7-phenylquinolone derivative, preparation method and organic electroluminescent device

Abstract

The invention belongs to the technical field of organic luminescent materials and semiconductors, and particularly relates to a 7-phenylquinolone derivative, a preparation method and an organic electroluminescent device. After the 7-phenylquinolone derivative is used as a host luminescent material or an object luminescent material to be applied to a luminescent layer of the organic electroluminescent device, the luminescent efficiency of the organic electroluminescent device is effectively improved, the service life of the organic electroluminescent device is effectively prolonged, meanwhile, smaller efficiency roll-off is obtained, and the 7-phenylquinolone derivative has higher glass transition temperature and can be applied to the field of organic electroluminescent devices. Therefore, the stability and the yield of the organic light-emitting device are effectively improved. In addition, the synthetic route of the 7-phenylquinolone derivative is relatively simple, and structure optimization and production cost reduction of the 7-phenylquinolone derivative are facilitated.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic light-emitting materials and semiconductors, and in particular relates to 7-phenylquinolone derivatives, a preparation method thereof, and an organic electroluminescent device. Background Art

[0002] With the increasing popularity of electronic devices, people's requirements for display technology are constantly increasing, such as higher resolution, contrast, wider color gamut, and faster response speed. Traditional liquid crystal display technology is gradually failing to meet these requirements in some aspects. Organic light-emitting diode technology has become a research hotspot due to its advantages of self-luminescence, wide viewing angle, and fast response.

[0003] A typical organic electroluminescent device structure consists of an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode. When a voltage is applied between the anode and cathode, holes are injected from the anode and move through the hole transport layer toward the light-emitting layer. Simultaneously, electrons are injected from the cathode and move through the electron transport layer toward the light-emitting layer. In the light-emitting layer, the electrons and holes recombine to form excitons, which transfer energy to the light-emitting material, causing it to emit light.

[0004] The fabrication process for organic electroluminescent devices is complex, and the evaporation of various functional layer materials results in significant material loss, leading to the waste of raw materials. This waste not only increases production costs but also hinders the large-scale adoption of organic electroluminescent technology. Therefore, finding a host and guest luminescent material that can achieve low-cost, large-scale, and sustainable production while also exhibiting good luminescence efficiency is a pressing challenge.

[0005] Quinolones are an important class of synthetic antibacterial drugs widely used in the pharmaceutical field. Since the synthetic pathway of these derivatives is relatively simple and easy to chemically modify, they are expected to be used in the field of organic electroluminescent luminescent materials. Patent CN115636819A discloses the general formula (9): The quinolone compounds shown are used as guest luminescent materials in the light-emitting layer of an organic electroluminescent device, which can effectively reduce the starting voltage and efficiency roll-off of the organic electroluminescent device, but the service life of the organic electroluminescent device is not significantly improved. Summary of the Invention

[0006] In response to the above-mentioned deficiencies in the prior art, the present invention provides 7-phenylquinolone derivatives, preparation methods, and organic electroluminescent devices. The 7-phenylquinolone derivatives of the present invention are applied as host luminescent materials or guest luminescent materials to the light-emitting layer of the organic electroluminescent device, which can effectively improve the luminous efficiency and service life of the organic electroluminescent device, thereby overcoming the technical defects of the prior art quinolone compounds.

[0007] The present invention is achieved through the following technical solutions: The first object of the present invention is to provide a 7-phenylquinolone derivative, the structural formula of the 7-phenylquinolone derivative is shown in Formula 1: ; 7-phenylquinolone derivatives are formed by Y and the main structure through a single bond, and the structural formula of the main structure is: In the general formula 1, Y and R are each independently selected from substituted or unsubstituted C6~C 40 aryl, substituted or unsubstituted C4~C 40 Heteroaryl; C4~C 40 The heteroaryl group contains at least one of N, O, S and Si as the heteroatom, and C4~C 40 The heteroaryl group is a monocyclic heteroaryl group, a polycyclic heteroaryl group or a condensed-ring heteroaryl group.

[0008] Preferably, substituted or unsubstituted C6~C 40 In the aryl group, the substituent is selected from phenyl, biphenyl, naphthyl, phenanthrenyl or C1~C6 alkyl; substituted or unsubstituted C4~C 40 In the heteroaryl group, the substituent is selected from C1~C 12 an alkyl group, a cyano group, a trifluoromethyl group, a F atom, a D atom, a deuterated methyl group, a deuterated tert-butyl group, a deuterated phenyl group, an N,N-dimethylallyl group, an N-methylcyclohexenyl group, a phenyl group, a naphthyl group, a biphenyl group, a benzyl group, a 9,10-triphenylene group, a dibenzofuranyl group, a dibenzothiophenyl group, a 9-benzofluorenyl group, a carbazolyl group, or a deuterated carbazolyl group.

[0009] Preferably, R is any one of the following groups r1 to r177, and the structural formulas of r1 to r177 are: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 .

[0010] * indicates the position where R is bonded to the main structure, among which R10, R11, R16, R17, R19~R28, R33, R34, R37, R39~R41, R45~R47, R56~R64, R67~R69, R136, R141, R144~R149, R151~R159, R165, R167, and R173 are all bonded to the main structure through only one *.

[0011] Preferably, Y is selected from any one of y1 to y107, and the structural formula of y1 to y107 is: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 .

[0012] In y107, L1 and L2 are independently selected from H, C1~C 10 Alkyl, C3~C 10 cycloalkyl, phenyl, naphthyl, biphenyl, phenanthrenyl or pyrenyl; in addition, * represents the position at which Y is bonded to the main structure, among which y1~y7, y9, y11, y12, y17, y18, y21, y22, y35, y61, y68, y94, y95, y105, and y106 are bonded to the main structure through only one *.

[0013] Preferably, the 7-phenylquinolone derivative is any one of Compound 1 to Compound 420, and the structural formula of Compound 1 to Compound 420 is: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 .

[0014] The second object of the present invention is to provide a method for preparing 7-phenylquinolone derivatives, when Y is y107, comprising the steps of: The synthetic route of 7-phenylquinolone derivatives is shown in the reaction formula: .

[0015] Using 4-biphenylacetophenone and N,N-dimethylformamide dimethyl acetal as raw materials, nucleophilic addition occurs, followed by protonation transfer and intramolecular dehydration to obtain the intermediate Mn-1.

[0016] The intermediate Mn-1 is mixed with 3-phenyl-1,4,2-dioxazol-5-one and then undergoes ring closure under the action of a metal catalyst to obtain the intermediate Mn-2.

[0017] The intermediate Mn-2 is allowed to interact with a diaryl trifluoromethanesulfonic acid iodine compound. The central iodine atom of the diaryl trifluoromethanesulfonic acid iodine compound is in a high-valence state and has strong electrophilicity. At the same time, the intermediate Mn-2 is deprotonated under alkaline conditions to generate a strongly nucleophilic amino anion. The two undergo a nucleophilic substitution reaction to generate the intermediate Mn-3.

[0018] Using intermediate Mn-3 and I2 as raw materials, in an alkaline environment, I2 first undergoes an electrophilic substitution reaction with the α-position of the carbonyl group of the intermediate Mn-3, and then undergoes electron transfer and rearrangement processes to obtain the intermediate Mn.

[0019] The intermediate Mn is used as a raw material, and under the action of catalyst, it reacts with reactant A through nucleophilic substitution reaction or Suzuki reaction to obtain 7-phenylquinolone derivatives.

[0020] Reactant A is selected from R-boronic ester, R-boronic acid or R-secondary amine.

[0021] A second object of the present invention is to provide a method for preparing 7-phenylquinolone derivatives, which, when Y is a substituent selected from y1 to y106, comprises the following steps: The synthetic route of 7-phenylquinolone derivatives is shown in the reaction formula: .

[0022] Using 4-biphenylacetophenone and N,N-dimethylformamide dimethyl acetal as raw materials, nucleophilic addition occurs, followed by protonation transfer and intramolecular dehydration to obtain the intermediate Mn-1.

[0023] The intermediate Mn-1 is mixed with 3-phenyl-1,4,2-dioxazol-5-one and then undergoes ring closure under the action of a metal catalyst to obtain the intermediate Mn-2.

[0024] Using intermediate Mn-2 and Boc anhydride as raw materials, a nucleophilic substitution reaction occurs to obtain intermediate Mn-3.

[0025] Using intermediates Mn-3 and I2 as raw materials, in an alkaline environment, I2 undergoes an electrophilic substitution reaction with the α-position of the carbonyl group of the intermediate Mn-3 to form an intermediate structure. The intermediate structure undergoes electron transfer and rearrangement to obtain the intermediate Mn-4.

[0026] Intermediate Mn-4 is used as a raw material and reacted with reactant A' through nucleophilic substitution reaction or Suzuki reaction to obtain intermediate Mn-5; reactant A' is selected from R-boronic ester, R-boric acid or R-secondary amine.

[0027] Using intermediate Mn-5 and trifluoroacetic acid as raw materials, Boc is removed to obtain intermediate Mn.

[0028] The intermediate Mn is used as a raw material and reacts with reactant B under catalysis to obtain 7-phenylquinolone derivatives through nucleophilic substitution reaction.

[0029] Wherein, the reactant B is selected from Y'-X, X is selected from Cl, Br or I, and Y' is selected from any one of y1~y106.

[0030] The original design of the present invention is: Y is y107, which plays the role of giving the main structure a spatial three-dimensional configuration, and R is an electron-donating substituent, and the overall matching is used as a hole-transporting main light-emitting material; the test results of the organic electroluminescent device show that in the embodiment with a larger R group volume, the organic electroluminescent device performance is better; based on this, the present invention defines R as a substituent with different large volumes, and Y is designed to be a substituent with electron-withdrawing properties, and the overall composition has a DA configuration, that is, an electron-donating-electron-withdrawing configuration. This type of compound has thermally activated delayed fluorescence properties and is therefore often used as a guest light-emitting material.

[0031] The third object of the present invention is to provide a host luminescent material prepared from the above-mentioned 7-phenylquinolone derivative, wherein the 7-phenylquinolone derivative is selected from any one of Compound 1 to Compound 208.

[0032] The fourth object of the present invention is to provide a guest luminescent material prepared from the above-mentioned 7-phenylquinolone derivative, wherein the 7-phenylquinolone derivative is selected from any one of Compound 209 to Compound 420.

[0033] The fifth object of the present invention is to provide an organic electroluminescent device, comprising a cathode, an anode, and an organic layer located between the cathode and the anode, wherein the organic layer is composed 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 stacked in sequence from bottom to top, and the hole injection layer is deposited on the anode, the anode is supported on a substrate, a covering layer is also provided on the cathode, and the light-emitting layer is made of the above-mentioned main light-emitting material.

[0034] The sixth object of the present invention is to provide an organic electroluminescent device, comprising a cathode, an anode, and an organic layer located between the cathode and the anode, wherein the organic layer is composed 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 stacked in sequence from bottom to top, and the hole injection layer is deposited on the anode, the anode is supported on a substrate, a covering layer is also provided on the cathode, and the light-emitting layer is made of the above-mentioned guest light-emitting material.

[0035] Preferably, the organic electroluminescent device is used in the fields of luminous lighting, image display or optoelectronic signal transmission.

[0036] Compared with the prior art, the present invention has the following beneficial effects: 1. The prior art quinolone compounds have strong carbonyl chemical activity and are easy to form hydrogen bonds with adjacent molecules, thereby damaging the life of the organic electroluminescent device; Mark the location and get Since the protecting group is inserted into the ortho position of the carbonyl group, the ortho position of the carbonyl group is the 3-position of the quinolone, which can effectively inhibit the formation of intermolecular hydrogen bonds; in addition, the N atom on the quinolone provides an n non-bonding orbital, and the substituent R and the Y substituent connected to the N atom provide a π* anti-bonding orbital. The n electrons on the n non-bonding orbital can transition to the π* anti-bonding orbital, forming a spatial n-π* transition. The spatial n-π* transition increases the reverse intersystem crossing rate, reduces the lifetime of triplet excitons, can effectively inhibit the annihilation of triplet excitons to produce high-energy intermediates, reduce chemical bond cleavage, and help to significantly improve the life of organic electroluminescent devices.

[0037] 2. The present invention uses quinolone as the main skeleton and simultaneously substitutes at the 7- and 3-positions of the quinolone. The 7-position substituent can enhance the conjugated system, increase the range of electron delocalization, and help improve the luminous efficiency; the bulky 3-position substituent can reduce intermolecular aggregation, reduce the aggregation quenching effect, and further improve the luminous efficiency of 7-phenylquinolone derivatives in the solid state. The combination of the two can maintain good luminescent properties in different states. Prior art application number 202211327865.X discloses a luminescent material and its application, as well as an organic electroluminescent device containing the same. Studies have shown that compared with the prior art publications in which the 3- and 5-positions, 2- and 5-positions, or 5- and 7-positions of the quinolone are simultaneously substituted, the electroluminescent device prepared using the 7-phenylquinolone derivative as the luminescent material of the present invention has a longer life and higher efficiency. The advantages of the electroluminescent device of the present invention are as follows: simultaneous substitution of the 5-position and 3-position of the prior art quinolone not only causes aggregation-induced quenching and reduces the luminous efficiency, but also makes the compound difficult to synthesize and has poor solubility; and simultaneous substitution of the 2-position and 5-position, or the 5-position and 7-position, of the prior art quinolone causes the carbonyl group to lose the protection of the adjacent substituent, and the entire compound will have a certain degree of photosensitivity, thereby affecting the life of the organic electroluminescent device.

[0038] 3. The synthesis route of the 7-phenylquinolone derivatives of the present invention is relatively simple, and the 7-phenylquinolone derivatives are easy to be chemically modified, which facilitates structural optimization and functional design to meet the material performance requirements of different organic electroluminescent devices, accelerate the development of new materials, and reduce production costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is a cross-sectional view of an organic electroluminescent device assembled using the 7-phenylquinolone derivatives of the present invention.

[0040] Figure 2 This is the H NMR spectrum of compound 16 in Example 1 of the present invention.

[0041] Figure 3 This is the H NMR spectrum of compound 91 of Example 2 of the present invention.

[0042] Figure 4 This is the H NMR spectrum of compound 37 of Example 3 of the present invention.

[0043] Figure 5 This is the H NMR spectrum of compound 110 according to Example 4 of the present invention.

[0044] Figure 6 This is the H NMR spectrum of compound 223 of Example 5 of the present invention.

[0045] Figure 7 This is the H NMR spectrum of compound 394 of Example 6 of the present invention.

[0046] Figure 8 This is the H NMR spectrum of compound 419 of Example 7 of the present invention.

[0047] Description of reference numerals: 1. Substrate, 2. Anode, 3. Hole injection layer, 4. Hole transport layer, 5. Electron blocking layer, 6. Light-emitting layer, 7. Hole blocking layer, 8. Electron transport layer, 9. Electron injection layer, 10. Cathode, 11. Covering layer. DETAILED DESCRIPTION

[0048] The following describes the specific embodiments of the present invention in conjunction with the examples. The raw materials and reagents of the present invention are all commercially available. The synthesis process of the 7-phenylquinolone derivatives of Compounds 1 to 208 of the present invention is described as follows: In the present invention, N,N-dimethylformamide dimethyl acetal is referred to as DMF-DMA, dichloroethane is referred to as DCE, and tetrahydrofuran is referred to as THF.

[0049] Example 1 The preparation method of compound 16 comprises the following steps: The reaction equation for the preparation of compound 16 is: .

[0050] S1. Under nitrogen protection, take a 5L three-necked flask, add 196g and 1.0mol of 4-biphenylacetophenone and 2.5L of N,N-dimethylformamide dimethyl acetal in sequence, stir and mix evenly, then heat to 102°C and react for 2h. After the reaction, cool the reaction solution to room temperature, concentrate the solvent in vacuo to obtain a solid residue, and recrystallize the solid residue from n-heptane to obtain 173g of intermediate M1-1 with a yield of 67%, HPLC purity of 97%, and LC-MS showing a molecular weight of 252.2.

[0051] S2. Under nitrogen protection, take a 5L three-necked flask and add 151g, 0.6mol of intermediate M1-1, 147g, 0.9mol of 3-phenyl-1,4,2-dioxazol-5-one, 14.3g, 0.03mol of Cp *Co(CO)I2, 11.7 g, 0.06 mol of AgBF4, and 1.5 L of dichloroethane were stirred and mixed evenly, then heated to 80 ° C and reacted for 12 hours. After the reaction, the reaction solution was filtered through diatomaceous earth while hot, and the filter cake was repeatedly rinsed with 1.0 L of DCE. The filtrate was concentrated to obtain a solid residue, which was recrystallized using dichloromethane / n-heptane with a volume ratio of 1:3 to obtain 117 g of intermediate M1-2 with a yield of 88%, HPLC purity of 97%, and LC-MS showing a molecular weight of 222.1.

[0052] S3, under nitrogen protection, take a 500mL three-necked flask, add 44g, 0.2mol intermediate M1-2,86g, 0.2mol diphenyltrifluoromethanesulfonic acid iodine, 24g, 0.3mol sodium hydroxide, and 250mL water in sequence, seal, stir and mix evenly, then warm to 80°C and react for 6h. After the reaction is completed, the reaction solution is cooled to room temperature and extracted three times with 1.5L of DCM, each time with 0.5L, and the organic phases are combined. The organic phases are dried, filtered, and concentrated to obtain a solid residue. The solid residue is purified by silica gel column chromatography using dichloromethane / n-heptane with a volume ratio of 1:3 to obtain intermediate M1-3, weighing 54g, with a yield of 91%, HPLC purity 98%, and LC-MS showing a molecular weight of 298.1.

[0053] S4. Under nitrogen protection, take a 1.0L three-necked flask and add 44g, 0.15mol intermediate M1-3, 57g, 0.23mol iodine, 36g, 0.34mol sodium carbonate, and 400mL tetrahydrofuran in sequence, stir and mix evenly, and react at room temperature for 6h until the reaction is complete; concentrate the organic phase, extract with 1.0L dichloromethane and 1.0L water in sequence, dry, filter, and concentrate the organic phase to obtain a solid residue, and purify the solid residue by silica gel column chromatography with dichloromethane / n-heptane in a volume ratio of 1:2 to obtain intermediate M1, weighing 76g, with a yield of 90%, HPLC purity of 98%, and LC-MS showing a molecular weight of 424.0.

[0054] S5. Under nitrogen protection, take a 100mL three-necked flask, add 4.2g, 0.01mol of M1, 2.4g, 0.01mol of 9,9-dimethylfluorene-2-boric acid, 40mL of THF, 10mL of H2O, and 5.5g, 0.04mol of K2CO3, stir and heat to 40°C. After the solution is clarified, add 0.23g, 0.2mmol of Pd(PPh3)4, then raise the temperature to 70°C and continue the reaction for 12h until the reaction is completed; cool the reaction solution to room temperature, extract with ethyl acetate, combine the organic phases, dry the organic phases with anhydrous magnesium sulfate, filter, concentrate, and purify by silica gel column chromatography with dichloromethane / n-heptane in a volume ratio of 1:2 to obtain compound 16, weighing 4.4g, with a yield of 80%, HPLC content of 99%, and LC-MS showing a molecular weight of 490.7.

[0055] The hydrogen spectrum data of compound 16 are as follows Figure 2 As shown: 1 H NMR (500 MHz, CD3OD) δ 10.80 (s, 1H),7.96 – 7.81 (m, 3H), 7.80 – 7.68 (m, 3H), 7.57 – 7.20 (m, 12H), 7.05 – 6.92(m, 2H), 1.69 (s, 6H).

[0056] Example 2 The preparation method of compound 91 comprises the following steps: The reaction equation for the preparation of compound 91 is: .

[0057] S1, under nitrogen protection, take a 500mL three-necked flask, add 44g, 0.2mol intermediate M1-2,108g, 0.2mol bis(4-tert-butylphenyl)iodine trifluoromethanesulfonate, 24g, 0.3mol sodium hydroxide, and 250mL water in sequence, seal, stir and mix evenly, then warm to 80 DEG C and react for 6h, after the reaction is completed, the reaction solution is cooled to room temperature, 1.5L of DCM is added and extracted three times, each time with 0.5L, the organic phase is combined, the organic phase is dried, filtered, and concentrated to give a solid residue, the solid residue is purified by silica gel column chromatography using dichloromethane / n-heptane with a volume ratio of 1:3 to obtain intermediate M2-3, weighing 64g, and a yield of 90%, HPLC purity 98%, and LC-MS show a molecular weight of 354.2.

[0058] S2. Under nitrogen protection, take a 1.0L three-necked flask, add 53g, 0.15mol intermediate M2-3, 57g, 0.23mol iodine, 36g, 0.34mol sodium carbonate, and 400mL of THF in sequence, stir and mix evenly, react at room temperature for 6h until the reaction is complete, concentrate the organic phase, add 1.0L dichloromethane and 1.0L water in sequence for extraction, dry, filter and concentrate the organic phase to obtain a solid residue, which is purified by silica gel column chromatography with dichloromethane / n-heptane in a volume ratio of 1:3 to obtain intermediate M2, weighing 87g, with a yield of 91%, HPLC purity of 98%, and LC-MS showing a molecular weight of 480.1.

[0059] S3. Under nitrogen protection, a 100 mL three-necked flask was added, 4.8 g, 0.01 mol of M2, 1.8 g, 0.01 mol of deuterated carbazole, and 50 mL of toluene were added, and stirred until the solution was clear. 0.18 g, 0.2 mmol of Pd2(dba)3, 0.13 g, 0.5 mmol of Am-phos, and 3.8 g, 0.04 mol of sodium tert-butoxide were added, and the temperature was raised to 110 ° C. and the reaction was continued for 10 h. After the reaction was completed, diatomaceous earth was used for hot filtration, the filtrate was cooled to room temperature, purified water was added for washing, the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, the organic phases were dried over anhydrous magnesium sulfate, concentrated, and purified by silica gel column chromatography with dichloromethane / n-heptane in a volume ratio of 1:3 to obtain compound 91, weighing 4.0 g, with a yield of 76%, an HPLC content of 99%, and a molecular weight of 527.3 according to LC-MS.

[0060] The hydrogen spectrum data of compound 91 are as follows Figure 3 As shown: 1 H NMR (500 MHz, CD3OD) δ 11.14 (s, 1H),7.97 – 7.85 (m, 1H), 7.81 – 7.66 (m, 2H), 7.58 – 7.33 (m, 5H), 7.10 (s, 4H), 1.33 (s, 9H).

[0061] Example 3 The preparation method of compound 37 comprises the following steps: The operation was the same as that in step S5 of Example 1, except that 4.2 g and 0.01 mol of M1 were replaced by 4.8 g and 0.01 mol of M2, and 2.4 g and 0.01 mol of 9,9-dimethylfluorene-2-boronic acid were replaced by 2.6 g and 0.01 mol of benzothiophene-3-boronic acid pinacol ester to obtain compound 37, weighing 3.7 g, with a yield of 77%, a purity of 99% by HPLC, and a molecular weight of 486.2 according to LC-MS.

[0062] The reaction equation for the preparation of compound 37 is: .

[0063] The hydrogen spectrum data of compound 37 are as follows Figure 4 As shown: 1 H NMR (500 MHz, CD3OD) δ 10.92 (s, 1H), 8.27 (s, 1H), 7.94 – 7.71 (m, 5H), 7.53 – 7.26 (m, 7H), 7.10 (s, 4H), 1.33 (s, 9H).

[0064] Example 4 The preparation method of compound 110 comprises the following steps: The reaction equation for the preparation of compound 110 is: .

[0065] The operation was the same as that in step S5 of Example 1, except that 4.2 g and 0.01 mol of M1 were replaced by 4.8 g and 0.01 mol of M2, and 2.4 g and 0.01 mol of 9,9-dimethylfluorene-2-boronic acid were replaced by 3.03 g and 0.01 mol of (10-phenyl-10H-phenoxazin-3-yl)boronic acid to obtain compound 110, weighing 4.8 g, with a yield of 78%, a purity of 99% by HPLC, and a molecular weight of 611.3 according to LC-MS.

[0066] The hydrogen spectrum data of compound 110 are as follows Figure 5 As shown: 1 H NMR (500 MHz, CD3OD) δ 10.84 (s, 1H),8.02 – 7.87 (m, 1H), 7.82 – 7.64 (m, 2H), 7.59 – 7.34 (m, 5H), 7.29 – 7.19(m, 2H), 7.17 – 7.05 (m, 8H), 7.04 – 6.89 (m, 5H), 6.84 (d, J = 2.9 Hz, 1H),1.33 (s, 9H).

[0067] Compounds 1 to 208 were synthesized with reference to the above examples.

[0068] Compounds 1 to 208 based on the above-mentioned 7-phenylquinolone derivatives are used as host luminescent materials in organic electroluminescent devices. The basic structure and preparation method of the organic electroluminescent device adopt the currently recognized preparation process technology in the industry. The schematic diagram of the organic electroluminescent device structure is shown in FIG. Figure 1 The preparation process is described in detail as follows:

[0069] Under high vacuum conditions, an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light-emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9 and a cathode 10 are sequentially deposited on a substrate 1 to obtain a test device. A covering layer 11 is then evaporated on the cathode 10 of the test device, and then packaging is performed to complete the preparation of the test device.

[0070] The test device used in the experiment consisted of five main components: an anode 2, a hole transport layer 4, a light-emitting layer 6, an electron transport layer 8, and a cathode 10. One or a combination of two 7-phenylquinolone derivatives was used in the light-emitting layer 6 as the primary luminescent material for evaluation. The specific test device preparation is briefly described below: Substrate 1 is made of glass or a polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. In this test, ITO conductive glass was used. Furthermore, substrate 1, used as a display, can also include arrays of thin-film transistors, and a specific display image formed by the arrays.

[0071] The organic layer includes a hole transport layer 4, a light emitting layer 6 and an electron transport layer 8. The hole transport layer 4 is located between the anode 2 and the light emitting layer 6, and the electron transport layer 8 is located between the cathode 10 and the light emitting layer 6. The light emitting layer 6 is composed of a host light emitting material and a guest light emitting material. The host light emitting material is any one or a combination of any two of the compounds 1 to 208 of the present invention, and the guest light emitting material is a high performance 、 、 The material is one of the materials, and the mass ratio of the host luminescent material to the guest luminescent material is 90:10~99:1.

[0072] The anode 2 is to enable holes to be smoothly injected into the organic layer, and is preferably made of a material with a large work function. Anode materials applicable to the present invention include indium tin oxide, indium zinc oxide, tin dioxide, or zinc oxide.

[0073] The cathode 10 is designed to facilitate electron injection into the organic layer, and is preferably made of a material with a small work function, including metals, alloys, or organic combinations thereof. The cathodes that can be used in the present invention include: magnesium, silver, aluminum, aluminum-lithium, calcium, magnesium-indium, or magnesium-silver.

[0074] The functional organic layer is formed by vacuum thermal evaporation, spin coating or printing, and the compound used as the organic layer is an organic small molecule, an organic macromolecule, a polymer or a combination thereof.

[0075] The hole transport layer 4 is a single-layer hole transport layer, including a single-layer hole transport layer containing only one compound and a composite hole transport layer containing multiple compounds; the single-layer hole transport layer not only realizes hole injection but also plays a hole transport role, and the composite hole transport layer is composed of multiple organic hole materials, which are arranged in accordance with the industry's common arrangement of hole injection layer 3, hole transport layer 4, and electron blocking layer 5.

[0076] In the present invention, the hole injection layer 3 is preferably a p-doped hole injection layer. A p-doped hole injection layer refers to a hole injection layer doped with a p-dopant. A p-dopant is a material that imparts p-type semiconductor properties. P-type semiconductor properties refer to the ability to inject or transport holes at the HOMO energy level, i.e., a material property with high hole conductivity.

[0077] The light-emitting layer 6 is located between the hole transport layer 4 and the electron transport layer 8. The host light-emitting material is any one or a combination of any two of the 7-phenylquinolone derivatives of the present invention, Compounds 1 to 208. The guest light-emitting material is one of the high-performance DP-1, DP-2, and DP-3 materials. The mass ratio of the host light-emitting material to the guest light-emitting material is preferably 96:4. After the functional layer for achieving organic light emission is prepared, an electron transport material is evaporated onto the light-emitting layer 6. The electron transport material is selected from one or more combinations of E1, E2, or E3 with excellent industry performance, to form the electron transport layer 8. After the electron transport material is evaporated, an electron injection material is evaporated to form the electron injection layer 9. A cathode 10 is then sputtered. Finally, the device is packaged using standard industry packaging methods. Test device samples are prepared into 30 mm x 30 mm specimens. The samples are tested for various luminescence performance indicators and efficiency. Compared with conventional light-emitting materials, the test devices show superior luminescence performance, efficiency, and stability.

[0078] The following is a comparison and evaluation of the organic electroluminescent devices using the experimental group and the control group, as shown below: The test device control group samples, control group 1 to control group 3, were prepared according to the following steps: Under vacuum conditions, an anode 2 of indium tin oxide with a thickness of 25 nm was sequentially evaporated on a cleaned conductive glass substrate; a mixture of HT1 and P1 with a thickness of 10 nm was evaporated as a hole injection layer 3, P1 was used as a p-dopant, and the mass ratio of the two was 97:3; HT-1 with a thickness of 50 nm was evaporated as a hole transport layer 4; EB-1 with a thickness of 10 nm was evaporated as an electron blocking layer 5; after the electron blocking layer 5 was evaporated, a light-emitting layer 6 with a thickness of 30 nm was prepared, the structure of which included one of B-224, B-1346, and B-1348 used in the OLED light-emitting layer as the main light-emitting material, and B-224, B-1346, and B-1348 are all prior art application numbers 202211327865.X The disclosed compound is combined with DP-1, DP-2 or DP-3 as a guest luminescent material, and the mass ratio of the host luminescent material to the guest luminescent material is 96:4; on the luminescent layer 6, HB-1 with a thickness of 16nm is evaporated as a hole blocking layer 7; on the hole blocking layer 7, E1 is evaporated to a vacuum evaporation thickness of 25nm as an electron transport layer 8; on the electron transport layer 8, a LiF layer with a thickness of 10nm is formed by a vacuum evaporation device, and this layer is the electron injection layer 9; on the electron injection layer 9, an Al electrode layer with a thickness of 50nm is formed by a vacuum evaporation device, and this layer is the cathode 10; finally, a covering material X is evaporated on the cathode 10 to form a covering layer 11, and then it is packaged to complete the preparation of the test device. The method is used to prepare the following Figure 1 The device shown.

[0079] The detailed composition scheme is as follows: Test device control group 1: conductive glass / indium tin oxide (25nm) / HT1:P1=97:3(10nm) / HT-1(50nm) / EB-1(10nm) / B-224:DP-1=96:4(30nm) / HB-1(16nm) / E1(25nm) / LiF(10nm) / Al(50nm).

[0080] Test device control group 2: conductive glass / indium tin oxide (25nm) / HT1:P1=97:3(10nm) / HT-1(50nm) / EB-1(10nm) / B-1346:DP-1=96:4(30nm) / HB-1(16nm) / E1(25nm) / LiF(10nm) / Al(50nm).

[0081] Test device control group 3: conductive glass / indium tin oxide (25nm) / HT1:P1=97:3(10nm) / HT-1(50nm) / EB-1(10nm) / B-1348:DP-1=96:4(30nm) / HB-1(16nm) / E1(25nm) / LiF(10nm) / Al(50nm).

[0082] Test device experimental group 1 to experimental group 3: The preparation method is the same as that of the test device control group 1, except that the main luminescent material CDBP is replaced by compound 8 of the present invention, and the mass ratios of the main luminescent material to the guest luminescent material are 90:10, 99:1, and 96:4, respectively, corresponding to experimental groups 1 to 3.

[0083] Test device experimental group 4 to experimental group 25: The preparation method is the same as that of the test device control group 1, except that the main light-emitting material CDBP is replaced by compound 10, compound 19, compound 22, compound 44, compound 106, compound 134, compound 45, compound 53, compound 67, compound 70, compound 83, compound 95, compound 116, compound 120, compound 129, compound 137, compound 146, compound 154, compound 163, compound 199, compound 206, and compound 208 of the present invention in sequence.

[0084] Test device experimental groups 26 to 34: The preparation method is the same as that of test device control group 1, except that the light-emitting layer 6 in this experimental group uses a dual-host light-emitting material. The selection of the host light-emitting material and the ratio of the host light-emitting material to the guest light-emitting material of the light-emitting layer 6 are shown in Table 1: Table 1 Ratios of host luminescent materials and guest luminescent materials in experimental groups 26 to 34

[0085] Note: The “ratio” in the table refers to the mass ratio of the first host luminescent material, the second host luminescent material and the guest luminescent material.

[0086] The conventional material structures used in the above test device preparation process are as follows: 、 、 、 、 、 、 、 、 、 、 、 、 、 .

[0087] The display performance data was collected for the control group test devices and the experimental group test devices. The collected data results are shown in Table 2: Table 2. Data collection of display performance of test devices in the control group and experimental group

[0088] Note: Tg is the glass transition temperature of the light-emitting layer material under high temperature; the current density during the test device detection process is 15mA / cm; LT90 refers to the time it takes for the brightness of the test device to decay to 90% of the initial brightness; “ / ” indicates that this type of data has not been tested.

[0089] As shown in Table 2, from the data of the test device, the test device prepared by using the preferred compound of the present invention as the main light-emitting material is compared with the main light-emitting materials in control groups 1 to 3. The driving voltage of the test device is reduced, the thermal stability is significantly improved, and the overall test device efficiency is significantly improved.

[0090] It can be seen from experimental groups 1 to 3 of the present invention that when the mass ratio of the main luminescent material in the luminescent layer 6 is in the range of 90:10 to 99:1, the comprehensive luminescent performance is improved. When the mass percentage is 96%, the luminescent performance of the prepared test device is the best.

[0091] Compared with Experimental Groups 3 to 6, Experimental Groups 7 to 9, and Experimental Group 15, the test device data from Experimental Groups 3 to 6 were slightly inferior. This may be due to the presence of bulky, fully deuterated R substituents in Compounds 44, 106, 134, and 95, corresponding to Experimental Groups 7 to 9 and 15. The introduction of D atoms into the compound molecules enhances spin-orbit coupling, which increases the intersystem crossing ability of the electrons in the molecules, increases the radiative transition rate, and reduces the non-radiative transition rate, thereby improving the quantum efficiency of the guest phosphorescent material.

[0092] Compared with experimental groups 1 to 24, experimental groups 26 to 34 of the present invention have significantly improved overall efficiency. This may be because the preferred compounds of the present invention are used as dual-host light-emitting materials, which can effectively balance holes and electrons while forming a wider carrier recombination area, thereby greatly improving the luminous efficiency of the test device.

[0093] The present invention discloses 7-phenylquinolone derivatives and an organic electroluminescent device. The 7-phenylquinolone derivatives are used as a main luminescent material in a luminescent layer of an organic electroluminescent device, which can effectively improve the luminous efficiency and service life of the organic electroluminescent device.

[0094] The synthetic route of the 7-phenylquinolone derivatives of the present invention is relatively simple and easy to chemically modify, facilitating structural optimization and functional design to meet the performance requirements of different organic electroluminescent devices for the main luminescent material, thereby accelerating the development of new materials and reducing production costs.

[0095] The synthesis process of 7-phenylquinolone derivatives of compounds 209 to 420 of the present invention is described as follows: The R group in compounds 209 to 420 is introduced via reactant A', wherein reactant A' is selected from one of A'01 to A'11, and the structural formulas of reactants A'01 to A'11 are as follows: 、 、 、 、 、 、 、 、 、 、 .

[0096] The Y group in compounds 209 to 420 of the present invention is introduced via reactant B, wherein reactant B is selected from one of B1 to B128, and the structural formulas of B1 to B128 are as follows: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 .

[0097] Example 5 The preparation method of compound 223 comprises the following steps: .

[0098] The preparation methods of S1 and intermediate M1-2 are the same as those in Example 1.

[0099] S2. Take a 2.0L three-necked flask, add 111g, 0.5mol of intermediate M1-2, 1.0L of DCM, and 164g, 0.75mol of Boc anhydride in sequence, and stir at room temperature for 2h. After the reaction is completed, concentrate under reduced pressure to obtain a solid residue. The solid residue is purified by silica gel column chromatography using dichloromethane / n-heptane in a volume ratio of 1:3 to obtain intermediate M10-1, weighing 146g, with a yield of 91%, a purity of 98% by HPLC, and a molecular weight of 322.2 according to LC-MS.

[0100] S3. Under nitrogen protection, take a 3.0L three-necked flask and add 145g, 0.45mol intermediate M10-1, 171g, 0.68mol iodine, 107, 1.01mol sodium carbonate, and 1.5L of THF in sequence. Stir and mix evenly. React at room temperature for 6h until the reaction is complete. Concentrate the organic phase, add 2.0L dichloromethane and 2.0L water in sequence for extraction. The organic phase is dried, filtered, and concentrated to obtain a solid residue. The solid residue is purified by silica gel column chromatography with dichloromethane / n-heptane in a volume ratio of 1:3 to obtain intermediate M10-2, weighing 181g, with a yield of 90%, HPLC purity of 98%, and LC-MS showing a molecular weight of 448.1.

[0101] S4. Under nitrogen protection, a 3.0L three-necked flask was added, 134g, 0.3mol of M10-2, 84g, 0.3mol of A'01, and 1500mL of toluene were added, and stirred until the solution was clear. 5.5g, 2mmol of Pd2(dba)3, 4.0g, 1.5mmol of Am-phos, and 58g, 0.6mol of sodium tert-butoxide were added, and then the temperature was raised to 120°C and the reaction was continued for 10h. After the reaction was completed, diatomaceous earth was used for hot filtration, the filtrate was cooled to room temperature, purified water was added for washing, the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, the organic phases were dried over anhydrous magnesium sulfate, concentrated, and purified by silica gel column chromatography with dichloromethane / petroleum ether in a volume ratio of 1:2 to obtain the intermediate M10-3, weighing 137g, with a yield of 76%, an HPLC content of 99%, and a molecular weight of 599.3 according to LC-MS.

[0102] S5. Under nitrogen protection, a 1.0 L three-necked flask was added with 60 g and 0.1 mol of M10-3, 500 mL of DCM, and 57 g of trifluoromethanesulfonic acid. The reaction was stirred at room temperature for 2 h until the reaction was complete. After the reaction was completed, the reaction was concentrated under reduced pressure to obtain a solid residue, which was purified by silica gel column chromatography using dichloromethane / n-heptane in a volume ratio of 1:2 to obtain intermediate M10, weighing 47 g, with a yield of 94%, a purity of 98% by HPLC, and a molecular weight of 499.3 according to LC-MS.

[0103] S6. Under nitrogen protection, a 100 mL three-necked flask was added with 5.0 g, 0.01 mol of M10, 1.6 g, 0.01 mol of 5-chloro-1,3-dicyanobenzene, and 50 mL of toluene. The mixture was stirred until the solution was clear, and 0.18 g, 0.2 mmol of Pd2(dba)3, 0.13 g, 0.5 mmol of Am-phos, and 6.5 g, 0.02 mol of cesium carbonate were added. The temperature was then raised to 120°C and the reaction was continued for 10 h. After the reaction was completed, the mixture was filtered while hot using diatomaceous earth. The filtrate was cooled to room temperature and washed with purified water. The organic phase was retained after separation and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, dried over anhydrous magnesium sulfate, concentrated, and purified by silica gel column chromatography using dichloromethane / petroleum ether in a volume ratio of 1:2 to obtain compound 223, weighing 4.8 g, with a yield of 77%, an HPLC content of 99%, and a molecular weight of 625.3 according to LC-MS.

[0104] The H NMR spectrum data of compound 223 are as follows Figure 6 As shown: 1 H NMR (500 MHz, CD3OD ) δ 11.06 (s,1H), 8.95 (d, J = 3.1 Hz, 1H), 8.36 (d,J = 3.1 Hz, 1H), 7.91 (t, J = 11.2 Hz, 1H),7.80 (d, J = 3.0 Hz, 2H), 7.78 – 7.72 (m, 2H), 7.65 – 7.58 (m, 3H), 7.53 – 7.37(m, 6H), 7.32 (d, J = 14.9 Hz, 1H), 1.43 (s, 18H).

[0105] Example 6 The preparation method of compound 394 comprises the following steps: .

[0106] S1. Under nitrogen protection, take a 3.0L three-necked flask, add 134g, 0.3mol of M10-2, 70g, 0.3mol of compound A'05, 83g, 0.6mol of K2CO3, 1200mL of THF, and 300mL of water, stir and heat to 40°C, after the solution is clarified, add 6.9g, 6mmol of Pd(PPh3)4, then raise the temperature to 70°C and continue the reaction for 12h until the reaction is complete; cool the reaction solution to room temperature, extract with ethyl acetate, combine the organic phases, dry the organic phases with anhydrous magnesium sulfate, filter and concentrate, and purify by silica gel column chromatography with dichloromethane / n-heptane in a volume ratio of 1:3 to obtain intermediate M11-1, weighing 124g, with a yield of 81%, HPLC purity of 98%, and LC-MS showing a molecular weight of 510.3.

[0107] S2. Synthesis of intermediate M11: Refer to step S5 of the synthesis process of compound 223, except that 60 g, 0.1 mol of intermediate M10-3 was replaced by 51 g, 0.1 mol of intermediate M11-1, to obtain intermediate M11, weighing 39 g, with a yield of 95%, a purity of 98% by HPLC, and a molecular weight of 410.3 according to LC-MS.

[0108] S3. The synthesis of compound 394 was carried out by referring to step S6 of the synthesis process of compound 223, except that 5.0 g and 0.01 mol of intermediate M10 were replaced by 4.1 g and 0.01 mol of intermediate M11 to obtain compound 394 with a weight of 4.4 g, a yield of 78%, a purity of 99% by HPLC, and a molecular weight of 561.3 according to LC-MS.

[0109] The H NMR spectrum data of compound 394 are as follows Figure 7 As shown: 1H NMR (500 MHz, CD3OD ) δ 10.75 (s,1H), 8.35 (dd, J = 14.8, 3.1 Hz, 1H), 7.96 – 7.88 (m, 2H), 7.79 – 7.60 (m, 4H), 7.55 – 7.33 (m, 8H), 7.11 (d, J = 2.9 Hz, 2H), 1.35 (s, 18H).

[0110] Example 7 The preparation method of compound 419 comprises the following steps: .

[0111] S1. The synthesis of intermediate M12-1 refers to step S1 of the synthesis process of intermediate M11, except that 70 g and 0.3 mol of compound A'05 are replaced by 134 g and 0.3 mol of compound A'08 to obtain intermediate M12-1 with a weight of 154 g, a yield of 80%, a purity of 98% by HPLC, and a molecular weight of 640.3 according to LC-MS.

[0112] S2. The synthesis of intermediate M12 refers to step S5 of the synthesis process of intermediate M1, except that 60 g and 0.1 mol of intermediate M10-3 are replaced by 64 g and 0.1 mol of intermediate M12-1 to obtain compound M12, weighing 50 g, with a yield of 93%, a purity of 98% by HPLC, and a molecular weight of 540.3 according to LC-MS.

[0113] S3. The synthesis of compound 431 was carried out by referring to step S6 of the synthesis process of compound 223, except that 5.0 g and 0.01 mol of intermediate M1 were replaced by 5.4 g and 0.01 mol of intermediate M8, to obtain compound 419 with a weight of 5.3 g, a yield of 72%, a purity of 99% by HPLC, and a molecular weight of 741.3 according to LC-MS.

[0114] The H NMR spectrum data of compound 419 are as follows Figure 8 As shown: 1 H NMR (500 MHz, CD3OD ) δ 10.75 (s,1H), 8.45 (dd, J = 14.7, 3.2 Hz, 2H), 8.16 (dt, J= 11.0, 5.6 Hz, 2H), 8.12 –8.03 (m, 2H), 8.02 – 7.89 (m, 2H), 7.82 – 7.33 (m, 21H), 1.69 (s, 6H).

[0115] Referring to the synthesis methods of Examples 5 to 7, the following compounds were synthesized. The reactants and mass spectrometry (M+1) data of some of the compounds are shown in Table 3.

[0116] Table 3 Reactants and mass spectrometry data of some compounds from Compound 209 to Compound 420

[0117] Based on compounds 209 to 420, the preferred compounds are used as guest luminescent materials in the test device, wherein the basic structure and preparation method of the test device adopt the device preparation process technology currently recognized in the industry. The schematic diagram of the test device structure is shown in FIG. Figure 1 As shown in the figure, the preparation process of the test device is described in detail as follows: The test device used in the experiment consisted of five main components: an anode 2, a hole transport layer 4, a light-emitting layer 6, an electron transport layer 8, and a cathode 10. Compounds 209 through 420, or any combination of two, were used in the light-emitting layer 6 region to serve as guest luminescent materials for evaluation. The specific test device preparation is briefly described below: Substrate 1 is made of glass or a polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. In this test, ITO conductive glass was used. Furthermore, substrate 1 used for a display may also include arrays of thin-film transistors, and a specific display image formed by the arrays.

[0118] The organic layer includes a hole transport layer 4, a light emitting layer 6 and an electron transport layer 8. The hole transport layer 4 is located between the anode 2 and the light emitting layer 6, and the electron transport layer 8 is located between the cathode 10 and the light emitting layer 6. The light emitting layer 6 is composed of a host light emitting material and a guest light emitting material. The host light emitting material is made of high performance, 、 、 、 One of the materials, the guest luminescent material is any one of Compound 209 to Compound 420 of the present invention, and the mass ratio of the host luminescent material to the guest luminescent material is 90:10 to 99:1.

[0119] The anode 2 is to enable holes to be smoothly injected into the organic layer, and is preferably made of a material with a large work function. Anode materials applicable to the present invention include indium tin oxide, indium zinc oxide, tin dioxide, or zinc oxide.

[0120] The cathode 10 is designed to facilitate electron injection into the organic layer, and is preferably made of a material with a small work function, including metals, alloys, or organic combinations thereof. The cathodes that can be used in the present invention include: magnesium, silver, aluminum, aluminum-lithium, calcium, magnesium-indium, or magnesium-silver.

[0121] The functional organic layer is formed by vacuum thermal evaporation, spin coating or printing, and the compound used as the organic layer is an organic small molecule, an organic macromolecule, a polymer or a combination thereof.

[0122] The hole transport layer 4 is a single-layer hole transport layer, including a single-layer hole transport layer containing only one compound and a composite hole transport layer containing multiple compounds; the single-layer hole transport layer not only realizes hole injection but also plays a hole transport role, and the composite hole transport layer is composed of multiple organic hole materials, which are arranged in accordance with the industry's common arrangement of hole injection layer 3, hole transport layer 4, and electron blocking layer 5.

[0123] In the present invention, the hole injection layer is preferably a p-doped hole injection layer, which means a hole injection layer doped with a p-dopant. A p-dopant is a material that can impart p-type semiconductor properties. P-type semiconductor properties refer to the property of injecting or transporting holes at the HOMO energy level, i.e., a material property of having high hole conductivity.

[0124] The light-emitting layer 6 is located between the hole transport layer 4 and the electron transport layer 8. The host light-emitting material is one of the high-performance materials PH-1, PH-2, PH-3, PH-4, and PH-5. The guest light-emitting material is any one of compounds 209 to 420. The mass ratio of the host light-emitting material to the guest light-emitting material is preferably 90:10 to 99:1. After the functional layer for achieving organic light emitting is prepared, the electron transport material is evaporated on the light-emitting layer 6. The electron transport material can be one or more combinations of E1, E2, or E3 with excellent industry performance to obtain the electron transport layer 8. After the electron transport material is evaporated, the electron injection material is evaporated to form the electron injection layer 9. Then, the metal cathode 10 is sputtered. Finally, the device is packaged using the industry's common device packaging method. The test device is prepared into a 30mm×30mm sample. The sample's various luminescence performance indicators and efficiency are tested. Compared with conventional light-emitting materials, the device has better luminescence performance, efficiency, and stability.

[0125] Test device control group samples, control group 4 to control group 6, were prepared according to the following steps: Under vacuum conditions, an anode 2 indium tin oxide with a thickness of 25 nm was sequentially evaporated on a cleaned conductive glass substrate; a mixture of HT1 and P1 with a thickness of 10 nm was evaporated as a hole injection layer 3, P1 was used as a p-dopant, and the mass ratio of the two was 97:3; HT-1 with a thickness of 50 nm was evaporated as a hole transport layer 4; EB-1 with a thickness of 10 nm was evaporated as an electron blocking layer 5; after the electron blocking layer 5 was evaporated, a light-emitting layer 6 with a thickness of 30 nm was prepared, the structure of which included PH-4 or PH-5 used in the OLED light-emitting layer, PH-4 or PH-5 as the main light-emitting material, and one of B-224, B-1346, and B-1348 as the guest light-emitting material, and B-224, B-1346 and B- 1348 are all compounds disclosed in prior art application number 202211327865.X, and the mass ratio of the main luminescent material to the guest luminescent material is 96:4; on the luminescent layer 6, HB-1 with a film thickness of 16nm is evaporated as the hole blocking layer 7; on the hole blocking layer 7, E1 is evaporated, and the vacuum evaporated film thickness of this material is 25nm, as the electron transport layer 8; on the electron transport layer 8, a LiQ layer with a film thickness of 10nm is made by a vacuum evaporation device, and this layer is the electron injection layer 9; on the electron injection layer 9, an Al electrode layer with a film thickness of 50nm is made by a vacuum evaporation device, and this layer is the cathode 10; finally, the covering layer material X-1 is evaporated on the cathode 10 to form a covering layer 11 and then packaged to complete the preparation of the test device. The method is used to prepare Figure 1 shown.

[0126] The detailed composition scheme is as follows: Test device control group 4: Indium Tin Oxide (25nm) / HT1:P1=97:3(10nm) / HT-1(50nm) / EB-1(10nm) / PH-4: B-224=96:4(30nm) / HB-1(16nm) / E1(25nm) / LiQ(10nm) / Al(50nm).

[0127] Test device control group 5: Indium Tin Oxide (25nm) / HT1:P1=97:3(10nm) / HT-1(50nm) / EB-1(10nm) / PH-4: B-1346=96:4(30nm) / HB-1(16nm) / E1(25nm) / LiQ(10nm) / Al(50nm).

[0128] Test device control group 6: Indium Tin Oxide (25nm) / HT1:P1=97:3(10nm) / HT-1(50nm) / EB-1(10nm) / PH-4: B-1348=96:4(30nm) / HB-1(16nm) / E1(25nm) / LiQ(10nm) / Al(50nm).

[0129] Test device experimental groups 35 to 64 were prepared in the same manner as the test device control group 4, except that the guest luminescent material BD-1 was replaced with the compound of the present invention. The specific replacement compounds are shown in Table 4.

[0130] Table 4. Guest luminescent materials corresponding to experimental groups 35 to 64

[0131] The conventional material structures used in the above test device preparation process are as follows: 、 、 、 、 、 、 、 、 、 、 、 、 、 .

[0132] Display performance data was collected for the control group test devices and the experimental group test devices. The collected data results are shown in Table 5: Table 5 Display performance data collection table of the control group and experimental group test devices

[0133] Note: Tg is the glass transition temperature of the light-emitting layer material under high temperature; the current density during the test device detection process is 15mA / cm 2 ; YT90 refers to the time it takes for the brightness of the test device to decay to 90% of its initial brightness.

[0134] As shown in Table 5, based on the test data of the test devices of experimental groups 35 to 64, the test devices prepared using the preferred compounds of the present invention as the guest luminescent materials have lower driving voltages, significantly improved thermal stability, significantly extended service life, and significantly improved overall test device efficiency, which has potential value for its promotion and application.

[0135] Compared with Experimental Groups 35 to 47, Experimental Groups 57 to 64, and Experimental Groups 48 to 56, the test data of the test devices in Experimental Groups 35 to 47, and Experimental Groups 57 to 64 were slightly inferior. This may be because the corresponding compounds 337, 339, 342, 344, 346, 348, 357, 361, and 366 in Experimental Groups 48 to 56 contain fully deuterated carbazole substituents. After the introduction of D atoms into the compound molecules, the spin-orbit coupling of the compound molecules is enhanced, which will increase the intersystem crossing ability of the electrons in the molecules, increase the radiative transition rate of the molecules, and reduce the non-radiative transition rate, thereby improving the quantum efficiency of the guest luminescent material and the service life of the test devices.

[0136] By comparison with the test devices prepared from a single main material, the overall efficiency of the test devices of Experimental Groups 35 to 64 of the present invention is significantly improved compared with Experimental Groups 1 to 25. This may be because the R groups in the compounds corresponding to Experimental Groups 35 to 64 have a large steric hindrance, which is beneficial to inhibiting the formation of intermolecular hydrogen bonds by the carbonyl group. At the same time, the Y groups in the compounds corresponding to Experimental Groups 35 to 64 are all electron-withdrawing groups. This design promotes effective polarization within the compound molecules, enhances the electrical transmission properties and improves the quantum efficiency, thereby improving the overall performance of the test device.

[0137] When compounds 209 to 420 of the present invention are used as guest luminescent materials in the light-emitting layer of an organic electroluminescent device, the luminous efficiency and service life of the organic electroluminescent device can be effectively improved.

[0138] The synthetic routes of compounds 209 to 420 of the present invention are relatively simple, and the main structures are easy to chemically modify, facilitating structural optimization and functional design to meet the material performance requirements of different organic electroluminescent devices, accelerate the development of new materials, and reduce production costs.

[0139] While preferred embodiments of the present invention have been described in detail above, the present invention is not limited to the aforementioned embodiments. Various modifications may be made within the scope of knowledge of those skilled in the art without departing from the spirit of the present invention. Numerous other changes and modifications may be made without departing from the spirit and scope of the present invention. It should be understood that the present invention is not limited to the specific embodiments, and the scope of the present invention is defined by the appended claims.

Claims

1. A 7-phenylquinolone derivative, characterized in that: The structural formula of the 7-phenylquinolone derivatives is shown in Formula 1: ; 7-phenylquinolone derivatives are formed by Y and the main structure through a single bond, and the structural formula of the main structure is: ; In the general formula 1, Y and R are each independently selected from substituted or unsubstituted C6~C 40 aryl, substituted or unsubstituted C4~C 40 heteroaryl; C4~C 40 The heteroaryl group contains at least one of N, O, S and Si as the heteroatom, and C4~C 40 The heteroaryl group is a monocyclic heteroaryl group, a polycyclic heteroaryl group or a condensed-ring heteroaryl group.

2. The 7-phenylquinolone derivative according to claim 1, characterized in that Substituted or unsubstituted C6~C 40 In the aryl group, the substituent is selected from phenyl, biphenyl, naphthyl, phenanthrenyl or C1~C6 alkyl; Substituted or unsubstituted C4~C 40 In the heteroaryl group, the substituent is selected from C1~C 12 an alkyl group, a cyano group, a trifluoromethyl group, a F atom, a D atom, a deuterated methyl group, a deuterated tert-butyl group, a deuterated phenyl group, an N,N-dimethylallyl group, an N-methylcyclohexenyl group, a phenyl group, a naphthyl group, a biphenyl group, a benzyl group, a 9,10-triphenylene group, a dibenzofuranyl group, a dibenzothiophenyl group, a 9-benzofluorenyl group, a carbazolyl group, or a deuterated carbazolyl group.

3. The 7-phenylquinolone derivative according to claim 2, characterized in that R is selected from any one of r1 to r177, and the structural formula of r1 to r177 is: ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； Wherein, * indicates the position where R is bonded to the main structure, among which R10, R11, R16, R17, R19~R28, R33, R34, R37, R39~R41, R45~R47, R56~R64, R67~R69, R136, R141, R144~R149, R151~R159, R165, R167, and R173 are all bonded to the main structure through only one *.

4. The 7-phenylquinolone derivative according to claim 3, characterized in that Y is selected from any one of y1 to y107, and the structural formula of y1 to y107 is: ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； In y107, L1 and L2 are independently selected from H, C1~C 10 Alkyl, C3~C 10 cycloalkyl, phenyl, naphthyl, biphenyl, phenanthrenyl or pyrenyl; In addition, * indicates the position where Y is bonded to the main structure, among which y1~y7, y9, y11, y12, y17, y18, y21, y22, y35, y61, y68, y94, y95, y105, and y106 are each bonded to the main structure through only one *.

5. The 7-phenylquinolone derivative according to claim 4, characterized in that The 7-phenylquinolone derivative is any one of Compound 1 to Compound 420, and the structural formula of Compound 1 to Compound 420 is: ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； ； 。 6. A method for preparing the 7-phenylquinolone derivatives according to claim 5, characterized in that: When Y is a substituent y107, the method comprises the following steps: The synthetic route of 7-phenylquinolone derivatives is shown in the reaction formula: ； Using 4-biphenylacetophenone and N,N-dimethylformamide dimethyl acetal as raw materials, nucleophilic addition occurs, followed by protonation transfer and intramolecular dehydration to obtain the intermediate Mn-1; After mixing the intermediate Mn-1 with 3-phenyl-1,4,2-dioxazol-5-one, the intermediate Mn-2 is obtained by ring closure under the action of a metal catalyst. The intermediate Mn-2 is allowed to interact with a diaryl trifluoromethanesulfonic acid iodine compound. The central iodine atom of the diaryl trifluoromethanesulfonic acid iodine compound is in a high-valence state and has strong electrophilicity. At the same time, the intermediate Mn-2 is deprotonated under alkaline conditions to generate a strongly nucleophilic amino anion. The two undergo a nucleophilic substitution reaction to generate the intermediate Mn-3. Using intermediate Mn-3 and I2 as raw materials, in an alkaline environment, I2 first undergoes an electrophilic substitution reaction with the α-position of the carbonyl group of the intermediate Mn-3, and then undergoes electron transfer and rearrangement to obtain the intermediate Mn; Using the intermediate Mn as the raw material, under the action of catalyst, it reacts with reactant A through nucleophilic substitution reaction or Suzuki reaction to obtain 7-phenylquinolone derivatives; Reactant A is selected from R-boronic ester, R-boronic acid or R-secondary amine.

7. A method for preparing the 7-phenylquinolone derivatives according to claim 5, characterized in that: When Y is a substituent y1 to y106, the method comprises the following steps: The synthetic route of 7-phenylquinolone derivatives is shown in the reaction formula: ； Using 4-biphenylacetophenone and N,N-dimethylformamide dimethyl acetal as raw materials, nucleophilic addition occurs, followed by protonation transfer and intramolecular dehydration to obtain the intermediate Mn-1; After mixing the intermediate Mn-1 with 3-phenyl-1,4,2-dioxazol-5-one, the intermediate Mn-2 is obtained by ring closure under the action of a metal catalyst. Using intermediate Mn-2 and Boc anhydride as raw materials, a nucleophilic substitution reaction occurs to obtain intermediate Mn-3; Using intermediates Mn-3 and I2 as raw materials, in an alkaline environment, I2 undergoes an electrophilic substitution reaction with the α-position of the carbonyl group of the intermediate Mn-3 to form an intermediate structure. The intermediate structure undergoes electron transfer and rearrangement to obtain the intermediate Mn-4. Intermediate Mn-4 is used as a raw material, and reacted with reactant A' through a nucleophilic substitution reaction or a Suzuki reaction to obtain intermediate Mn-5; reactant A' is selected from R-boronic ester, R-boric acid or R-secondary amine; Using intermediate Mn-5 and trifluoroacetic acid as raw materials, the Boc was removed to obtain intermediate Mn; Using the intermediate Mn as the raw material, it reacts with the reactant B under the catalysis of a nucleophilic substitution reaction to obtain 7-phenylquinolone derivatives; Wherein, the reactant B is selected from Y'-X, X is selected from Cl, Br or I, and Y' is selected from any one of y1~y106.

8. A host luminescent material, characterized in that: Prepared from any one of compound 1 to compound 208 in claim 5.

9. A guest luminescent material, characterized in that Prepared from any one of compounds 209 to 420 in claim 5.

10. An organic electroluminescent device comprising a cathode (10), an anode (2), and an organic layer located between the cathode (10) and the anode (2), wherein the organic layer comprises 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), and an electron injection layer (9) stacked in sequence from bottom to top, and the hole injection layer (3) is deposited on the anode (2), the anode (2) is supported on a substrate (1), and a covering layer (11) is further provided on the cathode (10), characterized in that: The light-emitting layer (6) is made of the main light-emitting material according to claim 8.

11. An organic electroluminescent device comprising a cathode (10), an anode (2), and an organic layer located between the cathode (10) and the anode (2), wherein the organic layer comprises 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), and an electron injection layer (9) stacked in sequence from bottom to top, and the hole injection layer (3) is deposited on the anode (2), the anode (2) is supported on a substrate (1), and a covering layer (11) is further provided on the cathode (10), characterized in that: The light-emitting layer (6) is made of the guest light-emitting material according to claim 9.

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