Polycyclic compound, application thereof and organic electroluminescent device

Abstract

The invention relates to the field of organic electroluminescent materials, and discloses a polycyclic compound, application thereof and an organic electroluminescent device, and the polycyclic compound has a structure as shown in a formula (I). When the polycyclic compound is applied to a device, the current density can be reduced and the service life of the device can be prolonged on the premise of ensuring certain brightness.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescent materials, specifically to a polycyclic compound and its applications, and an organic electroluminescent device. Background Technology

[0002] In 1987, Tang et al. of Kodak Corporation fabricated a double-layer organic light-emitting diode (OLED) using an aromatic diamine as the hole transport layer and 8-hydroxyquinoline aluminum as the light-emitting layer via vacuum evaporation. The OLED achieved a driving voltage of less than 10V, a luminous efficiency of 1.5 lm / W, and a luminous intensity as high as 1000 cd / m². 2 This makes organic light-emitting devices (OLEDs) practically useful.

[0003] OLEDs have received widespread attention in the fields of optoelectronic devices and flat panel displays due to their simple structure, low driving voltage, and ability to achieve flexible displays.

[0004] Through continuous development, OLED technology has now been commercialized in fields such as flat panel displays and solid-state lighting.

[0005] However, organic electroluminescent devices or screens still suffer from problems such as high driving voltage and low luminous efficiency. Among them, blue guest materials, especially dark blue guest materials, are the bottleneck affecting the overall performance of OLED screens, including low exciton utilization, low color purity, and low luminous efficiency caused by concentration quenching.

[0006] To improve these shortcomings, it is necessary to improve the performance of the guest material on the one hand, and further optimize the device structure and fabrication process on the other. Summary of the Invention

[0007] The purpose of this invention is to provide a new class of polycyclic compounds so that organic light-emitting devices containing these polycyclic compounds can have improved luminous efficiency and lifetime characteristics compared with existing devices.

[0008] To achieve the above objectives, a first aspect of the present invention provides a polycyclic compound having the structure shown in formula (I):

[0009]

[0010] In equation (I),

[0011] R1 is selected from C 1-20 The alkyl group, unsubstituted group, or C group substituted with at least one group from combination A, containing or not containing heteroatoms as cyclic atoms. 5-40 aryl;

[0012] R2 is selected from C atoms that are unsubstituted or substituted by at least one group from combination A, and may or may not contain heteroatoms as cyclic atoms. 5-40 aryl;

[0013] R3 is selected from H and C. 1-20 The alkyl group, unsubstituted group, or group substituted by at least one group from combination B, containing or not containing heteroatoms as cyclic atoms. 5-40 aryl;

[0014] The heteroatom is selected from at least one of N, S, and O; the combination A is composed of C 1-20 Composition B consists of alkyl groups and unsubstituted phenyl groups; the combination B is composed of C. 1-20 It consists of alkyl, carbazole, and unsubstituted phenyl groups.

[0015] A second aspect of the present invention provides the use of the polycyclic compounds described in the first aspect in organic electroluminescent devices.

[0016] A third aspect of the present invention provides an organic electroluminescent device comprising an anode, a hole injection layer, a hole transport layer, an emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode, which are sequentially stacked; wherein the emitting layer contains at least one of the polycyclic compounds described in the first aspect.

[0017] Compared with the prior art, the technical solution provided by the present invention has at least the following advantages:

[0018] 1. The polycyclic compound provided by the present invention contains a maleimide derivative, which is a chromophore, and the maleimide derivative is located on the parent nucleus, which can increase the spatial structure of the parent nucleus and weaken the quenching effect of dye concentration.

[0019] 2. The polycyclic compound provided by the present invention has a narrow half-width at half-maximum (WHM), which can improve the light emission efficiency of the top-emitting device using the polycyclic compound, thereby significantly improving the overall performance of the device without changing its electrical properties.

[0020] 3. Furthermore, when the aforementioned polycyclic compound of the present invention is applied in a device, it can reduce the current density and increase the lifespan of the device while ensuring a certain level of brightness. Detailed Implementation

[0021] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0022] In this invention, unless otherwise specified, groups of the same type have similar interpretations, and will not be described in detail here.

[0023] C 1-20 The alkyl group refers to a straight-chain or branched alkyl group with a total number of carbon atoms of 1-20 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20). Exemplarily, it can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, etc.

[0024] C that is unsubstituted or substituted by at least one group in combination A, containing or not containing heteroatoms as cyclic atoms. 5-40 The aryl group indicates that the group has a total number of carbon atoms of 5-40; the cyclic atoms on the group may or may not contain heteroatoms; the group may or may not contain substituents, and if it contains substituents, these substituents may be any one or at least two selected from combination A; the group may be bonded to the parent nucleus structure at any site that can bond to the parent nucleus structure, and there are no special requirements in this invention.

[0025] Unless otherwise specified, aryl in this case is interpreted broadly.

[0026] Unless otherwise specified, the substituents in R1, R2, and R3 in this case can be bonded to the parent nucleus structure at any possible bonding site. For example, when the substituent is a carbazoyl group, the carbazoyl group represents a group provided by the removal of any possible H from the carbazoyl substance. This invention will not be described in detail here, and those skilled in the art should not understand it as a limitation of the invention.

[0027] As previously stated, a first aspect of the present invention provides a polycyclic compound having the structure shown in formula (I):

[0028]

[0029] In equation (I),

[0030] R1 is selected from C 1-20 The alkyl group, unsubstituted group, or C group substituted with at least one group from combination A, containing or not containing heteroatoms as cyclic atoms. 5-40 aryl;

[0031] R2 is selected from C atoms that are unsubstituted or substituted by at least one group from combination A, and may or may not contain heteroatoms as cyclic atoms. 5-40 aryl;

[0032] R3 is selected from H and C. 1-20 The alkyl group, unsubstituted group, or group substituted by at least one group from combination B, containing or not containing heteroatoms as cyclic atoms. 5-40 aryl;

[0033] The heteroatom is selected from at least one of N, S, and O; the combination A is composed of C 1-20 Composition B consists of alkyl groups and unsubstituted phenyl groups; the combination B is composed of C. 1-20 It consists of alkyl, carbazole, and unsubstituted phenyl groups.

[0034] In the preferred case, in equation (I),

[0035] R1 is selected from C 1-16 The alkyl group, unsubstituted group, or C group substituted with at least one group from combination A, containing or not containing heteroatoms as cyclic atoms. 5-32 aryl;

[0036] R2 is selected from C atoms that are unsubstituted or substituted by at least one group from combination A, and may or may not contain heteroatoms as cyclic atoms. 5-32 aryl;

[0037] R3 is selected from H and C. 1-16 The alkyl group, unsubstituted group, or group substituted by at least one group from combination B, containing or not containing heteroatoms as cyclic atoms. 5-32 aryl;

[0038] The heteroatom is selected from at least one of N, S, and O; the combination A is composed of C 1-16 Composition B consists of alkyl groups and unsubstituted phenyl groups; the combination B is composed of C. 1-16 It consists of alkyl, carbazole, and unsubstituted phenyl groups.

[0039] More preferably, in equation (I),

[0040] R1 is selected from C 1-20 Alkyl, unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, unsubstituted or substituted anthraquinyl, unsubstituted or substituted phenanthryl, unsubstituted or substituted dibenzofuranyl, unsubstituted or substituted dibenzothiopheneyl, unsubstituted or substituted fluorenyl, unsubstituted or substituted quinolinyl, unsubstituted or substituted pyridyl, unsubstituted or substituted quinazolinyl, unsubstituted or substituted quinoxalinyl;

[0041] R2 is selected from phenyl (unsubstituted or substituted by at least one group in combination A), naphthyl (unsubstituted or substituted by at least one group in combination A), anthraceneyl (unsubstituted or substituted by at least one group in combination A), phenanthyl (unsubstituted or substituted by at least one group in combination A), fluorenyl (substituted by at least one group in combination A), dibenzothiopheneyl (unsubstituted or substituted by at least one group in combination A), pyridyl (unsubstituted or substituted by at least one group in combination A), quinolinyl (unsubstituted or substituted by at least one group in combination A), quinazolinyl (unsubstituted or substituted by at least one group in combination A), and quinoxalinyl (unsubstituted or substituted by at least one group in combination A).

[0042] R3 is selected from H and C. 1-20 Alkyl, unsubstituted or substituted phenyl, naphthyl, unsubstituted or substituted anthraquinone, phenanthrene, dibenzofuranyl, dibenzothiophene, carbazoyl substituted with at least one group in combination B, fluorenyl substituted with at least one group in combination B, diphenylamino, pyridinyl, quinolinyl, quinazolinyl, quinoxalinyl, pyrimidinyl, phenanthrolinel, benzofuranyl;

[0043] Combination A consists of C 1-20 Composition B consists of alkyl groups and unsubstituted phenyl groups; the combination B is composed of C. 1-20 It consists of alkyl, carbazole, and unsubstituted phenyl groups.

[0044] In a particularly preferred case, in equation (I),

[0045] R1 is selected from C 1-16 Alkyl, unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, unsubstituted or substituted anthraquinyl, unsubstituted or substituted phenanthryl, unsubstituted or substituted dibenzofuranyl, unsubstituted or substituted dibenzothiopheneyl, unsubstituted or substituted fluorenyl, unsubstituted or substituted quinolinyl, unsubstituted or substituted pyridyl, unsubstituted or substituted quinazolinyl, unsubstituted or substituted quinoxalinyl;

[0046] R2 is selected from phenyl (unsubstituted or substituted by at least one group in combination A), naphthyl (unsubstituted or substituted by at least one group in combination A), anthraceneyl (unsubstituted or substituted by at least one group in combination A), phenanthyl (unsubstituted or substituted by at least one group in combination A), fluorenyl (substituted by at least one group in combination A), dibenzothiopheneyl (unsubstituted or substituted by at least one group in combination A), pyridyl (unsubstituted or substituted by at least one group in combination A), quinolinyl (unsubstituted or substituted by at least one group in combination A), quinazolinyl (unsubstituted or substituted by at least one group in combination A), and quinoxalinyl (unsubstituted or substituted by at least one group in combination A).

[0047] R3 is selected from H and C. 1-16 Alkyl, unsubstituted or substituted phenyl, naphthyl, unsubstituted or substituted anthraquinone, phenanthrene, dibenzofuranyl, dibenzothiophene, carbazoyl substituted with at least one group in combination B, fluorenyl substituted with at least one group in combination B, diphenylamino, pyridinyl, quinolinyl, quinazolinyl, quinoxalinyl, pyrimidinyl, phenanthrolinel, benzofuranyl;

[0048] Combination A consists of C 1-16 Composition B consists of alkyl groups and unsubstituted phenyl groups; the combination B is composed of C. 1-16 It consists of alkyl, carbazole, and unsubstituted phenyl groups.

[0049] According to a particularly preferred embodiment, the compound represented by formula (I) is selected from any of the following:

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056] According to another particularly preferred embodiment, the compound represented by formula (I) is selected from any of the following:

[0057]

[0058]

[0059]

[0060] This invention does not impose any particular limitations on the specific methods for preparing the aforementioned polycyclic compounds. Those skilled in the art can obtain the aforementioned polycyclic compounds based on the specific structural formulas provided by this invention, combined with known knowledge in the field of organic synthesis. Furthermore, several examples are exemplarily provided below to illustrate the methods for preparing the polycyclic compounds of this invention. Those skilled in the art can also obtain specific methods for preparing all other polycyclic compounds by changing the types of raw materials according to the methods for preparing the polycyclic compounds described below. This invention will not elaborate on the preparation methods for all polycyclic compounds, and this should not be construed as a limitation of the invention.

[0061] As previously stated, the second aspect of the present invention provides the application of the polycyclic compounds described in the first aspect in organic electroluminescent devices.

[0062] Preferably, the polycyclic compound is present in the light-emitting layer of the organic electroluminescent device.

[0063] In a preferred embodiment, the polycyclic compound is a guest material in the light-emitting layer of the organic electroluminescent device.

[0064] As mentioned above, a third aspect of the present invention provides an organic electroluminescent device, which includes an anode, a hole injection layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode arranged in sequence.

[0065] The light-emitting layer contains at least one of the polycyclic compounds described in the first aspect.

[0066] Preferably, a hole transport layer is further provided between the hole injection layer and the light-emitting layer.

[0067] According to a preferred embodiment, the organic electroluminescent device includes an anode, a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode, which are stacked sequentially.

[0068] More preferably, an electron blocking layer is further disposed between the hole transport layer and the light-emitting layer.

[0069] According to another preferred embodiment, the organic electroluminescent device includes an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode, which are stacked sequentially.

[0070] According to some embodiments of the present invention, the anode material forming the anode is generally preferably a material with a high work function. For example, the anode material used in the present invention is selected from one or more of the following materials: metals, such as vanadium, chromium, copper and gold, or other alloys; metal oxides, such as zinc oxide, indium oxide, indium tin oxide, indium zinc oxide and tin dioxide; combinations of metals and oxides, such as zinc oxide and aluminum, but not limited thereto.

[0071] According to some embodiments of the present invention, the material forming the hole injection layer has the ability to transport holes. Therefore, the material of the hole injection layer has a hole injection effect in the anode, exhibits excellent hole injection effect on the light-emitting layer or light-emitting material, prevents excitons generated in the light-emitting layer from migrating to the electron injection layer or electron injection material, and further has excellent thin film forming ability. The HOMO of the hole injection material is preferably between that of the anode material and the HOMO of the surrounding organic material layer.

[0072] According to some embodiments of the present invention, the material forming the hole transport layer is a material capable of receiving holes from the anode or hole injection layer, moving holes to the light-emitting layer, and having a high mobility for holes.

[0073] According to some embodiments of the present invention, the hole injection material and the hole transport material include at least one of the following: aromatic amine derivatives (e.g., NPB, SqMA1), hexaazabenzophenanthrene derivatives (e.g., HACTN), indolecarbazole derivatives, conductive polymers (e.g., PEDOT / PSS), phthalocyanine or porphyrin derivatives, dibenzoindofluoreneamine, and spirodifluoreneamine, but are not limited thereto.

[0074] According to some embodiments of the present invention, the hole injection layer and the hole transport layer may, for example, be formed using aromatic amine derivatives of the following general formula:

[0075]

[0076] R in the above general formula 11 To R 19 The groups are each independently selected from single bonds, hydrogen, deuterium, alkyl, benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, fluorene, dimethylfluorene, spirodifluorene, carbazole, thiophene, benzo[a]thiophene, dibenzo[a]thiophene, furan, benzo[a]furan, dibenzo[a]furan, indole, indolecarbazole, indo[a]carbazole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, pyridazine, or triazine, etc., leaving any 1-2 H atoms that can leave the group.

[0077] According to some embodiments of the present invention, the material for forming the electron blocking layer is not particularly limited; generally, compounds that meet the first and / or second condition below can be considered for use:

[0078] First: It has a shallower LUMO energy level (smaller absolute value), the purpose of which is to reduce the number of electrons leaving the luminescent layer, thereby increasing the probability of recombination of electrons and holes in the luminescent layer.

[0079] Second: It possesses a large triplet energy, the purpose of which is to reduce the number of excitons leaving the luminescent layer, thereby improving the efficiency of exciton conversion luminescence.

[0080] According to some embodiments of the present invention, the materials forming the electron blocking layer include, but are not limited to, aromatic amine derivatives (e.g., NPB) and spirodifluoreneamine (e.g., SpMA2), wherein some electron blocking materials have structures similar to hole injection materials and hole transport materials.

[0081] According to some embodiments of the present invention, the luminescent material of the luminescent layer is a material capable of emitting light in the visible light region by receiving holes and electrons from the hole transport layer and the electron transport layer respectively and combining the holes and electrons, and preferably a material with good quantum efficiency for fluorescence or phosphorescence.

[0082] According to some embodiments of the present invention, the light-emitting layer may comprise a host material and a guest material.

[0083] According to some embodiments of the present invention, the main material may include anthracene derivatives, carbazole derivatives, fluorene derivatives, aromatic amine derivatives, organosilicon derivatives, carbazole-triazine derivatives, phosphorooxygen derivatives, phenanthroline derivatives, but is not limited thereto.

[0084] In some preferred embodiments of the present invention, the anthracene derivatives have the following general formula:

[0085]

[0086] The phosphorooxy derivatives have the following general formula:

[0087]

[0088] In the general formulas of the above anthracene derivatives and phosphorooxy derivatives, R11, R12, R13, R14, R15 and R16 are each independently selected from single bonds, hydrogen, deuterium, alkyl, benzene, biphenyl, terphenyl, tetraphenyl, naphthalene, phenylnaphthalene, anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, fluorene, carbazole, thiophene, benzo[a]thiophene, dibenzo[a]thiophene, furan, benzo[a]furan, dibenzo[a]furan, indole, indolecarbazole, indo[a]carbazole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carboline, pyrazine, pyridazine or triazine, and groups represented by their substituted derivatives.

[0089] The guest material in the luminescent layer of the present invention is any one of the polycyclic compounds described in the first aspect of the present invention.

[0090] According to some embodiments of the present invention, the material of the hole blocking layer may preferably be a compound having the following first and / or second conditions:

[0091] First: It has a deeper HOMO energy level (larger absolute value), the purpose of which is to reduce the number of holes leaving the luminescent layer, thereby increasing the probability of recombination of electrons and holes in the luminescent layer.

[0092] Second: It possesses a large triplet energy, the purpose of which is to reduce the number of excitons leaving the luminescent layer, thereby improving the efficiency of exciton conversion luminescence.

[0093] According to some embodiments of the present invention, the material forming the hole blocking layer may include, for example, a phenanthroline derivative (e.g., Bphen, BCP), a benzo[a]phenanthrene derivative, a benzimidazole derivative, but is not limited thereto.

[0094] According to some embodiments of the present invention, the electron injection layer is a layer that injects electrons from the electrode, and the electron injection material is preferably a compound that has the ability to transport electrons, has the effect of injecting electrons from the cathode, has an excellent effect of injecting electrons into the light-emitting layer or light-emitting material, prevents excitons generated in the light-emitting layer from migrating to the hole injection layer, and also has excellent thin film forming ability. Electron injection layer materials include, for example, LiF, CsF, Cs₂CO₃, and LiQ, but are not limited to these.

[0095] According to some embodiments of the present invention, the cathode material is generally preferably a material with a small work function, which allows electrons to be smoothly injected into the organic material layer. The cathode material that can be used in this disclosure can be selected from one or more of the following materials: Al, Mg and Ag.

[0096] According to some embodiments of the present invention, the organic electroluminescent device of the present invention preferably has one or more layers coated by vacuum evaporation. Before vacuum coating, different functional layer materials are placed in an evaporation boat, and a mechanical pump is used to evacuate the vacuum, which needs to reach a vacuum level of 10. -3 Pa or less, preferably less than 10 Pa -4 Below Pa, vacuum deposition of organic thin films begins. Organic small molecules, after being heated and sublimated in a vacuum, detach from the material surface at a certain initial velocity and fly outwards to the substrate surface, where they cool and deposit to form a thin film. Multiple layers are deposited according to the above vacuum deposition method. During the thin film deposition process, a quartz crystal oscillator is used to monitor the thickness and rate of thin film deposition on the substrate in real time.

[0097] According to some embodiments of the present invention, the organic electroluminescent device of the present invention preferably uses a solution method, that is, the polycyclic compound of the present invention is formulated into a solution and formed into one or more layers by spin coating or by any printing method, such as screen printing, flexographic printing, inkjet printing, or offset printing. However, when using this method to fabricate multiple layers, layer-to-layer damage is likely to occur. That is, when one layer is fabricated and another layer is fabricated using the solution, the solvent in the solution will destroy the already formed layer, which is detrimental to device fabrication. The polycyclic compound provided by the present invention can be structurally modified to allow the polycyclic compound of the present invention to undergo cross-linking under heating or ultraviolet exposure, thereby maintaining the integrity of the layers without damage. The polycyclic compound of the present invention can also be applied from the solution and subsequently cross-linked in the polymer network or fixed in the corresponding layers.

[0098] According to some embodiments of the present invention, preferred solvents for preparing organic electroluminescent devices are selected from toluene, anisole, o-xylene, m-xylene, p-xylene, methyl benzoate, mesitylene, naphthalene, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, phenoxytoluene, and especially 3-phenoxytoluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methyl anisole, 4-methyl anisole, 3,4-dimethyl anisole, and 3,5-dimethyl anisole. Acetophenone, benzothiazole, butyl benzoate, isopropanol, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, methyl benzoate, NMP, p-methylisopropylbenzene, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentobenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 2-heptanol, 3-heptanol, or mixtures of these solvents.

[0099] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all raw materials used are commercially available products. Unless otherwise specified, room temperature as mentioned below refers to 25±1℃.

[0100] Preparation Example 1: Synthesis of Compound 6

[0101]

[0102] Synthesis of intermediate 6-1: In a reactor, 0.2 mol of aniline, 0.1 mol of 2-chloro-1,3-dibromobenzene, 0.6 mmol of palladium acetate, 0.6 mmol of 4,5-bis(diphenylphosphine-9,9-dimethyloxanthracene), 0.4 mol of sodium tert-butoxide, and 270 mL of toluene were added, and the mixture was refluxed and stirred for 12 hours. After cooling to room temperature, ethyl acetate and water were added, and the organic layer was separated. Purification by silica gel column chromatography yielded intermediate 6-1 (yield: 71.0%).

[0103] Synthesis of intermediate 6-2: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 6-2 (yield: 70.7%).

[0104] Synthesis of intermediate 6-3: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 6-3 (yield: 71.2%).

[0105] Synthesis of Compound 6: 0.03 mol of intermediate 6-3 and 200 mL of tert-butylbenzene were added to a reactor, followed by the dropwise addition of 0.09 mol of a 1.7 M tert-butyllithium pentane solution at -78 °C. After heating to 60 °C and stirring for 2 hours, nitrogen gas was purged at 60 °C to completely remove the pentane. After cooling to -78 °C, 0.03 mol of boron tribromide was added dropwise. After heating to room temperature and stirring for 2 hours, the mixture was cooled to 0 °C, followed by the dropwise addition of 0.06 mol of N,N-diisopropylethylamine. The mixture was heated to 120 °C and stirred for 16 hours. After cooling to room temperature, 10 v / v sodium acetate aqueous solution and ethyl acetate were added, the organic layer was separated, and the mixture was concentrated under reduced pressure. Purification was performed by silica gel column chromatography to give Compound 6 (yield: 43.1%).

[0106] Mass spectrometry: C42H35BN4O4, theoretical value: 670.28, measured value: 670.30. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.39~1.44 (19H, s), 6.82~6.86 (2H, s), 6.96~7.04 (2H, d), 7.05~7.11 (4H, m), 7.20~7.28 (6H, m), 7.87~7.89 (2H, s).

[0107] Preparation Example 2: Synthesis of Compound 12

[0108]

[0109] Synthesis of intermediate 12-1: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 12-1 (yield: 71.7%).

[0110] Synthesis of intermediate 12-2: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 12-2 (yield: 70.2%).

[0111] Synthesis of compound 12: The synthesis method was the same as that for compound 6, yielding compound 12 (yield: 42.9%).

[0112] Mass spectrometry: C50H35BN4O4, theoretical value: 766.28, measured value: 766.30. 1H-NMR (400MHz, CDCl3) (ppm) δ=2.11~2.15 (13H, s), 6.82~6.86 (2H, d), 6.96~7.11 (6H, m), 7.16~7.34 (12H, m), 7.87~7.89 (2H, s).

[0113] Preparation Example 3: Synthesis of Compound 17

[0114]

[0115] Synthesis of intermediate 17-1: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 17-1 (yield: 71.3%).

[0116] Synthesis of intermediate 17-2: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 17-2 (yield: 70.9%).

[0117] Synthesis of compound 17: The synthesis method was the same as that of compound 6, yielding compound 17 (yield: 43.8%).

[0118] Mass spectrometry: C54H43BN4O4, theoretical value: 822.34, measured value: 822.35. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.30~1.35(19H, s), 6.82~6.86(2H, d), 6.96~7.04(2H, m), 7.05~7.11(4H, m), 7.20~7.28(14H, m), 7.87~7.89(2H, s).

[0119] Preparation Example 4: Synthesis of Compound 25

[0120]

[0121] Synthesis of intermediate 25-1: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 25-1 (yield: 69.7%).

[0122] Synthesis of intermediate 25-2: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 25-2 (yield: 70.4%).

[0123] Synthesis of intermediate 25-3: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 25-3 (yield: 71.1%).

[0124] Synthesis of compound 25: The synthesis method was the same as that for compound 6, yielding compound 25 (yield: 41.6%).

[0125] Mass spectrometry: C54H43BN4O4, theoretical value: 822.34, measured value: 822.35. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.30~1.35(20H, s), 6.83~6.85(2H, d), 7.08~7.11(8H, s), 7.22~7.26(1H, m), 7.41~7.45(4H, m), 7.54~7.59(6H, m), 7.87~7.89(2H, s).

[0126] Preparation Example 5: Synthesis of Compound 41

[0127]

[0128] Synthesis of intermediate 41-1: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 41-1 (yield: 70.2%).

[0129] Synthesis of intermediate 41-2: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 41-2 (yield: 68.7%).

[0130] Synthesis of compound 41: The synthesis method was the same as that for compound 6, yielding compound 41 (yield: 42.8%).

[0131] Mass spectrometry: C50H35BN4O4, theoretical value: 766.28, measured value: 766.30. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.30~1.34 (10H, s), 6.96~7.11 (9H, m), 7.20~7.28 (4H, m), 7.39~7.47 (4H, m), 7.52~7.62 (6H, m), 7.87~7.89 (2H, s).

[0132] Preparation Example 6: Synthesis of Compound 42

[0133]

[0134] Synthesis of intermediate 42-1: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 42-1 (yield: 70.1%).

[0135] Synthesis of intermediate 42-2: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 42-2 (yield: 69.7%).

[0136] Synthesis of intermediate 42-3: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 42-3 (yield: 70.2%).

[0137] Synthesis of compound 42: The synthesis method was the same as that for compound 6, yielding compound 42 (yield: 43.4%).

[0138] Mass spectrometry: C44H31BN4O4, theoretical value: 690.24, measured value: 690.25. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.15~1.23 (7H, m), 3.58~3.68 (4H, m), 6.91~6.94 (2H, s), 6.96~7.11 (7H, m), 7.20~7.28 (4H, m), 7.37~7.53 (3H, m), 7.72~7.78 (2H, m), 7.87~7.89 (2H, s).

[0139] Preparation Example 7: Synthesis of Compound 51

[0140]

[0141] Synthesis of intermediate 51-1: Under a nitrogen protective atmosphere, 0.1 mol of diphenylboramide acid and 0.1 mol of 1,3-dibromo-2-chloro-5-iodobenzene were added to a dry three-necked flask. 50 mL of concentrated sulfuric acid was added to dissolve them. The mixture was heated to 80 °C and refluxed for 12 hours. After the reaction was complete, water was added to quench the reaction. The mixture was extracted multiple times with dichloromethane. The organic phases from the multiple extractions were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated by rotary evaporation to obtain the crude product. The crude product was purified by rapid column chromatography to obtain intermediate 51-1 (yield: 64.5%).

[0142] Synthesis of intermediate 51-2: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 51-2 (yield: 69.2%).

[0143] Synthesis of intermediate 51-3: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 51-3 (yield: 69.2%).

[0144] Synthesis of compound 51: The synthesis method was the same as that for compound 6, yielding compound 51 (yield: 42.3%).

[0145] Mass spectrometry: C50H36BN4O4, theoretical value: 781.29, measured value: 781.30. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.16~1.22 (6H, m), 3.61~3.65 (4H, m), 6.47~6.50 (2H, s), 6.97~7.12 (13H, m), 7.21~7.27 (9H, m), 7.88~7.89 (2H, s).

[0146] Preparation Example 8: Synthesis of Compound 58

[0147]

[0148] Synthesis of intermediate 58-1: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 58-1 (yield: 68.9%).

[0149] Synthesis of intermediate 58-2: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 58-2 (yield: 69.2%).

[0150] Synthesis of compound 58: The synthesis method was the same as that for compound 6, yielding compound 58 (yield: 42.3%).

[0151] Mass spectrometry: C39H29BN4O4, theoretical value: 628.23, measured value: 628.25. 1H-NMR (400MHz, CDCl3) (ppm) δ=2.29~2.33(10H, s), 3.03~3.06(6H, s), 6.90~6.92(2H, s), 7.11~7.17(9H, m), 7.87~7.89(2H, s).

[0152] Preparation Example 9: Synthesis of Compound 61

[0153]

[0154] Synthesis of intermediate 61-1: The synthesis method is the same as that for intermediate 6-1, yielding intermediate 61-1 (yield: 69.8%).

[0155] Synthesis of intermediate 61-2: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 61-2 (yield: 70.3%).

[0156] Synthesis of compound 61: The synthesis method was the same as that for compound 6, yielding compound 61 (yield: 41.4%).

[0157] Mass spectrometry: C54H59BN4O4, theoretical value: 838.46, measured value: 838.45. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.30~1.34 (30H, s), 1.40~1.44 (19H, m), 7.05~7.11 (8H, s), 7.88~7.89 (2H, s).

[0158] Preparation Example 10: Synthesis of Compound 70

[0159]

[0160] Synthesis of intermediate 70-1: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 70-1 (yield: 70.8%).

[0161] Synthesis of compound 70: The synthesis method was the same as that for compound 6, yielding compound 70 (yield: 42.7%).

[0162] Mass spectrometry: C49H33BN4O4, theoretical value: 752.26, measured value: 752.25. 1H-NMR (400MHz, CDCl3) (ppm) δ=2.29~2.33 (10H, s), 6.90~6.92 (2H, s), 7.11~7.17 (9H, m), 7.41~7.45 (4H, m), 7.54~7.60 (6H, m), 7.87~7.89 (2H, s).

[0163] Preparation Example 11: Synthesis of Compound 83

[0164]

[0165] Synthesis of intermediate 83-1: 0.01 mol of 1,3-dibromo-2-chloro-5-iodobenzene was dissolved in 40 mL of toluene solvent. Nitrogen gas was introduced and the mixture was stirred. 0.01 mol of 4-tert-butylphenylboronic acid, 0.1 mol of potassium carbonate, and 0.3 mmol of tetra(triphenylphosphine)palladium were added sequentially. The mixture was heated to reflux. After 6 h, HPLC analysis showed that the starting material had basically reacted completely. The reaction was stopped, and the mixture was cooled and filtered to obtain the crude product. The crude product was completely dissolved in toluene, and the filtrate was evaporated to dryness under reduced pressure. The residue was subjected to column chromatography to obtain intermediate 83-1 (yield: 79.2%).

[0166] Synthesis of intermediate 83-2: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 83-2 (yield: 69.9%).

[0167] Synthesis of intermediate 83-3: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 83-3 (yield: 71.0%).

[0168] Synthesis of intermediate 83-4: The synthesis method is the same as that of intermediate 6-1, yielding intermediate 83-4 (yield: 70.6%).

[0169] Synthesis of compound 83: The synthesis method was the same as that for compound 6, yielding compound 83 (yield: 43.1%).

[0170] Mass spectrometry: C54H51BN4O4, theoretical value: 830.40, measured value: 830.39. 1H-NMR (400MHz, CDCl3) (ppm) δ=1.31~1.34 (9H, s), 1.38~1.44 (13H, d), 2.26~2.30 (13H, s), 4.34~4.48 (2H, m), 6.92~6.94 (2H, s), 6.99~7.01 (2H, m), 7.14~7.16 (4H, d), 7.35~7.40 (2H, m), 7.44~7.49 (2H, m), 7.87~7.89 (2H, s).

[0171] Device Example 1

[0172] 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 (volume ratio 1:1), baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0173] The glass substrate with the anode was placed in a vacuum chamber and evacuated to a vacuum level of 1×10⁻⁶. -5 Pa, HAT-CN is vacuum-deposited on the above-mentioned anodic layer as a hole injection layer at a deposition rate of 0.1 nm / s and a total film thickness of 10 nm; then, hole transport layer HT-1 is deposited at a deposition rate of 0.1 nm / s and a thickness of 60 nm.

[0174] An electron blocking layer TCTA of the device was vacuum-deposited on top of the hole transport layer at a deposition rate of 0.1 nm / s and a total film thickness of 10 nm.

[0175] The light-emitting layer of the device is vacuum-deposited on top of the electron blocking layer. The light-emitting layer includes a host material and a guest material. Using a multi-source co-evaporation method, the evaporation rate of the host material BH is adjusted to 0.1 nm / s, the evaporation rate of the guest material compound 6 is set to 5%, and the total evaporation film thickness is 30 nm.

[0176] A hole blocking layer (BCP) is vacuum-deposited on top of the light-emitting layer at a deposition rate of 0.1 nm / s and a thickness of 5 nm. Then, an electron transport layer is deposited by using a multi-source co-evaporation method, adjusting the deposition rates of ET-1 and ET-2 to 0.1 nm / s, with a total film thickness of 30 nm.

[0177] A 0.5 nm thick LiF layer was vacuum-deposited on the electron transport layer (ETL) as the electron injection layer, and a 150 nm thick Al layer was used as the cathode of the device.

[0178] Device Examples 2-11

[0179] Organic light-emitting devices of Device Examples 2-11 were prepared using a method similar to that of Device Example 1, except that compound 6 in Device Example 1 was replaced with the compounds shown in Table 1.

[0180] The molecular structures mentioned above are as follows:

[0181]

[0182] Device Comparison Examples 1-3

[0183] The organic electroluminescent device of Comparative Example 1 was prepared using a method similar to that of Device Example 1, except that compound 6 in Device Example 1 was replaced with Ref1, Ref2 and Ref3 respectively.

[0184] The molecular structures involved are as follows:

[0185]

[0186] Test Example 1

[0187] At a brightness of 1000 cd / m² 2 The driving voltage, current efficiency, and color coordinates of the organic electroluminescent devices prepared in Device Examples 1-11 and Device Comparative Examples 1-3 were measured, and the results are shown in Table 1.

[0188] Table 1

[0189]

[0190] The above results show that the polycyclic compounds of the present invention, when applied to organic electroluminescent devices, exhibit higher device luminous efficiency and lower driving voltage compared to comparative embodiments.

[0191] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A polycyclic compound, characterized by, The polycyclic compound has a structure shown in formula (I): In formula (I), R1is selected from C 1-20 alkyl, C 5-40 aryl, which contains or does not contain a heteroatom as a ring-forming atom, which is unsubstituted or substituted by at least one radical from combination A; R2 is selected from C atoms that are unsubstituted or substituted by at least one group from combination A, and may or may not contain heteroatoms as cyclic atoms. 5-40 aryl; R3is selected from H, C 1-20 alkyl, C 5-40 aryl, which can or can not contain heteroatoms as ring members, unsubstituted or substituted by at least one radical from combination B; The heteroatom is selected from at least one of N, S, O; the combination A consists of C 1-20 alkyl, unsubstituted phenyl; the combination B consists of C 1-20 alkyl, carbazolyl, unsubstituted phenyl.

2. The polycyclic compound of claim 1, wherein In formula (I), R1is selected from C 1-16 alkyl, C 5-32 aryl, which is unsubstituted or substituted by at least one radical from combination A; R2is selected from C6-Ci0aryl, which is unsubstituted or substituted by at least one radical from group A; and 5-32 C6-Ci0aryl, which is unsubstituted or substituted by at least one radical from group A; and R3is selected from H, C 1-16 alkyl, C 5-32 aryl, which can or can not contain heteroatoms as ring members; The heteroatom is selected from at least one of N, S, O; the combination A consists of C 1-16 alkyl, unsubstituted phenyl; the combination B consists of C 1-16 alkyl, carbazolyl, unsubstituted phenyl.

3. The polycyclic compound of claim 1, wherein In formula (I), R1is selected from C 1-20 alkyl, phenyl which is unsubstituted or substituted by at least one radical from combination A, naphthyl which is unsubstituted or substituted by at least one radical from combination A, anthryl which is unsubstituted or substituted by at least one radical from combination A, phenanthryl which is unsubstituted or substituted by at least one radical from combination A, dibenzofuranyl which is unsubstituted or substituted by at least one radical from combination A, dibenzothiophenyl which is unsubstituted or substituted by at least one radical from combination A, fluorenyl which is substituted by at least one radical from combination A, quinolinyl which is unsubstituted or substituted by at least one radical from combination A, pyridinyl which is unsubstituted or substituted by at least one radical from combination A, quinazolinyl which is unsubstituted or substituted by at least one radical from combination A, quinoxalinyl which is unsubstituted or substituted by at least one radical from combination A; R2 is selected from phenyl unsubstituted or substituted with at least one group from combination A, naphthyl unsubstituted or substituted with at least one group from combination A, anthryl unsubstituted or substituted with at least one group from combination A, phenanthryl unsubstituted or substituted with at least one group from combination A, fluorenyl substituted with at least one group from combination A, dibenzothiophenyl unsubstituted or substituted with at least one group from combination A, pyridyl unsubstituted or substituted with at least one group from combination A, quinolyl unsubstituted or substituted with at least one group from combination A, quinazolinyl unsubstituted or substituted with at least one group from combination A, quinoxalinyl unsubstituted or substituted with at least one group from combination A; R3is selected from H, C 1-20 alkyl, phenyl, naphthyl, anthryl, phenanthryl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, fluorenyl, diphenylamino, pyridyl, quinolyl, quinazolyl, quinoxalyl, pyrimidyl, phenanthrolinyl, benzofuranyl, unsubstituted or substituted by at least one radical from combination B; Combination A consists of C 1-20 Composition B consists of alkyl groups and unsubstituted phenyl groups; the combination B is composed of C. 1-20 It consists of alkyl, carbazole, and unsubstituted phenyl groups.

4. The polycyclic compound of claim 3, wherein In formula (I), R1is selected from C 1-16 alkyl, phenyl which is unsubstituted or substituted by at least one radical from combination A, naphthyl which is unsubstituted or substituted by at least one radical from combination A, anthryl which is unsubstituted or substituted by at least one radical from combination A, phenanthryl which is unsubstituted or substituted by at least one radical from combination A, dibenzofuranyl which is unsubstituted or substituted by at least one radical from combination A, dibenzothiophenyl which is unsubstituted or substituted by at least one radical from combination A, fluorenyl which is substituted by at least one radical from combination A, quinolinyl which is unsubstituted or substituted by at least one radical from combination A, pyridinyl which is unsubstituted or substituted by at least one radical from combination A, quinazolinyl which is unsubstituted or substituted by at least one radical from combination A, quinoxalinyl which is unsubstituted or substituted by at least one radical from combination A; R2 is selected from phenyl unsubstituted or substituted with at least one group from combination A, naphthyl unsubstituted or substituted with at least one group from combination A, anthryl unsubstituted or substituted with at least one group from combination A, phenanthryl unsubstituted or substituted with at least one group from combination A, fluorenyl substituted with at least one group from combination A, dibenzothiophenyl unsubstituted or substituted with at least one group from combination A, pyridyl unsubstituted or substituted with at least one group from combination A, quinolyl unsubstituted or substituted with at least one group from combination A, quinazolinyl unsubstituted or substituted with at least one group from combination A, quinoxalinyl unsubstituted or substituted with at least one group from combination A; R3is selected from H, C 1-16 alkyl, phenyl, naphthyl, anthryl, phenanthryl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, fluorenyl, diphenylamino, pyridyl, quinolyl, quinazolyl, quinoxalyl, pyrimidyl, phenanthrolinyl, benzofuranyl, unsubstituted or substituted by at least one radical from combination B; Combination A consists of C 1-16 Composition B consists of alkyl groups and unsubstituted phenyl groups; the combination B is composed of C. 1-16 It consists of alkyl, carbazole, and unsubstituted phenyl groups.

5. The polycyclic compound according to any one of claims 1 to 4, wherein The compound shown in formula (I) is selected from any one of the following:

6. The polycyclic compound of claim 5, wherein The compound shown in formula (I) is selected from any one of the following:

7. Use of the polycyclic compound according to any one of claims 1-6 in an organic electroluminescence device.

8. Use according to claim 7, characterized in that, The polycyclic compound is present in a light-emitting layer of the organic electroluminescence device.

9. Use according to claim 8, characterized in that, The polycyclic compound is a guest material in the light-emitting layer of the organic electroluminescence device.

10. An organic electroluminescent device, characterized by comprising The organic electroluminescence device comprises an anode, a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode which are sequentially stacked; The light-emitting layer contains at least one of the polycyclic compounds according to any one of claims 1-6.

Images