Metal complexes and their uses

Abstract

This article relates to a metal complex and its use. The metal complex has the structure shown in the following formula (1). This metal complex has advantages such as high optical, electrochemical, and thermal stability, high luminous efficiency, long device life, and high color saturation, and is used in organic electroluminescence devices. In particular, as a green-emitting phosphorescent material, it has the potential for use in the AMOLED industry. JPEG2023547490000051.jpg82160

Description

[Technical field]

[0001] The present invention relates to the technical field of organic electroluminescence, in particular to the technical field of organic electroluminescent devices, in particular to metal complexes and their use in organic electroluminescent devices. [Background technology]

[0002] At present, organic electroluminescence devices (OLEDs) as a new generation display technology are attracting more and more attention in both display and lighting technology fields, and have the prospect of being widely used. However, the performance of OLED devices, such as luminous efficiency, driving voltage, service life, etc., needs to be continuously enhanced and improved in comparison with market usage requirements.

[0003] Generally, the basic structure of an OLED device is a sandwich structure of thin organic functional material films with various functions between metal electrodes, in which holes and electrons are injected from the cathode and anode by current driving, and after the holes and electrons move a specified distance, they are recombined in the light-emitting layer and emitted in the form of light or heat, resulting in the emission of OLED light. However, organic functional materials are the core components of organic electroluminescence devices, and the thermal stability, photochemical stability, electrochemical stability, quantum yield, film formation stability, crystallinity, saturation, etc. of the materials are factors that affect the device performance.

[0004] Generally, organic functional materials include fluorescent materials and phosphorescent materials. Fluorescent materials are usually organic low-molecular-weight materials, and generally, only 25% of the singlet state can be used for emission, so that the luminous efficiency is relatively low. On the other hand, phosphorescent materials can utilize 75% of the energy of triplet excitons in addition to 25% of the singlet state due to the spin-orbit coupling action caused by the heavy atom effect, so that the luminous efficiency can be improved. However, phosphorescent materials are slower to utilize than fluorescent materials, and it is necessary to improve the material thermal stability, life, and color saturation, which is a challenging task. In the prior art, various organometallic compounds have been developed as such phosphorescent materials. However, the market is still expecting the development of new materials that can further improve the performance of organic electroluminescent elements. Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides organic electroluminescent devices with high performance and new materials that can achieve such organic electroluminescent devices. [Means for solving the problem]

[0006] As a result of extensive research conducted in order to achieve the above object, the inventors have discovered that a high-performance organic electroluminescence element can be obtained by using a metal complex containing a structure represented by the following formula (1) as a ligand.

[0007] One of the objects of the present invention is to provide a metal complex for use in an organic electroluminescence device, which has the advantages of low sublimation temperature, high optical and electrochemical stability, high saturation, high luminous efficiency, long device life, etc. In particular, as a green emitting dopant, it has the potential for use in the OLED industry.

[0008] A metal complex having a structure shown in formula (1):

[0009] JPEG0007624066000001.jpg82131

[0010] However, at least one of R1 to R18 is a structure represented by formula (2),

[0011] JPEG0007624066000002.jpg69139

[0012] however,

[0013] * indicates the position of connection to formula (1),

[0014] M is individually Pt, Pd;

[0015] X individually represents O, S, Se, or CRaRb;

[0016] L1-L3 are each independently selected from a directly bonded single bond, O, S, Se, NRc, CRdRe, SO, SO2, and PO(Rf)(Rg);

[0017] L4 is a single bond, O, a substituted or unsubstituted C1 to C20 alkylene, a substituted or unsubstituted C3 to C30 cycloalkylene, a substituted or unsubstituted C1 to C20 heteroalkylene, a substituted or unsubstituted C7 to C30 aralkylene, a substituted or unsubstituted C2 to C20 alkenylene, a substituted or unsubstituted C3 to C30 Alkylenesilyl , a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C3-C30 heteroarylene, a substituted or unsubstituted C3-C30 arylenesilyl, or a substituted or unsubstituted C0-C20 imidogen;

[0018] The remaining R1 to R18, R101 to R102 and Ra to Rg are each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C30 cycloalkyl, substituted or unsubstituted C1 to C20 heteroalkyl, substituted or unsubstituted C7 to C30 aralkyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C6 to C30 aryloxy, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C3 to C30 alkylsilyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C3 to C30 heteroaryl, substituted or unsubstituted C3 to C30 arylsilyl, and substituted or unsubstituted C0 to C20 amino. , nitriles, isonitriles and phosphino, or a cyclic or double-ring structure formed by connecting any two adjacent groups together, the substitution being substituted with deuterium, halogen, C1-C4 alkyl, or cyano;

[0019] The substitution numbers of R101 and R102 individually range from no substitution to the maximum substitution number in this metal complex.

[0020] Preferably, it has a structure shown in formula (3):

[0021] JPEG0007624066000003.jpg105152

[0022] However, at least one of R1 to R18 is a structure represented by formula (2),

[0023] JPEG0007624066000004.jpg56117

[0024] Here, the definitions of *, X, L4, R1 to R18, R101 to R102, and Ra to Rb are the same as above.

[0025] Preferably, it has a structure shown in formula (4):

[0026] JPEG0007624066000005.jpg86157

[0027] however, X individually represents O, S, Se, or CRaRb;

[0028] L4 is a single bond, O, a substituted or unsubstituted C1 to C10 alkylene, a substituted or unsubstituted C3 to C10 cycloalkylene, a substituted or unsubstituted C2 to C10 heteroalkylene, a substituted or unsubstituted C7 to C20 aralkylene, a substituted or unsubstituted C2 to C20 alkenylene, a substituted or unsubstituted C3 to C30 Alkylenesilyl , a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C3-C30 heteroarylene, a substituted or unsubstituted C3-C30 arylenesilyl, or a substituted or unsubstituted C0-C20 imidogen;

[0029] The definitions of R1, R2, R7, R8, R10, R11, R18, R101, R102, Ra and Rb are the same as above.

[0030] Preferably, with the proviso that L4 is a single bond, O, or one of the following structures:

[0031] JPEG0007624066000006.jpg58170

[0032] however, * indicates the connection position between formula (1) and formula (2),

[0033] The number of Rx represents a range from no substitution to the maximum substitution number. When Rx is polysubstituted, two adjacent substituents can be connected to each other to form a cyclic structure or a double-ring structure.

[0034] Rx and Ry are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C30 alkylsilyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 arylsilyl, substituted or unsubstituted C0-C20 amino; Nitriles, Isonitriles and phosphino.

[0035] Preferably, with the proviso that R1, R2, R7, R8, R10, R11, R18, R101, R102, Ra, Rb, Rx, and Ry are individually selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C8 heteroalkyl, substituted or unsubstituted C7-C10 aralkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C8 alkylsilyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C10 heteroaryl, substituted or unsubstituted C3-C10 arylsilyl, substituted or unsubstituted C0-C6 amino, and cyano.

[0036] Preferably, with the caveat that R1, R2, R7, R8, R10, R11, R18, R101, R102, Ra, Rb, Rx, and Ry are individually selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C8 heteroalkyl, substituted or unsubstituted phenylalkyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C10 heteroaryl.

[0037] Preferably, however, R18 is deuterium, a substituted or unsubstituted straight chain carbon atom C1-C4 alkyl, a substituted or unsubstituted C1-C6 cycloalkyl, and the substitution is with deuterium, halogen.

[0038] Preferably, however, at least one of R1 and R2 is not hydrogen.

[0039] Preferred metal complexes preferably have one of the following structural formulas:

[0040] JPEG0007624066000007.jpg255147JPEG0007624066000008.jpg255152JPEG0007624066000009.jpg255143JPEG0007624066000010.jpg255153 JPEG0007624066000011.jpg255144JPEG0007624066000012.jpg255143JPEG0007624066000013.jpg255159JPEG0007624066000014.jpg221170

[0041] The precursor of the metal complex has the following structure: JPEG0007624066000015.jpg90153

[0042] However, at least one of R1 to R18 is a structure represented by formula (2), JPEG0007624066000016.jpg56117

[0043] However, the definitions of R1 to R18, R101 and R102 are the same as above.

[0044] An object of the present invention is to provide an electroluminescence device comprising: a cathode; an anode; and an organic layer provided between the cathode and the anode, at least one of the organic layers containing a metal complex.

[0045] Another object of the present invention is to provide an electroluminescence device in which the organic layer includes a light-emitting layer, and the metal complex is used as a material in the light-emitting layer, particularly as a green light-emitting material.

[0046] Another object of the present invention is to provide an electroluminescent device, wherein the organic layer comprises a hole injection layer, and the metal complex is a material in the hole injection layer. Effect of the Invention

[0047] As can be seen from the results of the device, the compound according to the present invention has advantages such as high optical and electrochemical stability, high color saturation and luminous efficiency, and long device life, and can be used in organic electroluminescence devices. In particular, it has the potential to be used in the OLED industry as a green-emitting dopant. [Brief description of the drawings]

[0048] [Figure 1] FIG. 1 is the HNMR spectrum of compound A39. [Diagram 2] FIG. 2 is the HNMR spectrum of compound A82. [Diagram 3] FIG. 3 shows the UV / PL spectrum of compound A39. [Figure 4] FIG. 4 shows the UV / PL spectrum of compound A82. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0049] The described examples are merely for the purpose of making the technical invention easier to understand, and should not be regarded as specific limitations on the present invention.

[0050] All raw materials and solvents for the synthesis of the compounds of the present invention are purchased from suppliers well known to those skilled in the art, such as Alfa, Acros, etc.

[0051] Example 1 Synthesis of Compound A1 Synthesis of intermediate A1-6

[0052] JPEG0007624066000017.jpg53170

[0053] Synthesis of Compound A1-2 A1-1 (120g, 0.6mol, 1.0eq), iodine (168.3g, 0.6mol, 1.0eq), and pyridine (600ml) were sequentially placed in a 1L single-neck flask, evacuated and replaced with nitrogen three times, heated to reflux, and left overnight. A large amount of solid precipitated during the reaction, and the temperature was lowered to room temperature and filtered. The filter cake was washed twice with methanol, with a total of 200ml, and after draining, the solid was thermally slurried twice with methanol, with 200ml each time. The solid was collected and dried to obtain a whitish solid A1-2 (207.3g, 85.1% yield). Mass spectrum: 405.0 (M+H)

[0054] Synthesis of Compound A1-4 A1-3 (96g, 0.63mol, 1.0eq), benzaldehyde (74.6g, 0.7mol, 1.1eq), potassium hydroxide (179.3g, 3.2mol, 4.0eq), deionized water (195ml), and methanol (670ml) are sequentially placed in a 3L three-neck flask, purged with vacuum and nitrogen three times, heated to 50℃, and left overnight. A large amount of solid precipitates during the reaction, and the temperature is lowered to room temperature and filtered. The solid is collected and placed in ethyl acetate (500ml), stirred to dissolve, and washed twice with deionized water, each time with 200ml. The organic phase is concentrated until only a small amount remains, and methanol (250ml) is added to make a slurry, which is purified by suction and filtration. The filter cake is collected and dried to obtain a white solid A1-4 (93.5g, 61.4% yield). Mass spectrum: 239.2 (M+H)

[0055] Synthesis of Compound A1-5 A1-4 (80g, 0.33mol, 1.0eq), A1-2 (135.6g, 0.33mol, 1.0eq), ammonium acetate (155.2g, 2.0mol, 6.0eq), and acetic acid (350ml) are added in order to a 1L three-neck flask, purged with vacuum and nitrogen three times, heated to reflux and left overnight. The temperature is lowered to room temperature and concentrated to remove acetic acid, and dichloromethane (1.0L) is added to the rotary dried solid, stirred to dissolve, and deionized water is added and washed twice, with 300ml each time. The organic phase is concentrated until only a small amount remains, and methanol (250ml) is added for crystallization and purification, suction and filtration are performed, and the solid is collected and thermally slurried twice with methanol (300ml). Drying gives a white solid A1-5 (119.6g, 85.6% yield). Mass spectrum: 417.3 (M+H)

[0056] Synthesis of Compound A1-6 Compound A1-5 (110.0g, 0.260mol, 1.0eq), pinacol diboronate (80.5g, 0.31mol, 1.2eq), [1,1'-bis(diphenylphosphinoyl)ferrocene]palladium dichloride (3.87g, 5.28mmol, 0.02eq), potassium acetate (51.8g, 0.52mol, 2.0eq), and dioxane (900ml) were sequentially placed in a 1L single-neck flask, purged with nitrogen three times, heated to 100℃, kept warm and stirred for 6h, and TLC monitoring (developing solvent: ethyl acetate / n-hexane = 1 / 10) was performed to show that the reaction of raw material A1-5 was essentially complete. The reaction mixture was cooled to 40°C, filtered through diatomaceous earth, the filter cake was washed with a small amount of dioxane, the filtrate was concentrated under reduced pressure to 200ml, methanol (400ml) was added, stirred at room temperature for 2h, and filtered to obtain a solid. The solid was recrystallized twice from tetrahydrofuran / methanol (100ml / 200ml), filtered, and dried to obtain off-white solid compound A1-6 (84.1g, 68.7% yield). Mass spectrum: 464.3 (M+H).

[0057] Synthesis of Compound A1 JPEG0007624066000018.jpg86170

[0058] Synthesis of Compound A1-7 Compound A1-6 (75.0g, 0.16mol, 1.0eq), 2,4-dichloro-6-methylpyridine (39.3g, 0.24mol, 1.5eq), tetrakis(triphenylphosphine)palladium (9.35g, 8.09mmol, 0.05eq), sodium hydroxide (51.8g, 0.52mol, 3.0eq), dioxane (650ml), and deionized water (130ml) were sequentially charged into a 3L three-neck flask, purged with nitrogen three times, heated to 70℃, kept warm and stirred for 6h, and TLC monitoring (developing solvent: ethyl acetate / n-hexane=1 / 10) was performed to show that the reaction of raw material A1-6 was essentially complete. The reaction solution is cooled to room temperature, and dichloromethane (300 mL) and deionized water (300 mL) are added to the system, and the organic phase silica gel is extracted and collected. The silica gel is washed with dichloromethane (200 mL), and the filtrate is spun dry to obtain a solid. The solid is recrystallized three times in toluene (150 ml) / methanol (350 ml) and dried to obtain white solid compound A1-7 (54.1 g, 72.3% yield). Mass spectrum: 464.0 (M+H).

[0059] Synthesis of Compound A1-8 Compound A1-7 (10.5g, 22.6mmol, 1.0eq), dibenzofuran-4-boronic acid (7.2g, 34.0mmol, 1.5eq), dichloro-di-tert-butyl-(4-dimethylaminophenyl)phosphopalladium(II) (0.24g, 0.34mmol, 0.015eq), tripotassium phosphate (9.63g, 45.3mmol, 2.0eq), dioxane (300ml), and deionized water (100ml) were sequentially charged into a 1L three-neck flask, purged with nitrogen three times, heated to 60℃, kept warm and stirred for 3h, and monitored by TLC (developing solvent: ethyl acetate / n-hexane=1 / 20). The reaction of raw material A1-7 was essentially complete. The reaction mixture is cooled to room temperature, dichloromethane (200 mL) and deionized water (100 mL) are added to the system, and the organic phase is extracted and collected, spun dry, and purified by column chromatography (eluent: ethyl acetate / n-hexane = 1 / 40) and dried to obtain compound A1-8 (10.6 g, yield 79.1%) as a white solid. Mass spectrum: 595.7 (M+H).

[0060] Synthesis of Compound A1-9 A1-8 (10.6g, 17.8mmol, 1.0eq) and pyridine hydrochloride (98.8g, 0.85mol, 48eq) are added to a 500mL single-neck flask, and dichlorobenzene (24ml) is added and stirred. The mixture is purged with nitrogen three times, and the temperature is raised to 190°C. After reacting for 2.5h, TLC monitoring (eluent: ethyl acetate / n-hexane = 1 / 3) is performed. The raw materials are reacted to completion, and the reaction is cooled to room temperature. Saturated sodium bicarbonate solution (120ml) and toluene (120ml) are added to the reaction and stirred to dissolve and separate the liquid. The organic phase is washed with water twice (150ml each time), and the organic phase is collected and dried by rotary drying. The crude product is purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1 / 20) and dried to obtain a yellow solid A1-9 (8.33g, 80.5% yield). Mass spectrum: 581.2 (M+H).

[0061] Synthesis of Compound A1 A1-9 (6.5g, 11.19mmol, 1.0eq), potassium chloroplatinate (8.11g, 17.35mmol, 1.55eq), tetrabutylammonium bromide (541mg, 1.68mmol, 0.15eq), and acetic acid (650ml) are placed in a 1L single-neck flask, purged with vacuum and nitrogen three times, heated to 125℃ under nitrogen protection, and reacted for 72h. TLC monitoring (developing solvent: dichloromethane / n-hexane = 1 / 2) is performed, and the reaction of raw material A1-9 is completed. The reaction is cooled to room temperature. The reaction liquid is placed in a beaker containing deionized water (650ml) and stirred to precipitate a solid, which is then collected by filtration. The crude product was subjected to silica gel column chromatography (eluent: dichloromethane / n-hexane=1 / 8) to obtain an orange-yellow solid, which was recrystallized in one batch from dichloromethane (60 ml) / methanol (80 ml) to obtain orange-yellow compound A1 (5.23 g, 60.3% yield). After sublimation and purification of 5.23 g of the crude product of A1, sublimated pure A1 (3.64 g, 69.5% yield) was obtained. Mass spectrum: 774.2 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.65(s,1H),8.44(s,1H),8.23(d,J=30.0Hz,4H),8.12-7.94(m,3H),7.72(d,J=25.0Hz,3H),7.58-7.22(m,10H),6.97(s,1H),3.27(s,3H).

[0062] Example 2 Synthesis of Compound A3 JPEG0007624066000019.jpg136170

[0063] Synthesis of compound A3-2 Refer to the synthesis process and post-treatment purification method of compound A1-8, just change the corresponding raw materials. Mass spectrum: 671.8 (M+H).

[0064] Synthesis of compound A3-3 Refer to the synthesis process and post-treatment purification method of compound A1-9, just change the corresponding raw materials. Mass spectrum: 657.8 (M+H).

[0065] Synthesis of compound A3 Referring to the synthesis process and post-treatment purification method of compound A1, only changing the corresponding raw materials, orange-yellow compound A3 (4.66g, yield 59.4%) is obtained. After sublimation and purification of 4.66g of crude A3, sublimated pure A3 (2.91g, yield 61.4%) is obtained. Mass spectrum: 850.8 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.64(s,1H),8.42(s,1H),8.24(d,J=30.0Hz,4H),8.05(d,J=30.0Hz,4H),7.72(d, J=25.0Hz,3H),7.59-7.34(m,11H),7.29(d,J=5.0Hz,2H),6.98(s,1H),3.28(s,3H).

[0066] Example 3 Synthesis of Compound A28 Synthesis of intermediate A28-4

[0067] JPEG0007624066000020.jpg37170Synthesis of compound A28-2 Refer to the synthesis process and post-treatment purification method of compound A1-4, only change the corresponding raw materials. Mass spectrum: 257.3 (M+H).

[0068] Synthesis of compound A28-3 Refer to the synthesis process and post-treatment purification method of compound A1-5, just change the corresponding raw materials. Mass spectrum: 435.3 (M+H).

[0069] Synthesis of compound A28-4 Refer to the synthesis process and post-treatment purification method of compound A1-5, just change the corresponding raw materials. Mass spectrum: 482.4 (M+H).

[0070] Synthesis of compound A28 JPEG0007624066000021.jpg92170

[0071] Synthesis of compound A28-5 Refer to the synthesis process and post-treatment purification method of compound A1-7, only change the corresponding raw materials. Mass spectrum: 482.0 (M+H).

[0072] Synthesis of compound A28-6 Refer to the synthesis process and post-treatment purification method of compound A1-8, only change the corresponding raw materials. Mass spectrum: 595.7 (M+H).

[0073] Synthesis of compound A28-9 Refer to the synthesis process and post-treatment purification method of compound A1-9, only change the corresponding raw materials. Mass spectrum: 599.7 (M+H).

[0074] Synthesis of compound A28

[0075] Referring to the synthesis process and post-treatment purification method of compound A1, only the corresponding raw materials need to be changed, and deuterated acetic acid is used as the reaction solvent to obtain orange-yellow compound A28 (4.24 g, yield 64.1%). After sublimation and purification of 4.24 g of the crude A28, sublimated pure A28 (2.64 g, yield 62.2%) is obtained. Mass spectrum: 871.8 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.43(d,J=10.0Hz,2H),8.23(d,J=30.0Hz,4H),8.05(d,J=30.0Hz,4H),7.72(d,J=25.0Hz,3H),7.57-7.34(m,11H),7.09(d,J=35.0Hz,2H).

[0076] Example 4 Synthesis of Compound A39 Synthesis of intermediate A39-3

[0077] JPEG0007624066000022.jpg38170

[0078] Synthesis of compound A39-1 Refer to the synthesis process and post-treatment purification method of compound A1-4, only change the corresponding raw materials. Mass spectrum: 257.3 (M+H).

[0079] Synthesis of compound A39-2 Refer to the synthesis process and post-treatment purification method of compound A1-5, just change the corresponding raw materials. Mass spectrum: 435.3 (M+H).

[0080] Synthesis of compound A39-3 Refer to the synthesis process and post-treatment purification method of compound A1-5, just change the corresponding raw materials. Mass spectrum: 482.4 (M+H).

[0081] Synthesis of compound A39 JPEG0007624066000023.jpg108170

[0082] Synthesis of compound A39-4 Refer to the synthesis process and post-treatment purification method of compound A1-7, only change the corresponding raw materials. Mass spectrum: 576.2 (M+H).

[0083] Synthesis of compound A39-5 Refer to the synthesis process and post-treatment purification method of compound A1-8, only change the corresponding raw materials. Mass spectrum: 784.0 (M+H).

[0084] Synthesis of compound A39-6 Refer to the synthesis process and post-treatment purification method of compound A1-9, only change the corresponding raw materials. Mass spectrum: 770.0 (M+H).

[0085] Synthesis of compound A39 Referring to the synthesis process and post-treatment purification method of compound A1, only the corresponding raw materials need to be changed, and deuterated acetic acid is used as the reaction solvent to obtain orange-yellow compound A39 (4.37 g, yield 67.4%). After sublimation and purification of 4.37 g of the crude A39, sublimated pure A39 (2.66 g, yield 60.8%) is obtained. Mass spectrum: 963.0 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.22(d,J=15.9Hz,2H),7.98(dt,J=15.0,7.3Hz,5H),7.84-7.65(m,5H),7.64-7.3 1(m,11H),7.18(t,J=7.8Hz,1H),6.69(t,1H),3.28(s,3H),1.52(d,J=44.0Hz,18H).

[0086] Example 5 Synthesis of Compound A71 JPEG0007624066000024.jpg38170

[0087] Synthesis of compound A71-2 Refer to the synthesis process and post-treatment purification method of compound A1-8, only change the corresponding raw materials. Mass spectrum: 687.9 (M+H).

[0088] Synthesis of compound A71-3 Refer to the synthesis process and post-treatment purification method of compound A1-9, just change the corresponding raw materials. Mass spectrum: 672.8 (M+H).

[0089] Synthesis of compound A71 Referring to the synthesis process and post-treatment purification method of compound A1, if only the corresponding raw materials are changed, orange-yellow compound A71 (4.37g, yield 56.2%) can be obtained. After sublimation and purification of 4.37g of crude product A71, sublimated pure A71 (2.4g, yield 54.9%) is obtained. Mass spectrum: 866.9 (M+H). 1 H NMR (400 MHz, CDCl 3)δ8.63(s,1H),8.53(s,2H),8.41(s,1H),8.37-8.17(m,6H),7.72(d,J=25.0H z,3H)),7.55-7.37(m,11H),7.29(d,J=5.0Hz,2H),7.01(s,1H),3.28(s,3H).

[0090] Example 6 Synthesis of Compound A82 JPEG0007624066000025.jpg41170

[0091] Synthesis of compound A82-1 Refer to the synthesis process and post-treatment purification method of compound A1-8, only change the corresponding raw materials. Mass spectrum: 724.0 (M+H).

[0092] Synthesis of compound A82-2 Refer to the synthesis process and post-treatment purification method of compound A1-9, only change the corresponding raw materials. Mass spectrum: 710.0 (M+H).

[0093] Synthesis of compound A82 Referring to the synthesis process and post-treatment purification method of compound A1, if only the corresponding raw materials are changed, orange-yellow compound A82 (3.97g, 63.7% yield) can be obtained. After sublimation and purification of 3.97g of A82 crude product, sublimated pure A82 (2.58g, 64.9% yield) is obtained. Mass spectrum: 903.0 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.22(s,1H),8.18(d,J=5.9Hz,2H),7.98(d,J=7.7Hz,1H),7.88(s,1H),7.85-7.78(m,1H),7.71-7.41(m,10H) ,7.39-7.32(m,1H),7.31-7.23(m,2H),7.19(t,J=7.6Hz,1H),6.67(t,J=6.8Hz,1H),3.27(s,3H),1.59(s,18H).

[0094] Example 7 Synthesis of Compound A89 JPEG0007624066000026.jpg102170

[0095] Synthesis of compound A89-2 Refer to the synthesis process and post-treatment purification method of compound A1-8, only change the corresponding raw materials. Mass spectrum: 645.8 (M+H).

[0096] Synthesis of compound A89-3 Refer to the synthesis process and post-treatment purification method of compound A1-9, only change the corresponding raw materials. Mass spectrum: 631.7 (M+H).

[0097] Synthesis of compound A89 Referring to the synthesis process and post-treatment purification method of compound A1, if only the corresponding raw materials are changed, orange-yellow compound A89 (3.57g, yield 56.7%) can be obtained. After sublimation and purification of 3.57g of A89 crude product, sublimated pure A89 (2.16g, yield 60.5%) is obtained. Mass spectrum: 824.8 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.66(s,1H),8.45(s,1H),8.24(d,J=30.0Hz,4H),8.13-7.95(m,3H),7.73(d,J=25.0Hz,3H),7.58-7.22(m,10H),6.99(s,1H),3.28(s,3H).

[0098] Example 8 Synthesis of Compound A100 JPEG0007624066000027.jpg92170

[0099] Synthesis of compound A100-2 Refer to the synthesis process and post-treatment purification method of compound A1-8, only change the corresponding raw materials. Mass spectrum: 858.1 (M+H).

[0100] Synthesis of compound A100-3 Refer to the synthesis process and post-treatment purification method of compound A1-9, only change the corresponding raw materials. Mass spectrum: 844.1 (M+H).

[0101] Synthesis of compound A100 Referring to the synthesis process and post-treatment purification method of compound A1, if only the corresponding raw materials are changed, orange-yellow compound A100 (4.12g, yield 58.8%) can be obtained. After sublimation and purification of 4.12g of A100 crude product, sublimated pure A100 (2.59g, yield 62.86%) is obtained. Mass spectrum: 1037.2 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.66(s,1H),8.44(s,1H),8.22(d,J=30.0Hz,4H),8.11(s,1H),7.90(s,1H),7.83-7.66(m,4H ),7.54-7.38(m,4H),7.37-7.14(m,10H),7.10(s,4H),6.99(s,1H),3.28(s,3H),1.60(s,18H).

[0102] Example 9 Synthesis of Compound A111 JPEG0007624066000028.jpg108170

[0103] Synthesis of compound A111-1 Refer to the synthesis process and post-treatment purification method of compound A1-6, only change the corresponding raw materials. Mass spectrum: 555.5 (M+H).

[0104] Synthesis of compound A111-2 Compound A111-1 (11.5g, 20.7mmol, 1.0eq), 2,5-dibromofuran (7.03g, 31.1mmol, 1.5eq), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (0.3g, 0.41mmol, 0.02eq), potassium carbonate (5.73g, 41.8mmol, 2.0eq), toluene (115ml), ethanol (25ml), and deionized water (25ml) were sequentially charged into a 500ml three-neck flask, purged with nitrogen three times, heated to 65℃, kept warm and stirred for 6h, and TLC monitoring (developing solvent: dichloromethane / n-hexane=1 / 15) was performed, and the reaction of raw material A111-1 was basically completed. The reaction mixture was cooled to room temperature, dichloromethane (150 mL) and deionized water (100 mL) were added to the system, and the organic phase was extracted and collected, spun dry, and the crude product was subjected to silica gel column chromatography (eluent: dichloromethane / n-hexane = 1 / 40) to obtain orange off-white solid A111-2 (7.46 g, 62.7% yield). Mass spectrum: 574.5 (M+H).

[0105] Synthesis of compound A111-4 Refer to the synthesis process and post-treatment purification method of compound A1-8, only change the corresponding raw materials. Mass spectrum: 745.9 (M+H).

[0106] Synthesis of compound A111-5 Refer to the synthesis process and post-treatment purification method of compound A1-9, only change the corresponding raw materials. Mass spectrum: 731.7 (M+H).

[0107] Synthesis of compound A111 Referring to the synthesis process and post-treatment purification method of compound A1, if only the corresponding raw materials are changed, orange-yellow compound A111 (3.75g, 61.1% yield) can be obtained. After sublimation and purification of 3.75g of A111 crude product, sublimated pure A111 (2.17g, 57.8% yield) is obtained. Mass spectrum: 916.9 (M+H). 1 H NMR (400 MHz, CDCl 3)δ8.65(s,1H),8.32-8.17(m,5H),8.05(d,J=30.0Hz,2H),7.81-7.66(m,5H),7. 62-7.37(m,11H),7.29(d,J=5.0Hz,2H),7.05(s,2H),6.99(s,1H),3.28(s,3H).

[0108] Example 10 Synthesis of Compound A125 JPEG0007624066000029.jpg97170

[0109] Synthesis of compound A125-2 Refer to the synthesis process and post-treatment purification method of compound A111-2, only change the corresponding raw materials. Mass spectrum: 624.5 (M+H).

[0110] Synthesis of compound A125-3 Refer to the synthesis process and post-treatment purification method of compound A1-8, only change the corresponding raw materials. Mass spectrum: 711.8 (M+H).

[0111] Synthesis of compound A125-4 Refer to the synthesis process and post-treatment purification method of compound A1-8, only change the corresponding raw materials. Mass spectrum: 697.8 (M+H).

[0112] Synthesis of compound A125 Referring to the synthesis process and post-treatment purification method of compound A1, if only the corresponding raw materials are changed, orange-yellow compound A125 (3.93 g, yield 59.3%) can be obtained. After sublimation and purification of 3.93 g of A125 crude product, sublimated pure A125 (2.28 g, yield 58.0%) is obtained. Mass spectrum: 890.9 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.64(s,1H),8.32-8.17(m,5H),7.98(s,2H),7.81-7.67(m,6H),7.61-7.45(m,5H)),7.46-7.24(m,8H),6.98(s,1H),3.27(s,3H).

[0113] Example 11 Synthesis of Compound A168 JPEG0007624066000030.jpg68170

[0114] Synthesis of compound A168-1 Refer to the synthesis process and post-treatment purification method of compound A111-2, only change the corresponding raw materials. Mass spectrum: 590.5 (M+H).

[0115] Synthesis of compound A168-2 Refer to the synthesis process and post-treatment purification method of compound A1-8, only change the corresponding raw materials. Mass spectrum: 826.0 (M+H).

[0116] Synthesis of compound A168-3 Refer to the synthesis process and post-treatment purification method of compound A1-8, only change the corresponding raw materials. Mass spectrum: 811.0 (M+H).

[0117] Synthesis of compound A168 Referring to the synthesis process and post-treatment purification method of compound A1, if only the corresponding raw materials are changed, orange-yellow compound A168 (4.22g, yield 63.1%) can be obtained. After sublimation and purification of 4.22g of A168 crude product, sublimated pure A168 (2.69g, yield 63.7%) is obtained. Mass spectrum: 1005.1 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.66(s,1H),8.31-8.18(m,5H),8.09(s,1H),7.90(d,J=5.0Hz,6H),7.82-7.65(m,5H),7.54-7.18(m,14H),6.99(s,1H),3.28(s,3H).

[0118] Example 12 Synthesis of Compound A197 JPEG0007624066000031.jpg82170

[0119] Synthesis of compound A197-2 Refer to the synthesis process and post-treatment purification method of compound A111-2, only change the corresponding raw materials. Mass spectrum: 637.6 (M+H).

[0120] Synthesis of compound A197-3 Refer to the synthesis process and post-treatment purification method of compound A1-8, only change the corresponding raw materials. Mass spectrum: 724.9 (M+H).

[0121] Synthesis of compound A197-4 Refer to the synthesis process and post-treatment purification method of compound A1-8, only change the corresponding raw materials. Mass spectrum: 710.8 (M+H).

[0122] Synthesis of compound A197 Referring to the synthesis process and post-treatment purification method of compound A1, if only the corresponding raw materials are changed, orange-yellow compound A197 (3.67g, yield 55.8%) can be obtained. After sublimation and purification of 3.67g of A197 crude product, sublimated pure A197 (2.08g, yield 56.6%) is obtained. Mass spectrum: 903.9 (M+H). 1 H NMR (400 MHz, CDCl 3 )δ8.67(s,1H),8.33-8.17(m,5H),7.98(s,1H),7.75(dd,J=30.0,15.0Hz, 6H),7.61-7.23(m,12H),7.01(d,J=45.0Hz,2H),3.82(s,3H),3.27(s,3H).

[0123] Usage example: Fabrication of organic electroluminescence elements A 50mm x 50mm x 1.0mm glass substrate with an ITO (100nm) transparent electrode is ultrasonically cleaned in ethanol for 10 minutes, dried at 150 degrees, and then treated with N2Plasma for 30 minutes. The cleaned glass substrate is attached to a substrate bracket of a vacuum deposition device, and a compound HATCN is first evaporated on one side of the transparent electrode wire so as to cover the transparent electrode, forming a thin film with a thickness of 5nm, and a layer of HTM1 is evaporated to form a thin film with a thickness of 60nm, and a layer of HTM2 is evaporated on the HTM1 thin film to form a thin film with a thickness of 10nm, and a main material 1, a main material 2, and a dopant compound (comparative compound X, CPDX) are evaporated on the HTM2 film layer by co-evaporation mode, where the thickness is 30nm and the ratio of the main material to the dopant material is 45%:45%:10%. An ETL film layer (25 nm) and an LiQ film layer (1 nm) are deposited in this order on the light-emitting layer, and finally, a layer of metallic Al (100 nm) is deposited as an electrode.

[0124] JPEG0007624066000032.jpg122170

[0125] evaluation: The above-mentioned element is subjected to an element performance test, and in each example and comparative example, a constant current source (Keithley2400) is used to pass a fixed current density through the light-emitting member, and the emission spectrum is tested using a spectroradiometer (CS2000). In addition, the voltage value and the time (LT90) at which the test luminance becomes 90% of the initial luminance are measured. The results are as follows.

[0126] Table 0001 JPEG0007624066000033.jpg87170

[0127] As can be seen from comparing the data in the above table, the organic electroluminescent device using the compound according to the present invention as a green light dopant has superior performance in terms of driving voltage, luminous efficiency and device life compared to the comparative compound. [Industrial Applicability]

[0128] As can be seen from the above results, the compound according to the present invention has advantages such as high optical and electrochemical stability, high saturation, high luminous efficiency, and long device life, and can be used in organic electroluminescence devices. In particular, as a green-emitting dopant, it can be used in the OLED industry.

Claims

1. A metal complex represented by the following formula (4): In formula (4), X is O, S, Se or CRaRb; L4 is selected from a single bond, O, substituted or unsubstituted C1-C10 alkylene, substituted or unsubstituted C3-C10 cycloalkylene, substituted or unsubstituted C7-C20 aralkylene, substituted or unsubstituted C2-C20 alkenylene, substituted or unsubstituted C3-C30 alkylenesilyl, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene, and substituted or unsubstituted C3-C30 arylenesilyl; R1, R2, R7, R8, R10, R11, R18, R101, R102, Ra and Rb are each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C30 alkylsilyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 arylsilyl, substituted or unsubstituted C0-C20 amino, nitrile, isonitrile, and phosphino; The substitution is selected from the group consisting of deuterium, halogen, C1-C4 alkyl, and cyano; The number of substitutions of R101 and R102 is independently any number from no substitution to the maximum number of substitutions. A metal complex comprising:

2. 2. The metal complex according to claim 1, wherein L4 is any one selected from the group consisting of a single bond, O, and structures represented by the following formulas (a) to (l). (In the above formula, * indicates the connection position between formula (1) and formula (2), The number of Rx's ranges from no substitution to the maximum number of substitutions; When Rx is polysubstituted, two adjacent substituents are connected to each other to form a cyclic or bicyclic structure; Rx and Ry are each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C30 alkylsilyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 arylsilyl, substituted or unsubstituted C0-C20 amino, nitrile, isonitrile, and phosphino.

3. R1, R2, R7, R8, R10, R11, R18, R101, R102, Ra, Rb, Rx, and Ry are each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C7-C10 aralkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C8 alkylsilyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C3-C10 heteroaryl, substituted or unsubstituted C3-C10 arylsilyl, and substituted or unsubstituted C0-C6 amino, cyano; The metal complex according to claim 2 .

4. R1, R2, R7, R8, R10, R11, R18, R101, R102, Ra, Rb, Rx, and Ry are each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted phenylalkyl, substituted or unsubstituted C6-C10 aryl, and substituted or unsubstituted C3-C10 heteroaryl; The metal complex according to claim 3 .

5. R18 is selected from the group consisting of deuterium, substituted or unsubstituted straight chain carbon atom C1-C4 alkyl, and substituted or unsubstituted C1-C6 cycloalkyl, wherein the substitution is with deuterium or halogen; 5. The metal complex according to claim 4 .

6. At least one of R1 and R2 is not hydrogen; The metal complex according to claim 5 .

7. 3. The metal complex of claim 2, wherein L4 is a single bond or one selected from the following structures: (In the formula, * represents the connection position between formula (1) and formula (2), The number of Rx's ranges from no substitution to the maximum number of substitutions; When Rx is polysubstituted, two adjacent substituents are connected to each other to form a cyclic or bicyclic structure; Rx is independently hydrogen, deuterium, halogen, substituted or unsubstituted C1-C20 alkyl, nitrile, isonitrile, or phosphino; Ry is independently a substituted or unsubstituted C1 to C20 alkyl, a substituted or unsubstituted C3 to C30 cycloalkyl, a substituted or unsubstituted C7 to C30 aralkyl, a substituted or unsubstituted C6 to C30 aryl, or a substituted or unsubstituted C3 to C30 heteroaryl.

8. A metal complex, characterized in that it is a compound of one of the following structural formulas:

9. An electroluminescent device, A cathode; An anode; and an organic layer provided between the cathode and the anode, at least one layer of which contains the metal complex according to any one of claims 1 to 8. An electroluminescence element comprising:

10. the organic layer includes an emissive layer, and the metal complex is a green emissive material in the emissive layer; or the organic layer includes a vacancy injection layer, and the metal complex is a vacancy injection material of the vacancy injection layer; 10. The electroluminescence device according to claim 9.

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