Based on empirical summary, in order to achieve smooth injection of holes from the anode to the organic film layer, the HOMO energy level of the main organic material that conducts holes used in the anode interface buffer layer must have certain characteristics with the P-doped material, so that the charge transfer state between the main material and the dopant material can be realized, the ohmic contact between the buffer layer and the anode can be achieved, and the efficient injection from the electrode to the hole injection conduction can be achieved.

[0096] In view of the above empirical summary, for hole-type host materials with different HOMO energy levels, different P-doped materials need to be selected to match them in order to achieve ohmic contact at the interface and improve the hole injection effect.

[0097] Therefore, in one embodiment of the present invention, in order to better inject holes, the hole injection layer also includes a P-type doping material with charge conductivity selected from the following: quinone derivatives, such as tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinodimethane (F4-TCNQ); or hexaazatriphenylene derivatives, such as 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN); or cyclopropane derivatives, such as 4,4',4"-((1E,1'E,1"E)-cyclopropane-1,2,3-trimethylenetris(cyanoformyl))tris(2,3,5,6-tetrafluorobenzyl); or metal oxides, such as tungsten oxide and molybdenum oxide, but not limited to these.

[0098] In the hole injection layer of the present invention, the ratio of the hole transport material to the P-type doping material used is 99:1-95:5, preferably 99:1-97:3, based on mass.

[0099] The thickness of the hole injection layer of the present invention may be 5-100 nm, preferably 5-50 nm, and more preferably 5-20 nm, but the thickness is not limited to this range.

[0100] The thickness of the hole transport layer of the present invention may be 5-200 nm, preferably 10-150 nm, and more preferably 20-100 nm, but the thickness is not limited to this range.

[0101] The thickness of the electron blocking layer of the present invention may be 1-50 nm, preferably 5-40 nm, but the thickness is not limited to this range.

[0102] After forming the hole injection layer, the hole transport layer and the electron blocking layer, a corresponding light emitting layer is formed on the electron blocking layer.

[0103] The light-emitting layer may include a host material and a dopant material. The host material may be a common green light host material in the art, and the dopant material may be a boron-containing organic compound containing a diphenyl-substituted naphthoxypyrrole structure represented by the general formula (1) of the present invention.

[0104] The light-emitting layer may contain a single host material or a dual host material;

[0105] The dual-host material comprises a first host material and a second host material, and preferably at least one of the first host material and the second host material is a TADF material;

[0106] TADF materials refer to materials with thermally activated delayed fluorescence properties, characterized by a small energy level difference between the first excited singlet state and the first excited triplet state, so that the singlet excitons and triplet excitons generated can be used simultaneously in the device, making the utilization rate of the excitons generated by the device as close to 100% as possible. Compared with traditional fluorescent materials, TADF materials have a higher exciton utilization rate.

[0107] The light-emitting layer may include a host material, an exciton-sensitizing material, and a doping material;

[0108] Exciton sensitizing materials refer to materials that can make the luminescent material in the luminescent layer fully utilize the electroexcitons, so that the luminescent layer finally produces the emission spectrum of the sensitized material. Exciton sensitizers may assume functions such as exciton capture, exciton conversion, and exciton transfer in electroluminescent devices. The boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure shown in the general formula (1) of the present invention and the exciton sensitizing material are used in combination, which has a significant improvement effect on improving device efficiency, exciton annihilation in the device, and reducing efficiency.

[0109] In the light-emitting layer of the present invention, the ratio of the host material to the doping material used is 99:1-70:30, preferably 99:1-85:15 and more preferably 97:3-87:13, based on mass.

[0110] The thickness of the light-emitting layer can be adjusted to optimize the light-emitting efficiency and the driving voltage. The preferred thickness range is 5 nm to 50 nm, more preferably 10-50 nm, and more preferably 15-40 nm, but the thickness is not limited to this range.

[0111] In the present invention, the electron transport region may include, from bottom to top, a hole blocking layer, an electron transport layer, and an electron injection layer disposed on the light emitting layer, but is not limited thereto.

[0112] The hole blocking layer is a layer that blocks the holes injected from the anode from passing through the light-emitting layer and entering the cathode, thereby extending the life of the device and improving the efficiency of the device. The hole blocking layer of the present invention can be arranged on the light-emitting layer. As the hole blocking layer material of the organic electroluminescent device of the present invention, compounds with hole blocking effects known in the prior art can be used, for example, phenanthroline derivatives such as bathocuproin (referred to as BCP), metal complexes of hydroxyquinoline derivatives such as aluminum (III) bis (2-methyl-8-quinoline) -4-phenylphenolate (BAlq), various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, 9,9'-(5-(6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)-1,3-phenylene) bis (9H-carbazole) and the like pyrimidine derivatives. The thickness of the hole blocking layer of the present invention can be 2-200nm, preferably 5-150nm, but the thickness is not limited to this range.

[0113] The electron transport layer may be disposed on the light emitting layer or (if present) the hole blocking layer. The electron transport layer material is a material that easily receives electrons from the cathode and transfers the received electrons to the light emitting layer. Preferably, the material has a high electron mobility. As the electron transport layer of the organic electroluminescent device of the present invention, the electron transport layer materials for organic electroluminescent devices known in the prior art can be used, for example, metal complexes of hydroxyquinoline derivatives represented by Alq3, BAlq and Liq, various rare earth metal complexes, triazole derivatives, 2,4-bis(9,9-dimethyl-9H-fluorene-2-yl)-6-(naphthalene-2-yl)-1,3,5-triazine (CAS No.: 1459162-51-6) and other triazine derivatives, 2-(4-(9,10-di(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (CAS No.: 561064-11-7, commonly known as LG201) and other imidazole derivatives, oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silicon-based compound derivatives, etc. The thickness of the electron transport layer of the present invention may be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm, but the thickness is not limited to this range.

[0114] The electron injection layer may be disposed above the electron transport layer. The electron injection layer material is generally preferably a material having a low work function so that electrons are easily injected into the organic functional material layer. As the electron injection layer material of the organic electroluminescent device of the present invention, the electron injection layer material for organic electroluminescent devices known in the prior art can be used, for example, lithium; lithium salts such as 8-hydroxyquinoline lithium, lithium fluoride, lithium carbonate or lithium azide; or cesium salts, cesium fluoride, cesium carbonate or cesium azide. The thickness of the electron injection layer of the present invention may be 0.1-5 nm, preferably 0.5-3 nm and more preferably 0.8-1.5 nm, but the thickness is not limited to this range.

[0115] The second electrode may be disposed above the electron transport region. The second electrode may be a cathode. The second electrode may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode. When the second electrode is a transmissive electrode, the second electrode may include, for example, Li, Yb, Ca, LiF / Ca, LiF / Al, Al, Mg, BaF, Ba, Ag, or a compound or mixture thereof; when the second electrode is a semi-transmissive electrode or a reflective electrode, the second electrode may include Ag, Mg, Yb, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, or a compound or mixture thereof, but is not limited thereto. The thickness of the cathode depends on the material used.

[0116] The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass can or a metal can; or a thin film covering the entire surface of the organic layer.

[0117] The method for preparing the organic electroluminescent device of the present invention comprises laminating an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an organic film layer, an electron transport layer, an electron injection layer and a cathode successively on a substrate, and optionally a covering layer. In this regard, vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing or LITI methods can be used, but are not limited thereto. In the present invention, it is preferred to use a vacuum evaporation method to form the various layers. Those skilled in the art can conventionally select various process conditions in the vacuum evaporation method according to actual needs.

[0118] Synthesis Example

[0119] The raw materials involved in the synthesis examples of the present invention can be purchased from the market or prepared by conventional preparation methods in the art;

[0120] Example 1 Synthesis of Compound 58:

[0121]

[0122] Preparation of intermediate a-1:

[0123] In a three-necked flask, under nitrogen protection, add 10 mmol of raw material B-1, 12 mmol of NaH, and 20 mL of anhydrous DMF, stir at room temperature for 1 hour, then add 10 mmol of raw material A-1, heat to 120°C and react for 6 hours. Naturally cool to room temperature, add 100 mL of water, filter and collect the precipitate, dissolve the precipitate with 20 mL of dichloromethane, dry and filter with anhydrous sodium sulfate, concentrate and separate and purify by silica gel column chromatography to obtain intermediate a-1. LC-MS: Measured value: 568.13 ([M+H] + ), theoretical value: 567.10.

[0124] Preparation of intermediate b-1:

[0125] In a three-necked flask, under nitrogen protection, add 10 mmol of raw material B-2, 12 mmol of NaH, and 20 mL of anhydrous DMF, stir at room temperature for 1 hour, then add 10 mmol of intermediate a-1, heat to 130 ° C and react for 12 hours. Naturally cool to room temperature, add 100 mL of water, filter and collect the precipitate, dissolve the precipitate with 20 ml of dichloromethane, dry and filter with anhydrous sodium sulfate, concentrate and separate and purify by silica gel column chromatography to obtain intermediate b-1. LC-MS: Measured value: 867.21 ([M+H] + ), theoretical value: 866.23.

[0126] Preparation of compound 58:

[0127] In a sealed pressure tube, under nitrogen protection, 10 mmol of intermediate b-1 and 10 mL of anhydrous o-dichlorobenzene were added. After cooling to -78 °C, 12 mmol of 2.5 M n-butyl lithium-n-hexane solution was added dropwise. After transferring to 60 °C for a reverse reaction for 4 hours, the reaction was cooled to -42 °C, 15 mmol of boron tribromide was added dropwise, and the reaction was slowly restored to room temperature for 4 hours. After cooling to 0 °C, ultra-dry N, N-diisopropylamide lithium was added dropwise, and the reaction solution was heated to 180 °C for 18 hours. Cool to room temperature, remove the low boiling point solvent by vacuum distillation, dissolve with dichloromethane, filter, dry with anhydrous sodium sulfate, collect the filtrate by filtration, concentrate, separate and purify with column chromatography to obtain compound 58. Compound 58 was dissolved in toluene solution (1×10 -5 M) The half-peak width is 22 nm, measured by Horiba's Fluorolog-3 series fluorescence spectrometer.

[0128] Example 2 Synthesis of Compound 61:

[0129]

[0130] Preparation of intermediate b-2:

[0131] In a three-necked flask, under nitrogen protection, add 10 mmol of raw material B-3, 12 mmol of NaH, and 20 mL of anhydrous DMF, stir at room temperature for 0.5 hours, then add 10 mmol of intermediate a-1, heat to 120°C and react for 5 hours. Naturally cool to room temperature, add 100 ml of water, filter and collect the precipitate, dissolve the precipitate with 20 ml of dichloromethane, dry and filter with anhydrous sodium sulfate, concentrate and separate and purify by silica gel column chromatography to obtain intermediate b-2. LC-MS: Measured value: 880.28 ([M+H] + ), theoretical value: 879.22.

[0132] Preparation of compound 61:

[0133] In a sealed pressure tube, under nitrogen protection, 10mmol of intermediate b-2 and 10ml of anhydrous o-dichlorobenzene were added. After cooling to -78°C, 12mmol of 2.5M n-butyl lithium-n-hexane solution was added dropwise. After transferring to 60°C for reverse reaction for 2.5 hours, the reaction was cooled to -42°C, 15mmol of boron tribromide was added dropwise, and the reaction was slowly restored to room temperature for 2 hours. After cooling to 0°C, ultra-dry N,N-diisopropylamide lithium was added dropwise, and the reaction solution was heated to 180°C for 6 hours. Cool to room temperature, remove low-boiling solvents by vacuum distillation, dissolve with dichloromethane, filter, dry with anhydrous sodium sulfate, collect the filtrate by filtration, concentrate, separate and purify with column chromatography to obtain compound 61. Compound 61 was dissolved in toluene solution (1×10 -5 M) The half-peak width is 25 nm, which is measured by Horiba's Fluorolog-3 series fluorescence spectrometer. 1 H NMR (400 MHz, deuterated chloroform) δ 7.49 (1H, m), 7.51-7.82 (17H, m), 7.88-8.13 (9H, m), 8.30-8.55 (8H, m), 8.82 (1H, d).

[0134] Example 3 Synthesis of Compound 62:

[0135]

[0136] Preparation of intermediate b-3:

[0137] In a three-necked flask, under nitrogen protection, add 10 mmol of raw material B-4, 12 mmol of NaH, and 20 mL of anhydrous DMF, stir at room temperature for 2 hours, then add 10 mmol of intermediate a-1, heat to 120°C and react for 4 hours. Naturally cool to room temperature, add 100 ml of water, filter and collect the precipitate, dissolve the precipitate with 20 ml of dichloromethane, dry and filter with anhydrous sodium sulfate, concentrate and separate and purify by silica gel column chromatography to obtain intermediate b-3. LC-MS: Measured value: 878.20 ([M+H] + ), theoretical value: 877.21.

[0138] Preparation of compound 62:

[0139] In a sealed pressure tube, under nitrogen protection, add 10mmol intermediate b-3 and 10ml anhydrous o-dichlorobenzene, cool to -78°C, add 12mmol 2.5M n-butyl lithium-n-hexane solution dropwise, transfer to 60°C for reverse reaction for 2 hours, cool the reaction to -42°C, add 15mmol boron tribromide dropwise, slowly return to room temperature and react for 3 hours, cool to 0°C, add ultra-dry N,N-diisopropylamide lithium dropwise, heat the reaction solution to 180°C and react for 10 hours. Cool to room temperature, remove low boiling point solvents by vacuum distillation, dissolve with dichloromethane, filter, dry with anhydrous sodium sulfate and collect the filtrate by filtration, concentrate and separate and purify with column chromatography to obtain compound 62. Compound 62 in toluene solution (1×10 -5 M) The half-peak width is 23 nm, measured by Horiba's Fluorolog-3 series fluorescence spectrometer. 1 H NMR (400 MHz, deuterated chloroform) δ 7.33-8.01 (23H, m), 8.05-8.17 (3H, m), 8.23-8.69 (6H, m), 8.78 (1H, dd), 8.85 (1H, d).

[0140] Example 4 Synthesis of Compound 76:

[0141]

[0142] Preparation of intermediate b-4:

[0143] In a three-necked flask, under nitrogen protection, add 20 mmol of raw material B-1, 24 mmol of NaH, and 20 mL of anhydrous DMF, stir at room temperature for 2 hours, then add 10 mmol of raw material A-1, heat to 120°C and react for 6 hours. Naturally cool to room temperature, add 100 ml of water, filter and collect the precipitate, dissolve the precipitate with 20 ml of dichloromethane, dry and filter with anhydrous sodium sulfate, concentrate and separate and purify by silica gel column chromatography to obtain intermediate b-4. LC-MS: Measured value: 867.27 ([M+H] + ), theoretical value: 866.23.

[0144] Preparation of compound 76:

[0145] In a sealed pressure tube, under nitrogen protection, 10mmol of intermediate b-4 and 10ml of anhydrous o-dichlorobenzene were added. After cooling to -78°C, 12mmol of 2.5M n-butyl lithium-n-hexane solution was added dropwise. After transferring to 60°C for reverse reaction for 2.5 hours, the reaction was cooled to -42°C, 15mmol of boron tribromide was added dropwise, and the reaction was slowly restored to room temperature for 4 hours. After cooling to 0°C, ultra-dry N,N-diisopropylamide lithium was added dropwise, and the reaction solution was heated to 180°C for 4 hours. Cool to room temperature, remove low-boiling solvents by vacuum distillation, dissolve with dichloromethane, filter, dry with anhydrous sodium sulfate, collect the filtrate by filtration, concentrate, separate and purify with column chromatography to obtain compound 76. Compound 76 was dissolved in toluene solution (1×10 -5 M) The half-peak width is 25 nm, which is measured by Horiba's Fluorolog-3 series fluorescence spectrometer. 1 H NMR (400 MHz, deuterated chloroform) δ 7.52-7.80 (19H, m), 7.91-8.24 (10H, m), 8.53-8.62 (6H, m), 8.78 (2H, d).

[0146] Example 5 Synthesis of Compound 116:

[0147]

[0148] Synthesis of intermediate c-1:

[0149] In a three-necked flask, under nitrogen protection, add 10 mmol of raw material A-2, 10 mmol of raw material C-1, 20 mL of tetrahydrofuran, 1 mL of water, 12 mmol of potassium carbonate, and 0.1 mmol of Pd(PPh3)4, heat under reflux and stir for 6 hours, cool to room temperature, separate and collect the organic phase, dry and filter over anhydrous sodium sulfate, concentrate and separate and purify by silica gel column chromatography to obtain intermediate c-1. LC-MS: Measured value: 381.21 ([M+H] +), theoretical value: 380.10.

[0150] Preparation of intermediate a-2:

[0151] In a three-necked flask, under nitrogen protection, add 10 mmol of raw material B-1, 12 mmol of NaH, and 20 mL of anhydrous DMF, stir at room temperature for 2 hours, then add 10 mmol of intermediate c-1, heat to 120°C and react for 8 hours. Naturally cool to room temperature, add 100 mL of water, filter and collect the precipitate, dissolve the precipitate with 20 mL of dichloromethane, dry and filter with anhydrous sodium sulfate, concentrate and separate and purify by silica gel column chromatography to obtain intermediate a-2. LC-MS: Measured value: 680.37 ([M+H] + ), theoretical value: 679.22.

[0152] Preparation of intermediate b-5:

[0153] In a three-necked flask, under nitrogen protection, add 10 mmol of raw material B-5, 12 mmol of NaH, and 20 mL of anhydrous DMF, stir at room temperature for 2 hours, then add 10 mmol of intermediate a-2, heat to 100 ° C and react for 6 hours. Naturally cool to room temperature, add 100 ml of water, filter and collect the precipitate, dissolve the precipitate with 20 ml of dichloromethane, dry and filter with anhydrous sodium sulfate, concentrate and separate and purify by silica gel column chromatography to obtain intermediate b-5. LC-MS: Measured value: 992.41 ([M+H] + ), theoretical value: 991.35.

[0154] Preparation of compound 116:

[0155] In a sealed pressure tube, under nitrogen protection, 10mmol of intermediate b-5 and 10ml of anhydrous o-dichlorobenzene were added. After cooling to -78°C, 12mmol of 2.5M n-butyl lithium-n-hexane solution was added dropwise. After transferring to 60°C for reverse reaction for 2 hours, the reaction was cooled to -42°C, 15mmol of boron tribromide was added dropwise, and the reaction was slowly restored to room temperature for 2 hours. After cooling to 0°C, ultra-dry N,N-diisopropylamide lithium was added dropwise, and the reaction solution was heated to 180°C for 6 hours. Cool to room temperature, remove low-boiling solvents by vacuum distillation, dissolve with dichloromethane, filter, dry with anhydrous sodium sulfate, collect the filtrate by filtration, concentrate, separate and purify with column chromatography to obtain compound 116. Compound 116 was dissolved in toluene solution (1×10 -5 M) The half-peak width is 21 nm, measured by Horiba's Fluorolog-3 series fluorescence spectrometer. 1H NMR (400 MHz, deuterated chloroform) δ 1.88 (18H, s), 7.31-8.09 (23H, m), 8.15-8.44 (7H, m), 8.52-8.83 (3H, m), 8.97 (1H, d).

[0156] Example 6 Synthesis of Compound 245:

[0157]

[0158] Preparation of intermediate d-1:

[0159] In a three-necked flask, under nitrogen protection, add 10 mmol of raw material B-6, 12 mmol of NaH, and 20 mL of anhydrous DMF, stir at room temperature for 2 hours, then add 10 mmol of raw material A-3, heat to 120°C and react for 4 hours. Naturally cool to room temperature, add 100 ml of water, filter and collect the precipitate, dissolve the precipitate with 20 ml of dichloromethane, dry and filter with anhydrous sodium sulfate, concentrate and separate and purify by silica gel column chromatography to obtain intermediate d-1. LC-MS: Measured value: 417.30 ([M+H] + ), theoretical value: 416.23.

[0160] Preparation of intermediate b-6:

[0161] In a three-necked flask, under nitrogen protection, add 10 mmol of intermediate d-1, 12 mmol of NaH, and 20 mL of anhydrous DMF, stir at room temperature for 2 hours, then add 10 mmol of intermediate a-2, heat to 120°C and react for 10 hours. Naturally cool to room temperature, add 100 mL of water, filter and collect the precipitate, dissolve the precipitate with 20 ml of dichloromethane, dry and filter with anhydrous sodium sulfate, concentrate and separate and purify by silica gel column chromatography to obtain intermediate b-6. LC-MS: Measured value: 1076.33 ([M+H] + ), theoretical value: 1075.44.

[0162] Preparation of compound 245:

[0163] In a sealed pressure tube, under nitrogen protection, 10mmol of intermediate b-6 and 10ml of anhydrous o-dichlorobenzene were added. After cooling to -78°C, 12mmol of 2.5M n-butyl lithium-n-hexane solution was added dropwise. After transferring to 60°C for reverse reaction for 3 hours, the reaction was cooled to -42°C, 15mmol of boron tribromide was added dropwise, and the reaction was slowly restored to room temperature for 2 hours. After cooling to 0°C, ultra-dry N,N-diisopropylamide lithium was added dropwise, and the reaction solution was heated to 180°C for 10 hours. Cool to room temperature, remove low-boiling solvents by vacuum distillation, dissolve with dichloromethane, filter, dry with anhydrous sodium sulfate, collect the filtrate by filtration, concentrate, separate and purify with column chromatography to obtain compound 245. Compound 245 was dissolved in toluene solution (1×10 -5 M) The half-peak width is 21 nm, measured by Horiba's Fluorolog-3 series fluorescence spectrometer.

[0164] Example 7 Synthesis of Compound 262:

[0165]

[0166] Preparation of intermediate a-3:

[0167] In a three-necked flask, under nitrogen protection, add 10 mmol of raw material A-4, 12 mmol of potassium carbonate, 25 mL of anhydrous DMF, 12 mmol of raw material B-1, 0.2 mmol of Pd2(dba)3, and 0.6 mmol of RuPhos, and heat under reflux and stir for 6 hours. Naturally cool to room temperature, add 100 mL of water, filter and collect the precipitate, dissolve the precipitate with 20 mL of dichloromethane, dry and filter with anhydrous sodium sulfate, concentrate and separate and purify by silica gel column chromatography to obtain intermediate a-3. LC-MS: Measured value: 564.22 ([M+H] + ), theoretical value: 563.10.

[0168] Preparation of intermediate e-1:

[0169] In a three-necked flask, under nitrogen protection, add 10mmol of intermediate a-3, 12mmol of potassium tert-butoxide, 30mL of o-xylene, 12mmol of raw material D-1, 0.2mmol of Pd2(dba)3, and 0.6mmol of tri-tert-butylphosphine, and heat under reflux and stir for 12 hours. After removing the solvent under reduced pressure, dissolve it in 20ml of dichloromethane, dry it over anhydrous sodium sulfate, filter it, concentrate it, and separate and purify it by silica gel column chromatography to obtain intermediate e-1. LC-MS: Measured value: 765.44 ([M+H] + ), theoretical value: 764.39.

[0170] Preparation of intermediate b-7:

[0171] In a three-necked flask, under nitrogen protection, add 10 mmol of intermediate e-1, 12 mmol of potassium tert-butoxide, 30 mL of o-xylene, 12 mmol of raw material A-5, 0.2 mmol of Pd2(dba)3, and 0.6 mmol of tri-tert-butylphosphine, and heat under reflux and stir for 20 hours. After removing the solvent under reduced pressure, dissolve it in 20 mL of dichloromethane, dry it over anhydrous sodium sulfate, filter it, concentrate it, and separate and purify it by silica gel column chromatography to obtain intermediate b-7. LC-MS: Measured value: 1004.36 ([M+H] + ), theoretical value: 1003.46.

[0172] Preparation of compound 262:

[0173] In a sealed pressure tube, under nitrogen protection, 10 mmol of intermediate b-7 and 10 mL of anhydrous o-dichlorobenzene were added. After cooling to -78 °C, 12 mmol of 2.5 M n-butyl lithium-n-hexane solution was added dropwise. After transferring to 60 °C for 4 hours, the reaction was cooled to -42 °C, 15 mmol of boron tribromide was added dropwise, and the reaction was slowly restored to room temperature for 3 hours. After cooling to 0 °C, ultra-dry N, N-diisopropylamide lithium was added dropwise, and the reaction solution was heated to 180 °C for 17 hours. Cool to room temperature, remove low-boiling solvents by vacuum distillation, dissolve with dichloromethane, filter, dry with anhydrous sodium sulfate, collect the filtrate by filtration, concentrate, separate and purify with column chromatography to obtain compound 262. Compound 262 was dissolved in toluene solution (1×10 -5 M) The half-peak width is 25 nm, which is measured by Horiba's Fluorolog-3 series fluorescence spectrometer.

[0174] The structural characteristics of the compounds obtained in each example are shown in Table 1

[0175] Table 1

[0176]

[0177] Device Embodiment

[0178] The following describes in detail the application effect of the OLED material synthesized by the present invention in the device through device embodiments 1-7 and device comparative examples 1-4. The device manufacturing process of device embodiments 2-7 and device comparative examples 1-4 of the present invention is exactly the same as that of device embodiment 1, and the same substrate material and electrode material are used. The film thickness of the electrode material is also the same. The difference is that the light-emitting layer material in the device is replaced. The layer structure and test results of each device embodiment are shown in Table 2 and Table 3 respectively.

[0179] Device Example 1

[0180] like Figure 1As shown, the transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness is 150nm) is washed, that is, washing with a cleaning agent (Semiclean M-L20), washing with pure water, drying, and then ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, a vacuum evaporation device is used to evaporate HT-1 and HI-1 with a film thickness of 10nm as a hole injection layer 3, and the mass ratio of HT-1 and HI-1 is 97:3. Then evaporate HT-1 with a thickness of 60nm as a hole transport layer 4. Then evaporate EB-1 with a thickness of 30nm as an electron blocking layer 5. After the above electron blocking material is evaporated, the light-emitting layer 6 of the OLED light-emitting device is prepared, using GH-1 and GH-2 as the main materials, compound 58 as the doping material, GH-1, GH-2 and compound 58 The mass ratio is 69:30:1, and the film thickness of the light-emitting layer is 30nm. After the above-mentioned light-emitting layer 6, HB-1 was vacuum-deposited to a thickness of 5 nm, which was the hole blocking layer 7. After the above-mentioned hole blocking layer 7, ET-1 and Liq were vacuum-deposited to a thickness of 30 nm, with a mass ratio of ET-1 to Liq of 1:1. On the electron transport layer 8, a LiF layer with a thickness of 1 nm was made by vacuum evaporation, which was the electron injection layer 9. On the electron injection layer 9, a Mg:Ag electrode layer with a thickness of 80 nm was made by vacuum evaporation, with a mass ratio of Mg to Ag of 1:9, which was used as the cathode layer 10.

[0181] The following describes in detail the application effect of the OLED material synthesized by the present invention in the device through device embodiments 8-14 and device comparative examples 5-8. The device manufacturing process of device embodiments 8-14 and device comparative examples 5-8 of the present invention is exactly the same as that of device embodiment 8, and the same substrate material and electrode material are used. The film thickness of the electrode material is also the same. The difference is that the light-emitting layer material in the device is replaced. The layer structure and test results of each device embodiment are shown in Table 2 and Table 3 respectively.

[0182] Device Example 8

[0183] The transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness is 150nm) is washed, that is, washed with a cleaning agent (SemicleanM-L20), washed with pure water, dried, and then washed with ultraviolet-ozone to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, a vacuum evaporation device is used to evaporate HT-1 and HI-1 with a film thickness of 10nm as the hole injection layer 3, and the mass ratio of HT-1 to HI-1 is 97:3. Then, HT-1 with a thickness of 60nm is evaporated as the hole transport layer 4. Then, EB-1 with a thickness of 30nm is evaporated as the electron blocking layer 5. After the above-mentioned electron blocking material is deposited, the light-emitting layer 6 of the OLED light-emitting device is prepared, using GH-1 and GH-2 as the main materials, GD-1 as the first doping material, and compound 58 as the second doping material. The mass ratio of GH-1, GH-2, GD-1 and compound 58 is 66:30:3:1, and the thickness of the light-emitting layer is 30nm. After the above-mentioned light-emitting layer 6, HB-1 is vacuum-deposited with a film thickness of 5nm. This layer is the hole blocking layer 7. After the above-mentioned hole blocking layer 7, ET-1 and Liq are vacuum-deposited. The mass ratio of ET-1 and Liq is 1:1, and the film thickness is 30nm. This layer is the electron transport layer 8. On the electron transport layer 8, a LiF layer with a film thickness of 1nm is prepared by a vacuum evaporation device. This layer is the electron injection layer 9. On the electron injection layer 9, a Mg:Ag electrode layer with a film thickness of 80nm is prepared by a vacuum evaporation device. The mass ratio of Mg and Ag is 1:9. This layer is used as the cathode layer 10.

[0184] The molecular structure formula of the relevant materials is shown below:

[0185]

[0186]

[0187] After the OLED light emitting device is completed as described above, the anode and cathode are connected by a known driving circuit, and the current efficiency and life of the device are measured. The device examples and comparative examples prepared by the same method are shown in Table 2; the test results of the current efficiency and life of the obtained device are shown in Table 3.

[0188] Table 2

[0189]

[0190]

[0191] Table 3

[0192]

[0193] Note: Current efficiency and luminescence peak are tested using IVL (current-voltage-luminance) test system (Suzhou Fushida Scientific Instrument Co., Ltd.); life test system is EAS-62C OLED device life tester from Japan System Technology Co., Ltd.; LT95 refers to the time it takes for the device brightness to decay to 95%; all data are at 10mA / cm 2 Next test.

[0194] It can be seen from the device data results in Table 3 that, compared with the comparative compounds ref-1, ref-2, ref-3, and ref-4, the luminescence peak of the compound of the present invention is between 510 and 550 nm, and the green luminescence effect can be well achieved; compared with device comparison examples 1-8, the organic light-emitting device of the present invention, whether in a single-doping system or a double-doping system, has a greatly improved current efficiency and lifespan relative to OLED devices of known materials; when an exciton-sensitizing material is used as the first doping, the device efficiency is significantly improved compared with a single doping.

[0195] In summary, the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure, characterized in that: The structure of the boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure is shown in any one of the general formulas (14) to (18) and (31) to (32): In the general formulae (14) to (18), (31) and (32), Z is C-R1; R1, which is the same or different each time, is H, a deuterium atom, a cyano group, a substituted or unsubstituted C1-C 10 substituted or unsubstituted alkyl, substituted or unsubstituted adamantyl, substituted amino, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted terphenylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl; Z1, Z2, Z3, Z4, and Z5 are independently represented by CH or CR; Each occurrence of R is the same or different and represents a deuterium atom, a cyano group, a substituted or unsubstituted C1-C 10 substituted or unsubstituted alkyl, substituted or unsubstituted adamantyl, substituted amino, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted terphenylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl; Ar6, Ar7, Ar 14 ,Ar 15 Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted diphenylfluorenyl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group; The substituent for the substituent group is optionally selected from one or more of a deuterium atom, a cyano group, an adamantyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-amyl group, a tert-butyl group, a butyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a dibenzofuranyl group, a dibenzothienyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a carbazolyl group, and an N-phenylcarbazolyl group.

2. The boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure according to claim 1, characterized in that: The structure of the boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure is shown in any one of the general formulas (33) to (37): In general formula (33) to general formula (37), the definition of Z is the same as that in claim 1; Ar 16 -Ar 19 Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted diphenylfluorenyl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a substituted or unsubstituted carbazolyl group; R a , R b , R c , R d , R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , R o , R p , R q Each occurrence is the same or different and represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1~C 10 One of alkyl, substituted or unsubstituted adamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted terphenylene, substituted or unsubstituted triphenylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and substituted or unsubstituted carbazolyl; The substituent for the substituent group is optionally selected from one or more of a deuterium atom, a cyano group, an adamantyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-amyl group, a tert-butyl group, a butyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a dibenzofuranyl group, a dibenzothienyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a carbazolyl group, and an N-phenylcarbazolyl group.

3. The boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure according to claim 1, characterized in that: The R is the same or different each time it appears, and is represented by deuterium, methyl, deuterated methyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, adamantyl-substituted phenyl, diphenyl-substituted amino, and diphenyl-substituted amino; The R1 is the same or different each time it appears and is represented by hydrogen, deuterium, methyl, deuterated methyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, adamantyl-substituted phenyl, diphenyl-substituted amino, diphenyl-substituted amino; Ar6, Ar7, Ar 14 ,Ar 15 It represents one of phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, dibenzofuranyl, dibenzothienyl, tert-butyl-substituted dibenzothienyl, carbazolyl, tert-butyl-substituted carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, tert-butyl-substituted dibenzofuranyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, adamantyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, and tert-butyl-substituted biphenyl.

4. The boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure according to claim 2, characterized in that: The R1, R a , R b , R c , R d , R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , R o , R p , R q Each occurrence, which is the same or different, represents hydrogen, deuterium, methyl, deuterated methyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, adamantyl-substituted phenyl; The Ar 16 -Ar 19 It represents one of phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, dibenzofuranyl, dibenzothienyl, tert-butyl-substituted dibenzothienyl, carbazolyl, tert-butyl-substituted carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, tert-butyl-substituted dibenzofuranyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, adamantyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, and tert-butyl-substituted biphenyl.

5. A boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure, characterized in that: The structure of the boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure is shown in any one of the general formulas (14) to (18) and (31) to (32): In the general formulae (14) to (18), (31) and (32), Z is C-R1; R1, which is the same or different each time, is H, a deuterium atom, a cyano group, a substituted or unsubstituted C1-C 10 substituted or unsubstituted alkyl, substituted or unsubstituted adamantyl, substituted amino, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted terphenylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl; The substituent for the substituent group is selected from one or more of a deuterium atom, a cyano group, an adamantyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-amyl group, a tert-butyl group, a butyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a dibenzofuranyl group, a dibenzothienyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a carbazolyl group, and an N-phenylcarbazolyl group; Z1, Z2, Z3, Z4, and Z5 are independently represented by CH or CR; The R is represented by the following structure: Ar6, Ar7, Ar 14 ,Ar 15 They are independently represented as follows:

6. A boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure, characterized in that: The structure of the boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure is shown in any one of the general formulas (33) to (37): In the general formulae (33) to (37), Z is C-R1; R1, which is the same or different each time, is H, a deuterium atom, a cyano group, or a substituted or unsubstituted C1-C 10 substituted or unsubstituted alkyl, substituted or unsubstituted adamantyl, substituted amino, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted terphenylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl; The substituent for the substituent group is selected from one or more of a deuterium atom, a cyano group, an adamantyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-amyl group, a tert-butyl group, a butyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a dibenzofuranyl group, a dibenzothienyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a carbazolyl group, and an N-phenylcarbazolyl group; The R a , R b , R c , R d , R e , R f , R g , R h , R i , R j , R k , R l , R m , R n , R o , R p , R q It is represented by the following structure: The Ar 16 -Ar 19 They are independently represented as follows:

7. A boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure, characterized in that: The specific structural formula of the boron-containing organic compound is any one of the following structures:

8. An organic light-emitting device comprising a cathode, an anode and a functional layer, wherein the functional layer is located between the cathode and the anode, characterized in that: The functional layer of the organic light-emitting device comprises the boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure according to any one of claims 1 to 7.

9. The organic light-emitting device according to claim 8, wherein the functional layer comprises a light-emitting layer, and the light-emitting layer is the boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure according to any one of claims 1 to 7; 10. The organic light-emitting device according to claim 8, wherein the functional layer comprises a light-emitting layer, the light-emitting layer comprises a host material and a doping material, and the doping material of the light-emitting layer is the boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure according to any one of claims 1 to 7.

11. The organic light emitting device according to claim 9, characterized in that: The light-emitting layer comprises a first main material, a second main material and a doping material, at least one of the first main material and the second main material is a TADF material, and the doping material is a boron-containing organic compound containing a diphenyl-substituted naphthoxypyrrole structure as claimed in any one of claims 1 to 7.

12. The organic light-emitting device according to claim 9, wherein the light-emitting layer comprises a host material, an exciton sensitizing material and a doping material, wherein: The exciton sensitizing material is a complex containing a metal element, and the doping material is a boron-containing organic compound containing a diphenyl-substituted naphthopyrrole structure as claimed in any one of claims 1 to 7.

Images