Compound, preparation method, organic light-emitting device and display device

Abstract

The invention provides a compound, a preparation method, an organic light-emitting device and a display device. The compound has a structure as shown in a formula (I): # imgabs0 #. By adopting the compound disclosed by the invention, the light-emitting color purity and the light-emitting efficiency of a phosphorescent material can be improved, and the service life of an organic light-emitting device can be prolonged.

Description

Technical Field

[0001] The present application relates to the field of materials, and specifically to a compound, a preparation method, an organic light-emitting device, and a display device. Background Art

[0002] In the field of organic light-emitting diode (OLED) materials, phosphorescent OLED luminescent layer doping materials have developed rapidly and matured. They are mainly based on some heavy metal organic complexes, such as iridium, platinum (II), europium, osmium, etc. Phosphorescent materials can fully utilize the energy of singlet and triplet excitons in the luminescence process, so theoretically their quantum efficiency can reach 100%, and they are luminescent materials that are studied more in the industry and academia. At present, mainstream OLED luminescent materials (red light materials and green light materials) often use iridium complexes. Compared with iridium complexes, divalent platinum (hereinafter referred to as platinum (II)) complexes also have the advantages of heavy atom effect, d orbital participation in excited states (metal to ligand charge transfer & metal-metal-ligand charge transfer excited state luminescence), high photoluminescence quantum yield (PLQY), narrow half-peak width, high stability and easy molecular orientation control, and are a potential substitute for iridium complexes.

[0003] In recent years, phosphorescent OLED materials based on platinum (II) have been gradually developed and achieved good research results. Unlike the common trivalent iridium (III) that forms an octahedral coordination structure, platinum (II) is tetra-coordinated, and therefore generally forms a planar structure complex, and its ligands are mainly divided into bidentate, tridentate and tetradentate ligands. Compared with bidentate and tridentate ligands, tetradentate platinum (II) complexes do not contain auxiliary ligands, and the chelating effect is enhanced, and they usually have good stability. However, the existing phosphorescent materials of platinum (II) complexes usually have a planar configuration, and molecules are prone to interaction, resulting in multiple emission peaks and a wide half-peak width, which in turn leads to insufficient luminescent color purity of the phosphorescent materials of platinum (II) complexes. In addition, the luminescence efficiency of existing phosphorescent material devices of platinum (II) complexes needs to be improved. Summary of the invention

[0004] The present application provides a compound, a preparation method, an organic light-emitting device, and a display device to improve the luminescent color purity and luminescent efficiency of phosphorescent materials.

[0005] In a first aspect, the present application provides a compound having a structure as shown in formula (I):

[0006]

[0007] In formula (I), M is selected from divalent Pt;

[0008] Z1-Z4 are each independently a covalent bond, an oxygen atom, a sulfur atom or a selenium atom, and two of Z1-Z4 are coordinate covalent bonds;

[0009] X 10 ~X 40 and X 41 ~X 44 are each independently C or N, and X 40 ~X 44 At least one of them is selected from N;

[0010] Q1 and Q2 are each independently selected from a single bond, a divalent element or a divalent group;

[0011] C1 is a single bond, a divalent element, a divalent group, a C5-C30 carbocyclic group, or a C2-C30 heterocyclic structure;

[0012] A1 to A3 are each independently selected from a C5-C30 carbocyclic group or a C2-C30 heterocyclic structure;

[0013] B1-B4 are each independently selected from a C5-C30 carbocyclic group or a C2-C30 heterocyclic structure; B1-B4 are each independently present or absent and at least one of B1-B4 exists;

[0014] A5 is present or absent. When A5 is present, A5 is a C5-C30 carbocyclic group or a C2-C30 heterocyclic structure and B4 and A5 rings have common atoms; when A5 is absent, B4 and A4 have common atoms;

[0015] R A1 ~R A5 and R B1 ~R B4 Each independently exists or does not exist, R A1 ~R A5 and R B1 ~R B4 When present, R A1 and R B1 , R A2 and R B2 , R A3 and R B3 , R A4 and R A5 and R B4 They can be independently connected to form a ring or fused structure;

[0016] R A1 ~R A5 and R B1 ~R B4Each is independently selected from at least one of a hydrogen atom, a deuterium atom, a halogen, a hydroxyl group, a thiol group, a nitro group, a cyano group, an isocyano group, a sulfone group, a hydroxylamine group, a carboxyl group, a carbonyl group, an amino group, an aromatic hydrocarbon, a heteroaromatic hydrocarbon, a heterocycloalkane, a straight-chain alkane, a cycloalkane, an alkene, a cycloalkene, an alkyne, a cycloalkyne, a monosubstituted amino group, a disubstituted amino group, an alkoxy group, an aromatic ring oxygen group, an aromatic heterocyclic oxygen group, an amide group, an alkylthio group, an aromatic ring sulfur group, a heteroaromatic ring sulfur group, a silicon group, and a boron group.

[0017] The compound of the present application is a platinum (II) complex of a tetradentate ligand, and a peripheral group is introduced into the core skeleton of the tetradentate ligand to form a multi-substituted cyclic structure, thereby constructing a new type of ligand compound with stronger rigidity. Among them, in the structure of the compound of the present application, the periphery of its molecular structure is a cyclic group. After the cyclic group is introduced into the periphery, the peripheral group can increase the molecular distance, inhibit stacking, and thus reduce the half-peak width, which can be beneficial to improve the luminous color purity of the material and improve the luminous efficiency of the light-emitting device.

[0018] In an optional implementation, at least two of B1 to B4 exist. When B1 exists, A1 and B1 are connected in parallel rings or by a single bond. When B2 exists, A2 and B2 are connected in parallel rings or by a single bond. When B3 exists, A3 and B3 are connected in parallel rings or by a single bond. When B4 exists, A4 and B4 are connected in parallel rings or by a single bond.

[0019] In an optional implementation, at least one cycloalkyl group is present in B1 to B4. In an optional implementation, one cycloalkyl group is present in B1 to B4. For example, B1 is a cycloalkyl group, or B2 is a cycloalkyl group, or B3 is a cycloalkyl group, or B4 is a cycloalkyl group. In an optional implementation, two cycloalkyl groups are present in B1 to B4. For example, B1 and B2 are cycloalkyl groups, or B1 and B3 are cycloalkyl groups, or B1 and B4 are cycloalkyl groups, or B2 and B3 are cycloalkyl groups, or B3 and B4 are cycloalkyl groups. In an optional implementation, three cycloalkyl groups are present in B1 to B4. For example, B1, B2 and B3 are cycloalkyl groups, or B1, B2 and B4 are cycloalkyl groups, or B2, B3 and B4 are cycloalkyl groups. In an optional implementation, four cycloalkyl groups are present in B1 to B4. For example, B1, B2, B3 and B4 are all cycloalkyl groups.

[0020] In an optional implementation, the cycloalkyl group and the A1 to A5 connected thereto are connected in parallel rings. For example, when B1 is a cycloalkyl group, B1 is connected in parallel rings to A1; when B2 is a cycloalkyl group, B2 is connected in parallel rings to A2; when B3 is a cycloalkyl group, B3 is connected in parallel rings to A3; when B4 is a cycloalkyl group and A5 is present, B4 is connected in parallel rings to A5, and when A5 is absent, B4 is connected in parallel rings to A4.

[0021] In an optional implementation, the cycloalkyl group may be a substituted or unsubstituted cycloalkyl group, and the substituents of the substituted cycloalkyl group may be selected from alkyl substituents, such as methyl, ethyl, etc. The number of substitutions may be 1 to the maximum possible number. For example, when the cycloalkyl group is a C6 cycloalkyl group, the number of substituents may be 1-10.

[0022] In an optional implementation, formula (I-1) The connection structure of A1 is selected from one of the following structures:

[0023]

[0024]

[0025] Among them, *, ** and *** represent the connection sites.

[0026] In an optional implementation, formula (I-2) The connection structure of A2 is selected from one of the following structures:

[0027]

[0028] Among them, *, ** and *** represent the connection sites.

[0029] In an optional implementation, formula (I-3) The connection structure of A3 is selected from one of the following structures:

[0030]

[0031] Among them, *, ** and *** represent the connection sites.

[0032] In an optional implementation, formula (I-4) The connection structure of A4 is selected from one of the following structures:

[0033]

[0034] Among them, * and **** represent the connection sites.

[0035] In an optional implementation, formula (I-4) The connection structure of A5 is selected from one of the following structures:

[0036]

[0037] Among them, * and **** represent the connection sites.

[0038] In an optional implementation, the connection structure of B1-B4 in formula (I) is selected from one of the following structures:

[0039]

[0040] Among them, A 1-5 is one of A1-A4, R B1-4 For R B1 ~R B4 one of the.

[0041] In a second aspect, the present application provides a method for preparing a compound, comprising: mixing a precursor containing B1A1, a precursor containing B2A2, a precursor containing B3A3, a precursor containing B4A5A4, and an ionic compound of M, and adding at least one reaction solution to allow the resulting mixture to undergo a synthesis reaction, and extracting to obtain the compound represented by formula (I).

[0042] Wherein: in the precursor of B1A1, B1 is present or absent. In the precursor of B2A2, B2 is present or absent. In the precursor of B3A3, B3 is present or absent. In the precursor of B4A5A4, B4 is present or absent, and A5 is present or absent.

[0043] In a third aspect, the present application provides a method for preparing a light-emitting layer, the preparation method comprising: depositing a light-emitting material on a surface of a substrate to form the light-emitting layer on the surface of the substrate, wherein the light-emitting material is a compound of the present application.

[0044] In a fourth aspect, the present application provides an organic light-emitting device, comprising an anode layer and a cathode layer, and at least one organic layer between the anode layer and the cathode layer, wherein one of the organic layers comprises the compound of the present application.

[0045] The organic layer is selected from at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. In the implementation of the present application, a stacked hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer are provided between the anode layer and the cathode layer. The hole transport layer is provided close to the anode layer, and the electron injection layer is provided close to the electron injection layer. The light-emitting layer comprises compounds of each possible implementation of the present application.

[0046] In a fifth aspect, the present application provides a display device, including a display screen and the organic light-emitting device of the present application.

[0047] The display device of the present application includes devices such as mobile phones, tablet computers, laptop computers, flat-panel displays, flexible displays, or outdoor display panels.

[0048] The technical effects that can be achieved by the second to fifth aspects mentioned above can be described with reference to the corresponding effects in the first aspect mentioned above, and will not be repeated here. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 A schematic diagram of the structure of a light-emitting device provided in an embodiment of the present application;

[0050] Reference numerals:

[0051] 1-transparent substrate layer; 2-anode layer; 3-hole injection layer; 4-hole transport layer; 5-electron blocking layer; 6-luminescent layer; 7-hole blocking layer;

[0052] 8-electron transport layer; 9-electron injection layer; 10-cathode layer. DETAILED DESCRIPTION

[0053] In order to make the objectives, technical solutions and advantages of the present application clearer, the present application will be further described in detail below in conjunction with the accompanying drawings.

[0054] The terms used in the following embodiments are only for the purpose of describing specific embodiments and are not intended to be limiting of the present application. As used in the specification and appended claims of the present application, the singular expressions "a", "an", "above", "the" and "this" are intended to also include expressions such as "one or more", unless there is a clear contrary indication in the context.

[0055] References to "one embodiment" or "some embodiments" etc. described in this specification mean that a particular feature, structure or characteristic described in conjunction with the embodiment is included in one or more embodiments of the present application. Thus, the phrases "in one embodiment", "in some embodiments", "in some other embodiments", "in some other embodiments", etc. that appear at different places in this specification do not necessarily refer to the same embodiment, but mean "one or more but not all embodiments", unless otherwise specifically emphasized in other ways. The terms "including", "comprising", "having" and their variations all mean "including but not limited to", unless otherwise specifically emphasized in other ways.

[0056] The present invention provides a compound having a structure as shown in formula (I):

[0057]

[0058] In formula (I), M is selected from divalent Pt.

[0059] Z1 to Z4 are each independently a covalent bond, an oxygen atom, a sulfur atom or a selenium atom. There are two coordinate covalent bonds among Z1 to Z4.

[0060] X 10 ~X 40 and X 41 ~X 44 Each independently is C or N. M can be connected to C or N via a covalent bond. 40 ~X 44 At least one of them is selected from N.

[0061] Q1 and Q2 are each independently selected from a single bond, a divalent element or a divalent group. The divalent element may be, for example, an oxygen atom, a sulfur atom or a selenium atom.

[0062] C1 is a single bond, a divalent element, a divalent group, a C5-C30 carbocyclic group, or a C2-C30 heterocyclic structure. The divalent element may be, for example, an oxygen atom, a sulfur atom, or a selenium atom.

[0063] A1 to A3 are each independently selected from a C5-C30 carbocyclic group or a C2-C30 heterocyclic structure.

[0064] A5 may be present or absent. When A5 is present, it is a C5-C30 carbocyclic group or a C2-C30 heterocyclic structure.

[0065] B1 to B4 are each independently selected from a C5-C30 carbocyclic group or a C2-C30 heterocyclic structure. Wherein, B1 to B4 are each independently present or absent and at least one of B1 to B4 exists. When B1 exists, A1 and B1 are connected in a ring or connected by a single bond. When B2 exists, A2 and B2 are connected in a ring or connected by a single bond. When B3 exists, A3 and B3 are connected in a ring or connected by a single bond. When B4 exists, A4 and B4 are connected in a ring or connected by a single bond.

[0066] There may be one B1 to B4, in which case the compound shown in formula (I) may contain only B1, or B2, or B3, or B2. When there are two B1 to B4, the compound shown in formula (I) may contain two of B1 to B4, such as a combination of B1 and B2, a combination of B1 and B3, a combination of B1 and B4, a combination of B2 and B3, a combination of B2 and B4, and a combination of B3 and B4. When there are three B1 to B4, the compound shown in formula (I) may contain three of B1 to B4, such as a combination of B1, B2 and B3, a combination of B1, B2 and B4, a combination of B1, B3 and B4, and a combination of B2, B3 and B4. In addition, four of B1 to B4 may also exist at the same time.

[0067] Among them, at least one cycloalkyl group may exist in B1 to B4. The cycloalkyl group may be a substituted cycloalkyl group or an unsubstituted cycloalkyl group. The number of carbon atoms of the cycloalkyl group is C5-C30. When the cycloalkyl group is a substituted cycloalkyl group, the substituent may be an alkyl group, such as a methyl group or an ethyl group. Among them, the number of substitutions may be at least one, and the maximum number of replaceable hydrogens of the cycloalkyl group may be. Exemplarily, the cycloalkyl groups of B1 to B4 may be, for example, cyclopentane, cyclohexane, cyclooctane, etc. Among them, the hydrogen in alkanepentane may be replaced by 1-6 methyl or ethyl groups. The hydrogen in alkanehexane may be replaced by 1-8 methyl or ethyl groups. The hydrogen in cyclooctane may be replaced by 1-10 methyl or ethyl groups. Among them, when B1 is a cycloalkyl group, B1 is connected to A1 in a ring. When B2 is a cycloalkyl group, B2 is connected to A2 in a ring. When B3 is a cycloalkyl group, B3 is connected to A3 in a ring. When B4 is a cycloalkyl group and A5 is present, B4 and A5 are cyclically linked; when A5 is not present, B4 and A4 are cyclically linked.

[0068] B1-B3 share common atoms with A1-A3 respectively, and can be connected to form a ring. When A5 exists, B4 and A5 rings share common atoms, and when A5 does not exist, B4 and A4 share common atoms, and can be connected to form a ring.

[0069] The connection structure of the connection part of A1 and B1 is as shown in formula (I-1): As shown, the connection structure of A1 and B1 can be selected from one of the following structures:

[0070]

[0071]

[0072] Among them, *, ** and *** represent the connection sites.

[0073] The connection structure of the connection part of A2 and B2 is as shown in formula (I-2): As shown, the connection structure of A2 and B2 can be selected from one of the following structures:

[0074]

[0075] The connection structure of the connection part of A3 and B3 is as shown in formula (I-3): As shown, the connection structure of A3 and B3 can be selected from one of the following structures:

[0076]

[0077] The connection structure of the connection part of A4 and B4 is as shown in formula (I-4): As shown, the connection structure of A4, A5 and B4 can be selected from one of the following structures:

[0078]

[0079] The connection structure of the connection part of A4 and B4 is as shown in formula (I-4): As shown, A4, A5 and A5 in B4 can be selected from one of the following structures:

[0080]

[0081] In addition, the connection structure of B1-B4 in formula (I) is selected from one of the following structures:

[0082]

[0083] A 1-5 is one of A1-A4, R B1-4 For R B1 ~R B4 one of the.

[0084] In addition, in formula (I), R A1 ~R A5 and R B1 ~R B4 Each independently exists or does not exist, R A1 ~R A5 and R B1 ~R B4 When present, R A1 and R B1 , R A2 and R B2 , R A3 and R B3 , R A4 and R A5 and R B4 They can be independently connected to form a ring or condensed structure. A1 ~R A5 and R B1 ~R B4 Each is independently selected from at least one of a hydrogen atom, a deuterium atom, a halogen, a hydroxyl group, a thiol group, a nitro group, a cyano group, an isocyano group, a sulfone group, a hydroxylamine group, a carboxyl group, a carbonyl group, an amino group, an aromatic hydrocarbon, a heteroaromatic hydrocarbon, a heterocycloalkane, a straight-chain alkane, a cycloalkane, an alkene, a cycloalkene, an alkyne, a cycloalkyne, a monosubstituted amino group, a disubstituted amino group, an alkoxy group, an aromatic ring oxygen group, an aromatic heterocyclic oxygen group, an amide group, an alkylthio group, an aromatic ring sulfur group, a heteroaromatic ring sulfur group, a silicon group, and a boron group.

[0085] Illustratively, the compound of the embodiment of the present application can be selected from one of the following structures:

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111] The preparation method of the embodiment compound of the present application comprises: mixing a precursor containing B1A1, a precursor containing B2A2, a precursor containing B3A3, a precursor containing B4A5A4, and an ionic compound of M, and adding at least one reaction solution, allowing the obtained mixture to undergo a synthesis reaction, and obtaining the compound represented by formula (I) through extraction.

[0112] Wherein: in the precursor of B1A1, B1 is present or absent. In the precursor of B2A2, B2 is present or absent. In the precursor of B3A3, B3 is present or absent. In the precursor of B4A5A4, B4 is present or absent, and A5 is present or absent.

[0113] Based on the same invention purpose, an embodiment of the present application provides a method for preparing a light-emitting layer, comprising: depositing a light-emitting material on the surface of a substrate to form the light-emitting layer on the surface of the substrate, wherein the light-emitting material is a compound of the present application.

[0114] Based on the same invention purpose, an embodiment of the present application provides an organic light-emitting device, comprising an anode layer and a cathode layer, and at least one organic layer between the anode layer and the cathode layer, wherein one layer of the organic layer comprises a compound as described in the present application. Wherein, the organic layer is selected from at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. In the implementation of the present application, a stacked hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer are provided between the anode layer and the cathode layer. Wherein, the hole transport layer is arranged close to the anode layer, and the electron injection layer is arranged close to the electron injection layer. The light-emitting layer comprises compounds of various possible implementations of the present application.

[0115] Based on the same invention purpose, the embodiment of the present application provides a display device, including a display screen and an organic light-emitting device of the present application. The display device of the present application includes a mobile phone, a tablet computer, a notebook computer, a flat-panel display, a flexible display, or an outdoor display panel.

[0116] The compounds of the present application, as well as their preparation process and properties, will be further described in detail below in conjunction with specific examples and comparative examples.

[0117] Example 1

[0118] The specific preparation route of the compound of this example is as follows:

[0119]

[0120] The specific synthesis process includes the following steps:

[0121] Step S11, synthesis of intermediate 2: 6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene (100g, 375mmol) is evenly dispersed in a 1L three-necked flask containing 450mL glacial acetic acid, placed in an ice salt bath at 0°C, and 150mL concentrated nitric acid (67-69%) is slowly dripped into the system using a constant pressure dropping funnel, and the dripping is completed in about 1h. After the dripping is completed, the ice water bath is removed, and the system is slowly heated to room temperature and placed in a 120°C metal bath for reaction for 3 days. After the reaction system is cooled to room temperature, it is slowly poured into 500mL ice water, and a large amount of white precipitate is precipitated. A white solid is obtained by vacuum filtration, which is dissolved in dichloromethane, dried with anhydrous magnesium sulfate (MgSO4), and the solvent is spin-dried. Finally, 46g of a white solid (intermediate 2) is obtained by purification by silica gel column chromatography (eluting liquid: petroleum ether / ethyl acetate), with a yield of 40%.

[0122] Step S12, synthesis of intermediate 3: Add intermediate 2 (20g, 64.3mmol), 3,5-di-tert-butylaniline (14.4g, 70.3mmol), palladium acetate (300mg), tri(tert-butylphosphine) tetrafluoroborate (1.8g), sodium tert-butoxide (15.3g, 153mmol) and xylene (600mL) to a 1000mL round-bottom flask, and evacuate and fill with argon for 3 times. React at 130°C for 24 hours. After cooling to room temperature, extract with dichloromethane and water, and collect the organic layer. Remove the organic solvent by vacuum distillation. The crude product is purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 21g of a white product (intermediate 3) with a yield of 75%.

[0123] Step S13, synthesis of intermediate 4: Add intermediate 3 (10 g, 22.9 mmol), reduced iron powder (6.4 g, 114.3 mmol), ammonium chloride (6.4 g, 120 mmol) and ethanol / water (400 / 200 mL) to a 1000 mL round-bottom flask, and evacuate and fill with argon for 3 times. React at 180 ° C for 4 hours. After cooling to room temperature, vacuum filtration is performed to obtain a filter cake, which is first dissolved with dichloromethane, then extracted with dichloromethane and water, and the organic layer is collected. The organic solvent is removed by vacuum distillation. The crude product is purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 5.6 g of a light yellow product (intermediate 4) with a yield of 60%.

[0124] Step S14, synthesis of intermediate 7: Add intermediate 5 (50g, 203.2mmol), intermediate 6 (50g, 230.2mmol), CuI (3.8g, 20mmol), K2CO3 (55.2g, 400mmol) and N,N-dimethylformamide (DMF) (600mL) to a 1000mL round-bottom flask, and evacuate and fill with argon for 3 times. React at 130°C for 24 hours. After cooling to room temperature, extract with dichloromethane and water, and collect the organic layer. Remove the organic solvent by vacuum distillation. The crude product is purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 61g of a light yellow product (intermediate 7) with a yield of 80%.

[0125] Step S15, synthesis of intermediate 9: Add intermediate 7 (20 g, 52.7 mmol), intermediate 8 (10.6 g, 70.2 mmol), CuI (950 mg, 5 mmol), K2CO3 (13.8 g, 100 mmol) and DMF (300 mL) into a 500 mL round-bottom flask, and repeat the vacuum and argon filling for 3 times. React at 130 ° C for 24 hours. After cooling to room temperature, extract with dichloromethane and water, and collect the organic layer. Remove the organic solvent by reduced pressure distillation. The crude product is purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 17.3 g of a light yellow product (intermediate 9) with a yield of 73%.

[0126] Step S16, synthesis of intermediate 10: Add intermediate 9 (10 g, 22.3 mmol), 30 mL of concentrated hydrochloric acid and 200 mL of dioxane to a 500 mL round-bottom flask. React at 110 ° C for 16 hours. After cooling to room temperature, pour the system into 1000 mL of 10M sodium hydroxide solution to precipitate, and filter under reduced pressure to obtain a filter cake. The filter cake is first dissolved with dichloromethane, then extracted with dichloromethane and water, and the organic layer is collected. The organic solvent is removed by vacuum distillation. The crude product is purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 8.6 g of a light yellow product (intermediate 10) with a yield of 95%.

[0127] Step S17, synthesis of intermediate 11: intermediate 10 (5 g, 12.3 mmol), CuBr2 (3 g, 13.3 mmol) and 30 mL of acetonitrile were added to a 100 mL round-bottom flask. Isoamyl nitrite (1.8 g, 15.3 mmol) was slowly added dropwise at 60°C for 30 minutes. After cooling to room temperature, 40 g of silica gel was added to the system and the sample was directly mixed. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 4.6 g of a light yellow product (intermediate 11) with a yield of 80%.

[0128] Step S18, synthesis of intermediate 12: Add intermediate 11 (10 g, 21.2 mmol), intermediate 4 (10.2 g, 25.2 mmol), palladium acetate (300 mg), tri(tert-butylphosphine) tetrafluoroborate (1.8 g), sodium tert-butoxide (7.7 g, 75 mmol) and xylene (300 mL) to a 500 mL round-bottom flask, and evacuate and fill with argon for 3 times. React at 130 ° C for 24 hours. After cooling to room temperature, extract with dichloromethane and water, and collect the organic layer. Remove the organic solvent by vacuum distillation. The crude product is purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 12.6 g of a white product (intermediate 12) with a yield of 75%.

[0129] Step S19, synthesis of intermediate 13: Add intermediate 12 (8g, 10.2mmol), ammonium hexafluorophosphonate (1.79g, 11mmol) and 20mL of triethyl orthoformate to a 100mL round-bottom flask, evacuate and fill with argon for 3 times. React at 130°C for 24 hours. Stop the reaction and cool to ambient temperature, add a small amount of ethyl acetate to the reaction bottle, and add petroleum ether. After the crude product is precipitated, take petroleum ether and wash repeatedly, retain the precipitated solid and dry it, without further purification, it can be directly used in the next step of the reaction. Finally, 9.12g of off-white solid (intermediate 13) was obtained with a yield of 95%.

[0130] Step S20, synthesis of B-Pt-1: Add intermediate 13 (5g, 5.3mmol), PtCl2 (1.43g, 5.45mmol) and 160mL DMF to a 100mL round-bottom flask, and evacuate and fill with nitrogen for 3 times. React at 130°C for 72 hours. Stop the reaction and cool to ambient temperature, add a small amount of water to quench the reaction completely, then add an equal amount of dichloromethane, filter the mixed solution, wash the dichloromethane solution several times, and extract the mixed solution. Wash the organic phase with saturated sodium chloride aqueous solution and dry with anhydrous magnesium sulfate. Concentrate by low-pressure rotary evaporation, and separate and purify the crude product by column chromatography with eluent petroleum ether / dichloromethane = 4:1, and finally obtain 1.84g of bright yellow powder (compound B-Pt-1) with a yield of 35%.

[0131] NMR data of compound B-Pt-1: 1H NMR (400MHz, CDCl3): δ (ppm) 8.71 (d, J = 6.3Hz, 1H), 8.15 (d, J = 8.3Hz, 1H), 7.9 9-7.98(m,1H),7.82(d,J=8.3Hz,1H),7.60-7.58(m,1H),7.54(s,1H),7.51-7. 47(m,3H),7.43(d,J=8.38Hz,1H),7.29-7.26(m,4H),7.09(d,J=8.1Hz,1H),7. 01(t,J=7.7Hz,1H),5.52(d,J=3.2Hz,1H),1.50(br,9H),1.23-0.82(br,34H).

[0132] Example 2

[0133] The preparation route of the compound of this example is as follows:

[0134]

[0135] The specific synthesis process includes the following steps:

[0136] Step S21, synthesis of intermediate 14: intermediate 10 (5.1 g, 12.3 mmol), 5,6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene (4.3 g, 12.5 mmol), palladium acetate (300 mg), tri(tert-butylphosphine) tetrafluoroborate (1.8 g), sodium tert-butoxide (7.7 g, 75 mmol) and xylene (300 mL) were added to a 500 mL round-bottom flask, and the mixture was vacuumed and filled with argon gas for 3 times. The mixture was reacted at 130°C for 24 hours. After cooling to room temperature, the mixture was extracted with dichloromethane and water, and the organic layer was collected. The organic solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 6.2 g of a white product (intermediate 14) with a yield of 75%.

[0137] Step S22, synthesis of intermediate 17: intermediate 14 (10.1 g, 15.0 mmol), 2,4,6-triisopropylaniline (4.4 g, 20.1 mmol), palladium acetate (100 mg), tri(tert-butylphosphine) tetrafluoroborate (0.6 g), sodium tert-butoxide (2.6 g, 25 mmol) and xylene (300 mL) were added to a 500 mL round-bottom flask, and the vacuum and argon filling were repeated 3 times. React at 130 ° C for 24 hours. After cooling to room temperature, extract with dichloromethane and water, and collect the organic layer. The organic solvent was removed by vacuum distillation. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 7.9 g of a white product (intermediate 17) with a yield of 65%.

[0138] Step S23, synthesis of intermediate 18: Add intermediate 17 (8.2 g, 10.1 mmol), ammonium hexafluorophosphonate (1.79 g, 11 mmol) and 20 mL of triethyl orthoformate to a 100 mL round-bottom flask, evacuate and fill with argon for 3 times. React at 130 ° C for 24 hours. Stop the reaction and cool to ambient temperature, add a small amount of ethyl acetate to the reaction bottle, and add petroleum ether. After the crude product is precipitated, take petroleum ether and wash repeatedly, retain the precipitated solid and dry it, without further purification, it can be directly used in the next step of the reaction. Finally, 9.57 g of off-white solid (intermediate 18) was obtained with a yield of 95%.

[0139] Step S24, synthesis of B-Pt-3: Add intermediate 18 (4.9 g, 5.0 mmol), PtCl2 (1.43 g, 5.45 mmol) and 160 mL DMF to a 100 mL round-bottom flask, and evacuate and fill with nitrogen for 3 times. React at 130 ° C for 72 hours. Stop the reaction and cool to ambient temperature, add a small amount of water to quench the reaction completely, then add an equal amount of dichloromethane, filter the mixed solution, wash the dichloromethane solution several times, and extract the mixed solution. Wash the organic phase with saturated sodium chloride aqueous solution and dry it with anhydrous magnesium sulfate. Concentrate by low-pressure rotary evaporation, and separate and purify the crude product by column chromatography with eluent petroleum ether / dichloromethane = 4:1, and finally obtain 1.68 g of bright yellow powder (compound B-Pt-3) with a yield of 33%.

[0140] NMR data of compound B-Pt-3: 1H NMR (400MHz, CDCl3): δ (ppm) 8.71 (d, J = 6.3Hz, 1H), 8.15 (d, J = 8.3Hz, 1H), 7.9 9-7.98(m,1H),7.82(d,J=8.3Hz,1H),7.60-7.58(m,1H),7.54(s,1H),7.51-7. 47(m,3H),7.43(d,J=8.38Hz,1H),7.29-7.26(m,4H),7.09(d,J=8.1Hz,1H),7. 01(t,J=7.7Hz,1H),5.52(d,J=3.2Hz,1H),1.50(br,9H),1.23-0.82(br,37H).

[0141] Example 3

[0142] The specific preparation route of the compound of this example is as follows:

[0143]

[0144] The specific synthesis process includes the following steps:

[0145] Step S31, synthesis of intermediate 14: intermediate 10 (5.1 g, 12.3 mmol), 5,6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene (4.3 g, 12.5 mmol), palladium acetate (300 mg), tri(tert-butylphosphine) tetrafluoroborate (1.8 g), sodium tert-butoxide (7.7 g, 75 mmol) and xylene (300 mL) were added to a 500 mL round-bottom flask, and the mixture was vacuumed and filled with argon gas for 3 times. The mixture was reacted at 130°C for 24 hours. After cooling to room temperature, the mixture was extracted with dichloromethane and water, and the organic layer was collected. The organic solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 6.2 g of a white product (intermediate 14) with a yield of 75%.

[0146] Step S32, synthesis of intermediate 15: intermediate 14 (10.1 g, 15.0 mmol), 2,6-diisopropylaniline (3.6 g, 20.1 mmol), palladium acetate (100 mg), tri(tert-butylphosphine) tetrafluoroborate (0.6 g), sodium tert-butoxide (2.6 g, 25 mmol) and xylene (300 mL) were added to a 500 mL round-bottom flask, and the vacuum and argon filling were repeated 3 times. React at 130 ° C for 24 hours. After cooling to room temperature, extract with dichloromethane and water, and collect the organic layer. The organic solvent was removed by vacuum distillation. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 7.2 g of a white product (intermediate 15) with a yield of 63%.

[0147] Step S33, synthesis of intermediate 16: Add intermediate 15 (7.7g, 10.1mmol), ammonium hexafluorophosphonate (1.79g, 11mmol) and 20mL of triethyl orthoformate to a 100mL round-bottom flask, evacuate and fill with argon for 3 times. React at 130°C for 24 hours. Stop the reaction and cool to ambient temperature, add a small amount of ethyl acetate to the reaction bottle, and add petroleum ether. After the crude product is precipitated, take petroleum ether and wash repeatedly, retain the precipitated solid and dry it, without further purification, it can be directly used in the next step of the reaction. Finally, 8.88g of off-white solid (intermediate 16) was obtained with a yield of 95%.

[0148] Step S34, synthesis of B-Pt-4: Add intermediate 13 (4.9 g, 5.3 mmol), PtCl2 (1.43 g, 5.45 mmol) and 160 mL DMF to a 100 mL round-bottom flask, and evacuate and fill with nitrogen for 3 times. React at 130 ° C for 72 hours. Stop the reaction and cool to ambient temperature, add a small amount of water to quench the reaction completely, then add an equal amount of dichloromethane, filter the mixed solution, wash the dichloromethane solution several times, and extract the mixed solution. Wash the organic phase with saturated sodium chloride aqueous solution and dry it with anhydrous magnesium sulfate. Concentrate by low-pressure rotary evaporation, and separate and purify the crude product by column chromatography with eluent petroleum ether / dichloromethane = 4:1, and finally obtain 2.06 g of bright yellow powder (compound B-Pt-4) with a yield of 40%.

[0149] NMR data of compound B-Pt-4: 1H NMR (400MHz, CDCl3): δ (ppm) 8.71 (d, J = 6.3Hz, 1H), 8.15 (d, J = 8.3Hz, 1H), 7.9 9-7.98(m,1H),7.82(d,J=8.3Hz,1H),7.60-7.58(m,1H),7.54(s,1H),7.51-7. 47(m,3H),7.43(d,J=8.38Hz,1H),7.29-7.26(m,4H),7.09(d,J=8.1Hz,1H),7. 01(t,J=7.7Hz,1H),5.52(d,J=3.2Hz,1H),1.50(br,9H),1.23-0.82(br,30H).

[0150] Example 4

[0151] The specific preparation route of the compound of this example is as follows:

[0152]

[0153] The specific synthesis process includes the following steps:

[0154] Step S41, synthesis of intermediate 3: Add intermediate 1 (31.9 g, 102.2 mmol), intermediate 2 (20.3 g, 100.1 mmol), Pd(PPh3)4 (5.4 g, 5.2 mmol), K2CO3 (22.4 g, 206.2 mmol), 460 mL of dioxane and 160 mL of ionized water to a 1000 mL round-bottom flask, and vacuumize and fill with nitrogen for 3 times. React at 60°C for 12 hours. After the reaction stops and cools to ambient temperature, the upper organic phase is taken from the separatory funnel and dried by spin drying. The organic phase is washed with a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. Concentrate by low-pressure rotary evaporation, and the crude product is separated and purified by column chromatography with an eluent of petroleum ether / dichloromethane = 4:1, and finally 36.6 g of white powder (intermediate 3) is obtained with a yield of 65%.

[0155] Step S42, synthesis of intermediate 4: Add intermediate 3 (20.3 g, 52.3 mmol), tricyclohexylphosphine tetrafluoroborate (3.9 g, 10.6 mmol), Pd(OAc)2 (1.2 g, 5.2 mmol), K2CO3 (106.4 g, 100.2 mmol), 300 mL DMAc solution to a 500 mL round-bottom flask, and repeat the vacuum filling with nitrogen 3 times. React at 180 ° C for 24 hours. Stop the reaction and cool to ambient temperature, add dichloromethane and aqueous solution for separation, take the lower organic phase and spin dry, wash the organic phase with saturated sodium chloride aqueous solution, and dry it with anhydrous magnesium sulfate. Concentrate by low-pressure rotary evaporation, and separate and purify the crude product by column chromatography with eluent petroleum ether / ethyl acetate = 6:1, and finally obtain 10.7 g of white powder (intermediate 4) with a yield of 67%.

[0156] Step S43, synthesis of intermediate 6: Add intermediate 4 (9.2g, 30.2mmol), intermediate 5 (7.5g, 35.1mmol), CuI (570mg, 3.2mmol), N-methylimidazole (5mL), K2CO3 (10.8g, 100.2mmol), 300mL DMF to a 500mL round-bottom flask, and evacuate and fill with nitrogen for 3 times. React at 130°C for 16 hours. Stop the reaction and cool to ambient temperature, use dichloromethane and water to separate, take the lower organic phase and spin dry, wash the organic phase with saturated sodium chloride aqueous solution, and dry it with anhydrous magnesium sulfate. Concentrate by low-pressure rotary evaporation, and separate and purify the crude product by column chromatography with eluent petroleum ether / ethyl acetate = 8:1, and finally obtain 10.6g of white powder (intermediate 6) with a yield of 80%.

[0157] Step S44, synthesis of intermediate 7: Add intermediate 6 (8.8g, 20.3mmol), pyridine hydrochloride (11.6g, 106mmol), and 100mL DMI solution to a 250mL round-bottom flask, and evacuate and fill with nitrogen for 3 times. React at 180°C for 36 hours. Stop the reaction and cool to ambient temperature, add dichloromethane and aqueous solution for separation, take the lower organic phase and spin dry, wash the organic phase with saturated sodium chloride aqueous solution, and dry it with anhydrous magnesium sulfate. Concentrate by low-pressure rotary evaporation, and separate and purify the crude product by column chromatography with eluent petroleum ether / ethyl acetate = 4:1, and finally obtain 7.9g of white powder (intermediate 7) with a yield of 92%.

[0158] Step S45, synthesis of intermediate 10: 2-nitrofluorobenzene (14.1 g, 100.2 mmol), m-bromoaniline (34.3 g, 200.1 mmol), KF (6.3 g, 108.1 mmol) were added to a 100 mL round-bottom flask, and the vacuum and nitrogen filling were repeated 3 times. React at 180 ° C for 16 hours. The reaction was stopped and cooled to ambient temperature, and dichloromethane and water were used to separate, and the lower organic phase was taken and dried by spin drying, and the organic phase was washed with saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. Concentrated by low-pressure rotary evaporation, the crude product was separated and purified by column chromatography with eluent petroleum ether / ethyl acetate = 8:1, and finally 25 g of white powder (intermediate 10) was obtained with a yield of 85%.

[0159] Step S46, synthesis of intermediate 11: intermediate 7 (12.9 g, 30.2 mmol), intermediate 10 (10.3 g, 35.1 mmol), CuI (570 mg, 3.2 mmol), dimethylglycine (721 mg, 7.0 mmol), K2CO3 (10.8 g, 100.2 mmol), 300 mL DMSO were added to a 500 mL round-bottom flask, and the vacuum was repeated for 3 times. React at 130 ° C for 16 hours. The reaction was stopped and cooled to ambient temperature, and dichloromethane and water were used to separate, and the lower organic phase was taken and dried by spin drying, and the organic phase was washed with saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. Concentrated by low-pressure rotary evaporation, the crude product was separated and purified by column chromatography with eluent petroleum ether / ethyl acetate = 8:1, and finally 1.9 g of white powder (intermediate 11) was obtained with a yield of 28%.

[0160] Step S47, synthesis of intermediate 12: Add intermediate 11 (12.9 g, 20.3 mmol), reduced iron powder (6.0 g, 106 mmol), ammonium chloride (8.3 g, 156 mmol), 100 mL ethanol, and 35 mL aqueous solution to a 250 mL round-bottom flask, and repeat the vacuum filling with nitrogen 3 times. React at 100 ° C for 4 hours. Stop the reaction and cool to ambient temperature. First add 6M sodium hydroxide to neutralize to PH = 8, then add dichloromethane to the system for liquid separation, take the lower organic phase and spin dry, wash the organic phase with saturated sodium chloride aqueous solution, and dry it with anhydrous magnesium sulfate. Concentrate by low-pressure rotary evaporation, and separate and purify the crude product by column chromatography with eluent petroleum ether / ethyl acetate = 4:1, and finally obtain 9.1 g of white powder (intermediate 12) with a yield of 74%.

[0161] Step S48, synthesis of intermediate 13: intermediate 12 (9.1 g, 15.0 mmol), 3,5-di-tert-butyl bromobenzene (5.4 g, 20.1 mmol), palladium acetate (100 mg), tri(tert-butylphosphine) tetrafluoroborate (0.6 g), sodium tert-butoxide (2.6 g, 25 mmol) and xylene (300 mL) were added to a 500 mL round-bottom flask, and the vacuum was evacuated and filled with argon gas for 3 times. React at 130°C for 24 hours. After cooling to room temperature, extract with dichloromethane and water, and collect the organic layer. The organic solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 8.8 g of a white product (intermediate 133) with a yield of 74%.

[0162] Step S49, synthesis of intermediate 14: Add intermediate 13 (8.0 g, 10.1 mmol), ammonium hexafluorophosphonate (1.79 g, 11 mmol) and 20 mL of triethyl orthoformate to a 100 mL round-bottom flask, evacuate and fill with argon for 3 times. React at 130 ° C for 24 hours. Stop the reaction and cool to ambient temperature, add a small amount of ethyl acetate to the reaction bottle, and add petroleum ether. After the crude product is precipitated, take petroleum ether and wash repeatedly, retain the precipitated solid and dry it, without further purification, it can be directly used in the next step of the reaction. Finally, 9.15 g of off-white solid (intermediate 14) was obtained with a yield of 95%.

[0163] Step S50, synthesis of B-Pt-6: intermediate 14 (4.8 g, 5.0 mmol), PtCl2 (1.43 g, 5.45 mmol) and 160 mL DMF were added to a 100 mL round-bottom flask, and the mixture was vacuumed and filled with nitrogen for 3 times. The reaction was carried out at 130 ° C for 72 hours. The reaction was stopped and cooled to ambient temperature, a small amount of water was added to completely quench the reaction, and then an equal amount of dichloromethane was added, the mixed solution was filtered, the dichloromethane solution was washed several times, and the mixed solution was extracted. The organic phase was washed with a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. Concentrated by low-pressure rotary evaporation, the crude product was separated and purified by column chromatography with an eluent of petroleum ether / dichloromethane = 4:1, and finally a bright yellow powder (compound B-Pt-6) of 1.68 g was obtained with a yield of 35%.

[0164] Compound B-Pt-6 NMR detection data: 1H NMR (400MHz, CDCl3): δ (ppm) 8.71 (d, J = 6.3Hz, 1H), 8.15 (d, J = 8.3Hz, 1H), 7.9 9-7.98(m,1H),7.82(d,J=8.3Hz,1H),7.60-7.58(m,1H),7.54(s,1H),7.51-7. 47(m,3H),7.43(d,J=8.38Hz,1H),7.29-7.26(m,4H),7.09(d,J=8.1Hz,1H),7. 01(t,J=7.7Hz,1H),5.52(d,J=3.2Hz,1H),1.50(br,9H),1.23-0.82(br,34H).

[0165] Example 5

[0166] The specific preparation route of the compound of this example is as follows:

[0167]

[0168] The specific synthesis process includes the following steps:

[0169] Step S51, synthesis of intermediate 15: intermediate 12 (9.1 g, 15.0 mmol), 2-bromo-1,3-diisopropylbenzene (4.8 g, 20.1 mmol), palladium acetate (100 mg), tri(tert-butylphosphine) tetrafluoroborate (0.6 g), sodium tert-butoxide (2.6 g, 25 mmol) and xylene (300 mL) were added to a 500 mL round-bottom flask, and the vacuum and argon filling were repeated 3 times. React at 130 ° C for 24 hours. After cooling to room temperature, extract with dichloromethane and water, and collect the organic layer. The organic solvent was removed by vacuum distillation. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 8.0 g of a white product (intermediate 15) with a yield of 70%.

[0170] Step S52, synthesis of intermediate 16: Add intermediate 15 (8.0 g, 10.4 mmol), ammonium hexafluorophosphonate (1.79 g, 11 mmol) and 20 mL of triethyl orthoformate to a 100 mL round-bottom flask, and evacuate and fill with argon for 3 times. React at 130 ° C for 24 hours. Stop the reaction and cool to ambient temperature, add a small amount of ethyl acetate to the reaction bottle, and add petroleum ether. After the crude product is precipitated, take petroleum ether and wash repeatedly, retain the precipitated solid and dry it, without further purification, it can be directly used in the next step of the reaction. Finally, 7 g of off-white solid (intermediate 16) was obtained with a yield of 90%.

[0171] Step S53, synthesis of B-Pt-8: Add intermediate 16 (3.9 g, 5.0 mmol), PtCl2 (1.43 g, 5.45 mmol) and 160 mL DMF to a 100 mL round-bottom flask, and evacuate and fill with nitrogen for 3 times. React at 130 ° C for 72 hours. Stop the reaction and cool to ambient temperature, add a small amount of water to quench the reaction completely, then add an equal amount of dichloromethane, filter the mixed solution, wash the dichloromethane solution several times, and extract the mixed solution. Wash the organic phase with saturated sodium chloride aqueous solution and dry it with anhydrous magnesium sulfate. Concentrate by low-pressure rotary evaporation, and separate and purify the crude product by column chromatography with eluent petroleum ether / dichloromethane = 4:1, and finally obtain 1.1 g of bright yellow powder (compound B-Pt-8) with a yield of 25%.

[0172] The nuclear magnetic detection data of compound B-Pt-8: 1H NMR (500MHz, Chloroform-d) δ9.08 (d, J = 8.3Hz, 1H), 8.04 (dd, J = 8.3, 1.9Hz, 1H), 8.00 (d, J = 7.2Hz, 1H), 7.93 (s, 1H), 7.45 (s, 1H), 7.40 (d, J = 2.0Hz, 1H), 7.16 (t, J = 7.6Hz, 1H), 7.1 1–7.03(m,4H),7.04–6.97(m,1H),6.91(dd,J=5.7,3.4Hz,2H),6.85–6.76(m,2H),6.58(d d, J=7.6, 1.2Hz, 1H), 2.87 (ddd, J=9.6, 4.8, 4.2Hz, 2H), 1.48 (s, 4H), 1.35–1.22 (m, 33H).

[0173] Example 6

[0174] The specific preparation route of the compound of this example is as follows:

[0175]

[0176] The specific synthesis process includes the following steps:

[0177] Step S61, synthesis of intermediate 18: intermediate 17 (9.1 g, 15.0 mmol, custom synthesis), 2-bromo-1,3-diisopropylbenzene (4.8 g, 20.1 mmol), palladium acetate (100 mg), tri(tert-butylphosphine) tetrafluoroborate (0.6 g), sodium tert-butoxide (2.6 g, 25 mmol) and xylene (300 mL) were added to a 500 mL round-bottom flask, and the vacuum was evacuated and filled with argon gas for 3 times. React at 130 ° C for 24 hours. After cooling to room temperature, extract with dichloromethane and water, and collect the organic layer. The organic solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 8.0 g of a white product (intermediate 18) with a yield of 70%.

[0178] Step S62, synthesis of intermediate 19: Add intermediate 15 (8.0g, 10.4mmol), ammonium hexafluorophosphonate (1.79g, 11mmol) and 20mL of triethyl orthoformate to a 100mL round-bottom flask, evacuate and fill with argon for 3 times. React at 130°C for 24 hours. Stop the reaction and cool to ambient temperature, add a small amount of ethyl acetate to the reaction bottle, and add petroleum ether. After the crude product is precipitated, take petroleum ether and wash repeatedly, retain the precipitated solid and dry it, without further purification, it can be directly used in the next step of the reaction. Finally, 7g of off-white solid (intermediate 19) was obtained with a yield of 90%.

[0179] Step S63, synthesis of B-Pt-9: Add intermediate 19 (3.9 g, 5.0 mmol), PtCl2 (1.43 g, 5.45 mmol) and 160 mL DMF to a 100 mL round-bottom flask, and evacuate and fill with nitrogen for 3 times. React at 130 ° C for 72 hours. Stop the reaction and cool to ambient temperature, add a small amount of water to quench the reaction completely, then add an equal amount of dichloromethane, filter the mixed solution, wash the dichloromethane solution several times, and extract the mixed solution. Wash the organic phase with saturated sodium chloride aqueous solution and dry it with anhydrous magnesium sulfate. Concentrate by low-pressure rotary evaporation, and separate and purify the crude product by column chromatography with eluent petroleum ether / dichloromethane = 4:1, and finally obtain 1.1 g of bright yellow powder (compound B-Pt-9) with a yield of 25%.

[0180] NMR data of compound B-Pt-9: 1 H NMR(500MHz,Chloroform-d)δ9.08(d,J=8.3Hz,1H),8.23–8.17(m,1H),8.04(dd,J=8.3,1.9Hz,1H ),8.00(d,J=7.3Hz,1H),7.63(dd,J=6.1,1.6Hz,1H),7.40(d,J=2.0Hz,1H),7.39–7.33(m,1H),7.2 9(ddd,J=7.2,6.0,1.3Hz,1H),7.10–7.03(m,4H),7.06–6.97(m,1H),6.91(dd,J=5.7,3.4Hz,2H),6 .82–6.76(m,2H),4.50(s,1H),2.87(ddd,J=9.6,4.8,4.2Hz,2H),1.50(s,4H),1.35–1.22(m,33H).

[0181] Example 7

[0182] The specific preparation route of the compound of this example is as follows:

[0183]

[0184] The specific synthesis process includes the following steps:

[0185] Step S71, synthesis of intermediate 21: intermediate 20 (9.1 g, 15.0 mmol), 3,5-di-tert-butyl bromobenzene (5.4 g, 20.1 mmol), palladium acetate (100 mg), tri(tert-butylphosphine) tetrafluoroborate (0.6 g), sodium tert-butoxide (2.6 g, 25 mmol) and xylene (300 mL) were added to a 500 mL round-bottom flask, and the vacuum and argon filling were repeated 3 times. React at 130 ° C for 24 hours. After cooling to room temperature, extract with dichloromethane and water, and collect the organic layer. The organic solvent was removed by vacuum distillation. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate) to obtain 8.0 g of a white product (intermediate 21) with a yield of 70%.

[0186] Step S72, synthesis of intermediate 22: Add intermediate 21 (8.0g, 10.4mmol), ammonium hexafluorophosphonate (1.79g, 11mmol) and 20mL of triethyl orthoformate to a 100mL round-bottom flask, evacuate and fill with argon for 3 times. React at 130°C for 24 hours. Stop the reaction and cool to ambient temperature, add a small amount of ethyl acetate to the reaction bottle, and add petroleum ether. After the crude product is precipitated, take petroleum ether and wash repeatedly, retain the precipitated solid and dry it, without further purification, it can be directly used in the next step of the reaction. Finally, 7g of off-white solid (intermediate 22) was obtained with a yield of 90%.

[0187] Step S73, synthesis of B-Pt-10: intermediate 22 (3.9 g, 5.0 mmol), PtCl2 (1.43 g, 5.45 mmol) and 160 mL DMF were added to a 100 mL round-bottom flask, and the mixture was vacuumed and filled with nitrogen for 3 times. React at 130 ° C for 72 hours. The reaction was stopped and cooled to ambient temperature, a small amount of water was added to completely quench the reaction, and then an equal amount of dichloromethane was added, the mixed solution was filtered, the dichloromethane solution was washed several times, and the mixed solution was extracted. The organic phase was washed with a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. Concentrated by low-pressure rotary evaporation, the crude product was separated and purified by column chromatography with an eluent of petroleum ether / dichloromethane = 4:1, and finally 1.1 g of bright yellow powder (compound B-Pt-10) was obtained with a yield of 25%.

[0188] NMR data of compound B-Pt-10: 1H NMR(500MHz,Chloroform-d)δ9.06(d,J=7.5Hz,1H),8.23–8.17(m,1H),8.00(d,J=7.3Hz,1H),7.6 3(dd,J=6.1,1.6Hz,1H),7.39–7.33(m,1H),7.32–7.26(m,2H),7.16(t,J=7.6Hz,1H),7.10–7.03(m ,4H),7.00(t,J=2.1Hz,1H),6.91(dd,J=5.7,3.4Hz,2H),6.85–6.76(m,2H),6.58(dd,J=7.6,1.2H z,1H),4.50(s,1H),1.52–1.45(m,4H),1.33(d,J=5.9Hz,6H),1.29(s,18H),1.28(d,J=6.0Hz,6H).

[0189] Example 8

[0190] The specific preparation route of the compound of this example is as follows:

[0191]

[0192] The specific synthesis process includes the following steps:

[0193] Step S81, synthesis of intermediate 24: intermediate 23 (29.9g, 30.2mmol), intermediate 25 (9.2g, 35.1mmol), CuI (570mg, 3.2mmol), dimethylglycine (721mg, 7.0mmol), K2CO3 (10.8g, 100.2mmol), 300mL DMSO were added to a 500mL round-bottom flask, and vacuumed and filled with nitrogen for 3 times. Reacted at 130°C for 16 hours. The reaction was stopped and cooled to ambient temperature, and dichloromethane and water were used to separate, the lower organic phase was taken and dried, and the organic phase was washed with saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. Concentrated by low-pressure rotary evaporation, the crude product was separated and purified by column chromatography with eluent petroleum ether / ethyl acetate = 8:1, and finally 5.2g of white powder (intermediate 24) was obtained with a yield of 28%.

[0194] Step S82, synthesis of B-Pt-11: Add intermediate 24 (4.1 g, 5.0 mmol), PtCl2 (1.43 g, 5.45 mmol) and 160 mL DMF to a 100 mL round-bottom flask, and repeat the vacuum and nitrogen filling for 3 times. React at 130 ° C for 72 hours. Stop the reaction and cool to ambient temperature, add a small amount of water to quench the reaction completely, then add an equal amount of dichloromethane, filter the mixed solution, wash the dichloromethane solution several times, and extract the mixed solution. Wash the organic phase with saturated sodium chloride aqueous solution and dry it with anhydrous magnesium sulfate. Concentrate by low-pressure rotary evaporation, and separate and purify the crude product by column chromatography with eluent petroleum ether / dichloromethane = 4:1, and finally obtain 2.1 g of bright yellow powder (compound B-Pt-11) with a yield of 50%.

[0195] NMR data of compound B-Pt-11: 1 H NMR(500MHz,Chloroform-d)δ9.06(d,J=8.1Hz,1H),8.23–8.17(m,1H),8.00 (d,J=7.3Hz,1H),7.66–7.56(m,2H),7.56–7.49(m,3H),7.46–7.39(m,2H),7 .42–7.32(m,2H),7.35–7.26(m,2H),7.21(dd,J=6.8,1.3Hz,1H),6.79(d,J= 7.1Hz, 1H), 2.55 (d, J = 1.4Hz, 6H), 1.52–1.45 (m, 4H), 1.29 (d, J = 2.9Hz, 12H).

[0196] Example 9

[0197] The specific preparation route of the compound of this example is as follows:

[0198]

[0199] The specific synthesis process includes the following steps:

[0200] Step S91, synthesis of intermediate 27: intermediate 26 (29.9 g, 30.2 mmol), intermediate 25 (9.2 g, 35.1 mmol), CuI (570 mg, 3.2 mmol), dimethylglycine (721 mg, 7.0 mmol), K2CO3 (10.8 g, 100.2 mmol), 300 mL DMSO were added to a 500 mL round-bottom flask, and the vacuum was repeated for 3 times. React at 130 ° C for 16 hours. The reaction was stopped and cooled to ambient temperature, and dichloromethane and water were used to separate, and the lower organic phase was taken and dried by spin drying, and the organic phase was washed with saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. Concentrated by low-pressure rotary evaporation, the crude product was separated and purified by column chromatography with eluent petroleum ether / ethyl acetate = 8:1, and finally 5.5 g of white powder (intermediate 27) was obtained with a yield of 32%.

[0201] Step S92, synthesis of B-Pt-12: Add intermediate 27 (4.1 g, 5.0 mmol), PtCl2 (1.43 g, 5.45 mmol) and 160 mL DMF to a 100 mL round-bottom flask, and evacuate and fill with nitrogen for 3 times. React at 130 ° C for 72 hours. Stop the reaction and cool to ambient temperature, add a small amount of water to quench the reaction completely, then add an equal amount of dichloromethane, filter the mixed solution, wash the dichloromethane solution several times, and extract the mixed solution. Wash the organic phase with a saturated sodium chloride aqueous solution and dry it over anhydrous magnesium sulfate. Concentrate by low-pressure rotary evaporation, and separate and purify the crude product by column chromatography with an eluent of petroleum ether / dichloromethane = 4:1, and finally obtain 2.7 g of bright yellow powder (compound B-Pt-12) with a yield of 67%.

[0202] NMR data of compound B-Pt-12: 1 H NMR(500MHz,Chloroform-d)δ9.08(d,J=8.8Hz,1H),8.04(dd,J=8.8,2.0Hz,1H), 8.00(d,J=7.2Hz,1H),7.93(s,1H),7.59(t,J=6.6Hz,1H),7.56–7.49(m,3H),7.47 –7.39(m,3H),7.40(d,J=1.9Hz,1H),7.38–7.31(m,1H),7.21(dd,J=6.8,1.3Hz,1 H), 6.79 (d, J = 7.1Hz, 1H), 2.55 (d, J = 1.4Hz, 6H), 1.48 (s, 4H), 1.33–1.27 (m, 21H).

[0203] Example 10

[0204] The specific preparation route of the compound of this example is as follows:

[0205]

[0206] The specific synthesis process includes the following steps:

[0207] Step S101, synthesis of intermediate 29: intermediate 28 (11.4 g, 30.2 mmol), intermediate 25 (13.1 g, 35.1 mmol), CuI (570 mg, 3.2 mmol), dimethylglycine (721 mg, 7.0 mmol), K2CO3 (10.8 g, 100.2 mmol), 300 mL DMSO were added to a 500 mL round-bottom flask, and the vacuum was evacuated and nitrogen was filled for 3 times. React at 130 ° C for 16 hours. The reaction was stopped and cooled to ambient temperature, and dichloromethane and water were used to separate, and the lower organic phase was taken and dried by spin drying, and the organic phase was washed with saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. Concentrated by low-pressure rotary evaporation, the crude product was separated and purified by column chromatography with eluent petroleum ether / ethyl acetate = 8:1, and finally 4.8 g of white powder (intermediate 29) was obtained, with a yield of 31%.

[0208] Step S102, synthesis of B-Pt-13: Add intermediate 29 (4.1 g, 5.0 mmol), PtCl2 (1.43 g, 5.45 mmol) and 160 mL DMF to a 100 mL round-bottom flask, and evacuate and fill with nitrogen for 3 times. React at 130 ° C for 72 hours. Stop the reaction and cool to ambient temperature, add a small amount of water to quench the reaction completely, then add an equal amount of dichloromethane, filter the mixed solution, wash the dichloromethane solution several times, and extract the mixed solution. Wash the organic phase with saturated sodium chloride aqueous solution and dry it with anhydrous magnesium sulfate. Concentrate by low-pressure rotary evaporation, and separate and purify the crude product by column chromatography with eluent petroleum ether / dichloromethane = 4:1, and finally obtain 3.2 g of bright yellow powder (compound B-Pt-13) with a yield of 67%.

[0209] NMR data of compound B-Pt-13: 1H NMR(500MHz,Chloroform-d)δ9.08(d,J=8.8Hz,1H),8.23–8.17(m,1H),8.04(dd,J= 8.8,2.0Hz,1H),8.00(d,J=7.3Hz,1H),7.63(dd,J=6.1,1.6Hz,1H),7.55–7.49(m,2 H),7.46–7.39(m,3H),7.39–7.32(m,2H),7.29(ddd,J=7.2,6.0,1.3Hz,1H),7.10(s ,1H),6.79(d,J=7.1Hz,1H),2.55(d,J=1.4Hz,6H),1.50(s,4H),1.33–1.27(m,21H).

[0210] Comparative Example 1

[0211]

[0212] Comparative Example 2

[0213]

[0214] Comparative Example 3

[0215]

[0216] Comparative Example 4

[0217]

[0218] The above compounds were placed in a dichloromethane solution, and the intrinsic spectra of the compounds in each embodiment and comparative example were tested using a fluorescence spectrometer to obtain the emission wavelength λ of each embodiment and comparative example. PL The test results are listed in Table 1.

[0219] Table 1

[0220]

[0221] Device Embodiment

[0222] The compounds of the examples of the present application and the comparative compounds ref-1 to ref-4 were used to prepare OLED devices. The structures of the compounds and comparative compounds used in the preparation of the OLED devices are as follows:

[0223]

[0224] Figure 1 A schematic diagram of the structure of an OLED device is shown in the present application. Figure 1As shown, the structure of the OLED device includes a transparent substrate layer 1, an anode layer 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light-emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9 and a cathode layer 10 which are stacked in sequence. Among them, the hole injection layer 3, the hole transport layer 4, the electron blocking layer 5, the light-emitting layer 6, the hole blocking layer 7, the electron transport layer 8 and the electron injection layer 9 which are stacked in sequence can constitute the functional layers of the OLED device, and the compound of the present application can be formed in the light-emitting layer 6.

[0225] The method for preparing the OLED device of the embodiment of the present application is as follows:

[0226] Refer to Figure 1 , the transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness of 150nm) provided on the surface of the transparent substrate layer 1 is washed, that is, washing with a cleaning agent (Semiclean M-L20), washing with pure water, drying, and then ultraviolet-ozone washing are performed in sequence to remove organic residues on the surface of the ITO anode layer 2. 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 and HI-1 is 97:3. Then, HT-1 with a thickness of 60nm is evaporated as the hole transport layer 4. Subsequently, EB-1 with a thickness of 30nm is evaporated as the electron blocking layer 5. After the above-mentioned electron blocking material is evaporated, the light-emitting layer 6 of the OLED light-emitting device is prepared, using Host-1 and Host-2 as dual-host materials, and the compounds of Examples 1-10 are respectively used as guest light-emitting materials, and the film thickness of the light-emitting layer is 40nm. 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.

[0227] The device comparative examples were prepared by replacing the compounds of the present embodiment in the above steps with compounds ref-1 to ref-4 respectively.

[0228] The performance parameters of the device embodiment and the device comparison example were tested respectively, and the test results are listed in Table 2. The specific test process of each test index is as follows: electroluminescence peak λ EL, external quantum efficiency EQE, CIEy and half-peak width and lifetime LT95@1000nit. Among them, the electroluminescence peak λ EL , external quantum luminous efficiency EQE, CIEy and half-peak width are tested using a spectrometer. LT95 refers to the time it takes for the device brightness to decay to 95%, and the test light intensity is 1000cd / m 2 .

[0229] Table 2

[0230]

[0231] The above are only specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any technician familiar with the technical field can easily think of changes or substitutions within the technical scope disclosed in the present application, which should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. A compound, characterized in that The compound has a structure as shown in formula (I): In formula (I), M is selected from divalent Pt; Z1-Z4 are each independently a covalent bond, an oxygen atom, a sulfur atom or a selenium atom, and two of Z1-Z4 are coordinate covalent bonds; X 10 ~X 40 and X 41 ~X 44 are each independently C or N, and X 40 ~X 44 At least one of them is selected from N; Q1 and Q2 are each independently selected from a single bond, a divalent element or a divalent group; C1 is a single bond, a divalent element, a divalent group, a C5-C30 carbocyclic group, or a C2-C30 heterocyclic structure; A1 to A3 are each independently selected from a C5-C30 carbocyclic group or a C2-C30 heterocyclic structure; B1-B4 are each independently selected from a C5-C30 carbocyclic group or a C2-C30 heterocyclic structure; B1-B4 are each independently present or absent and at least one of B1-B4 exists; A5 is present or absent. When A5 is present, A5 is a C5-C30 carbocyclic group or a C2-C30 heterocyclic structure and B4 and A5 rings have common atoms; when A5 is absent, B4 and A4 have common atoms; R A1 ~R A5 and R B1 ~R B4 Each independently exists or does not exist, R A1 ~R A5 and R B1 ~R B4 When present, R A1 and R B1 , R A2 and R B2 , R A3 and R B3 , R A4 and R A5 and R B4 They can be independently connected to form a ring or fused structure; R A1 ~R A5 and R B1 ~R B4 Each is independently selected from at least one of a hydrogen atom, a deuterium atom, a halogen, a hydroxyl group, a thiol group, a nitro group, a cyano group, an isocyano group, a sulfone group, a hydroxylamine group, a carboxyl group, a carbonyl group, an amino group, an aromatic hydrocarbon, a heteroaromatic hydrocarbon, a heterocycloalkane, a straight-chain alkane, a cycloalkane, an alkene, a cycloalkene, an alkyne, a cycloalkyne, a monosubstituted amino group, a disubstituted amino group, an alkoxy group, an aromatic ring oxygen group, an aromatic heterocyclic oxygen group, an amide group, an alkylthio group, an aromatic ring sulfur group, a heteroaromatic ring sulfur group, a silicon group, and a boron group.

2. The compound according to claim 1, characterized in that There is at least one cycloalkyl group among B1 to B4. When B1 is a cycloalkyl group, B1 and A1 are connected in a ring manner; when B2 is a cycloalkyl group, B2 and A2 are connected in a ring manner; when B3 is a cycloalkyl group, B3 and A3 are connected in a ring manner; when B4 is a cycloalkyl group and A5 is present, B4 and A5 are connected in a ring manner; when A5 is not present, B4 and A4 are connected in a ring manner.

3. The compound according to claim 2, characterized in that The cycloalkyl group is a substituted or unsubstituted cycloalkyl group, and the substituent in the substituted cycloalkyl group is selected from an alkyl group.

4. The compound according to any one of claims 1 to 3, characterized in that Formula (I-1) The connection structure of A1 is selected from one of the following structures: Among them, *, ** and *** represent the connection sites.

5. The compound according to any one of claims 1 to 4, characterized in that Formula (I-2) The connection structure of A2 is selected from one of the following structures: Among them, *, ** and *** represent the connection sites.

6. The compound according to any one of claims 1 to 5, characterized in that Formula (I-3) The connection structure of A3 is selected from one of the following structures: Among them, *, ** and *** represent the connection sites.

7. The compound according to any one of claims 1 to 6, characterized in that Formula (I-4) The connection structure of A4 is selected from one of the following structures: Among them, * and **** represent the connection sites.

8. The compound according to any one of claims 1 to 7, characterized in that Formula (I-4) The connection structure of A5 is selected from one of the following structures: Among them, * and **** represent the connection sites.

9. The compound according to any one of claims 1 to 8, characterized in that The connection structure of B1-B4 in formula (I) is selected from one of the following structures: Among them, A 1-5 is one of A1-A4, R B1-4 For R B1 ~R B4 one of the.

10. The compound according to any one of claims 1 to 9, characterized in that The compound is selected from one of the following structures:

11. The method for preparing the compound according to any one of claims 1 to 10, characterized in that: include: A precursor containing B1A1, a precursor containing B2A2, a precursor containing B3A3, a precursor containing B4A5A4, and an ionic compound of M are mixed, and at least one reaction solution is added to allow the resulting mixture to undergo a synthesis reaction, and then the compound represented by formula (I) is obtained through extraction; in: In the precursor of B1A1, B1 is present or absent; In the precursor of B2A2, B2 is present or absent; In the precursor of B3A3, B3 is present or absent; In the B4A4 precursor, B4 may be present or absent.

12. A method for preparing a light-emitting layer, characterized in that: include: The light-emitting material is deposited on the surface of the substrate to form the light-emitting layer on the surface of the substrate, wherein the light-emitting material is the compound according to any one of claims 1 to 10.

13. An organic light-emitting device, characterized in that: The invention comprises an anode layer and a cathode layer, and at least one organic layer between the anode layer and the cathode layer, wherein one of the organic layers comprises the compound according to any one of claims 1 to 10.

14. A display device, characterized in that: The device comprises a display screen and the organic light emitting device as claimed in claim 13.

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