Green phosphorescent doped material as well as preparation method and application thereof

Abstract

According to the green phosphorescent doped material, the preparation method thereof and the application of the green phosphorescent doped material in an organic electroluminescent device, a platinum-containing ONCN tetradentate ligand structure is introduced into the structure of the phosphorescent doped material, so that the stability of a compound can be effectively improved, and a tetramethyl-substituted cyclohexane acene structure is further connected, so that the stability of the compound is improved. The tetramethyl-substituted cycloalkyl phenyl structure has a hyperconjugation effect, the structure is more stereoscopic in space, the tetramethyl-substituted cycloalkyl phenyl structure can be used as a steric hindrance structure, aggregation quenching can be reduced, the electron mobility in the whole structure can be enhanced, close packing between molecules can be effectively prevented, and the concentration of excitons can be effectively reduced; and more efficient energy transmission can be realized, so that the luminous efficiency and the service life of the organic light-emitting device are improved and prolonged, and meanwhile, relatively low driving voltage can be maintained.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic electroluminescence, and in particular, it relates to a green phosphorescent dopant material, a preparation method thereof, and applications thereof in an organic electroluminescence device and an organic electroluminescence apparatus. BACKGROUND

[0002] In the field of OLED materials, the development of phosphorescent OLED light-emitting layer dopant materials is relatively rapid and mature, which is mainly based on some heavy metal organic complexes. The electronic absorption of metal complexes is in the ultraviolet region, and the electron emission is in the visible light region, which can be used as excellent light-emitting materials. Phosphorescent materials have strong spin-orbit coupling, and the energy of singlet and triplet excitons can be fully utilized in the luminescence process, so theoretically its quantum efficiency can reach 100%. Metal complex luminescent materials have been applied in industry, and traditional industrialized phosphorescent OLED light-emitting layer dopant materials are mainly based on iridium complexes. However, metal platinum has a natural advantage over iridium in terms of price, and its complex has excellent material stability due to its planarity, which has also been greatly developed in recent years. In recent years, metal platinum complexes have shown properties that surpass iridium complexes, but their performance, such as luminous efficiency and service life, still needs to be improved. Therefore, there is an urgent need for high-efficiency and long-service-life luminescent materials in the industry.

[0003] Among them, the platinum complex molecule of ONCN tetradentate ligand has simple synthesis steps, many modifiable sites, and great improvement space. The tetramethyl-substituted cycloalkyl and benzene structure has a superconjugation effect, and the combination of the two can well solve the problems of material efficiency and service life. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application aims to provide a phosphorescent dopant material applied in a green device, a preparation method and application thereof. The device prepared by the material has the advantages of high luminous efficiency, long service life, and low driving voltage.

[0005] By introducing the ONCN tetradentate ligand structure containing platinum, the stability of the compound can be effectively improved, and then the tetramethyl-substituted cyclohexane and benzene structure is connected to the whole molecular structure. The tetramethyl-substituted cycloalkyl and benzene structure has a superconjugation effect, and its structure is more three-dimensional in space. As a steric hindrance structure, it can reduce the aggregation quenching, enhance the electron flow in the whole structure, prevent the close packing of molecules and reduce the concentration of excitons, and achieve more efficient energy transmission. In addition, the luminous efficiency and service life of the organic electroluminescence device are improved, and the driving voltage is also kept low.

[0006] To achieve the above objectives, according to one aspect of the present invention, a phosphorescent doping material for use in green light devices is provided, the phosphorescent doping material having the general structural formula as shown in Chemical Formula I:

[0007]

[0008] R1 is independently selected from hydrogen, deuterium, halogen group, cyano group, TMS, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C6-C 18 aryl;

[0009] R2 is independently selected from hydrogen, deuterium, halogen group, cyano group, TMS, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C6-C 18 aryl;

[0010] R3 is independently selected from hydrogen, deuterium, halogen group, cyano group, TMS, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C6-C 18 aryl;

[0011] A is independently selected from hydrogen, deuterium, halogen group, cyano group, TMS, substituted or unsubstituted C1-C. 20 Alkyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C6-C 30 One of the heteroaryl groups, wherein the heteroatom contains at least one of O, S, N, Si, or Se, and the structure...

[0012] B is independently selected from substituted or unsubstituted C6-C. 30 aryl, substituted or unsubstituted C6-C 30 One of the heteroaryl groups, wherein the heteroatom contains at least one of O, S, N, Si, or Se, and the structure...

[0013] And at least one of A and B contains a structure

[0014] n1 and n2 are integers independently selected from 0, 1, 2, and 3, respectively;

[0015] n3 is an integer independently selected from 0, 1, 2, 3, and 4.

[0016]

[0017] More preferably, R1 is independently selected from hydrogen, substituted or unsubstituted C1-C6 alkyl groups; substituted or unsubstituted phenyl groups, substituted or unsubstituted biphenyl groups;

[0018] It is further preferred that R2is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, TMS, substituted or unsubstituted C1-C6alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl;

[0019] It is further preferred that R3is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, TMS, substituted or unsubstituted C1-C6alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl;

[0020] It is further preferred that A is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, TMS, substituted or unsubstituted C1-C6alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 9,9-dimethylfluorene group, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted dibenzothiophene group, and the structure

[0021] It is further preferred that B is independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 9,9-dimethylfluorene group, substituted or unsubstituted furan group, substituted or unsubstituted thiophene group, and the structure

[0022] It is further preferred that R1, R2, R3are independently selected from the group consisting of hydrogen and the following structures:

[0023]

[0024] wherein R4-R9may be independently selected from F, CF3, CN, TMS, and one of the following alkyl groups:

[0025]

[0026] wherein n4, n5, n7, n9are independently selected from the group consisting of 0, 1, 2, 3, 4, 5 integers;

[0027] wherein n6, n8are independently selected from the group consisting of 0, 1, 2, 3, 4 integers;

[0028] It is further preferred that A is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, TMS, and one of the following structures:

[0029]

[0030] B is independently selected from the following structures:

[0031]

[0032] wherein R 10 , R 11 may be selected from F, CF3, CN, TMS and one of the following alkyl groups, respectively:

[0033]

[0034] wherein n10 is independently selected from an integer of 0, 1, 2, 3, 4, 5, 6, 7, respectively;

[0035] wherein n11 is independently selected from an integer of 0, 1, 2, 3, 4;

[0036] The above-mentioned alkyl groups can be deuterated, respectively;

[0037] The above-mentioned * in the formulae represent the connection points;

[0038] The term "substituted" in the term "substituted" in the present application is selected from deuterium, halogen, cyano, TMS, trifluoromethyl, methyl, ethyl, n-propyl, i-propyl, butyl, n-butyl, i-butyl, t-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, i-pentyl, neopentyl, t-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, 1-methylhexyl, cyclopentane, cyclohexane, phenyl, biphenyl, naphthyl, fluorenyl, dimethylfluorenyl, phenanthryl, anthryl, indenyl, triphenylenyl, pyrenyl, pyrrolyl, furanyl, thienyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzoindolyl, benzothiadiazolyl, carbazolyl, benzocarbazolyl, adamantyl, or a substituent connected by two or more substituents shown above.

[0039] Further preferably, the dopant material is any one of the following structures, but is not limited thereto:

[0040]

[0041]

[0042]

[0043]

[0044] ​

[0045]

[0046]

[0047] The phosphorescent dopant material applied in the green light device of the present application can be prepared by a synthetic method known to those skilled in the art or by the preparation method of the present application.

[0048] According to another aspect of the present application, there is also provided a preparation method of the phosphorescent dopant material applied in the green light device, specifically as follows:

[0049]

[0050] In the above formula, A, B, R1-R3, n1-n3 are defined as in the above Chemical Formula I, and X represents or -B(OH)2.

[0051] In comparison with the complex raw materials not disclosed, the classic Suzuki coupling reaction, Buchwald-Hartwig coupling reaction is used for synthesis and applied to the present application.

[0052] The specific preparation method is as follows:

[0053] Step 1 specifically includes the following process:

[0054] In a reaction bottle, raw material A (1.0 eq), raw material B (1.0 eq), Na2S2O3 (0.05-0.1 eq) and DMF (N, N-dimethylformamide) are added, replaced by N2, and reacted at 70-90°C for 3-12h. After determining the end of the reaction by thin layer chromatography, ethyl acetate and water are added for extraction and separation to obtain an organic layer for concentration. The intermediate 1 is obtained by column chromatography using a mixed solution of cyclohexane / ethyl acetate (V 环己烷 / V 乙酸乙酯 =12:1-8:1).

[0055] Step 2 specifically includes the following process:

[0056] In a reaction bottle, intermediate 1 (1.0 eq), raw material C (2.0-4.0 eq), Cu (0.5 eq), CuI (0.5 eq), 1,10-phenanthroline (1.0 eq), cesium carbonate (2.0-4.0 eq) and anhydrous dimethyl are added, replaced by nitrogen, and reacted at an oil bath temperature of 150-180°C for 18-40h and then cooled to room temperature. After direct suction filtration of the reaction using ethyl acetate as the eluent to remove inorganic salts, the intermediate 2 is obtained by column chromatography using a mixed solution of cyclohexane / ethyl acetate (V 环己烷 / V 乙酸乙酯= 3:1-8:1) and purified by column chromatography to obtain intermediate 2.

[0057] Step 3 specifically includes the following process:

[0058] In a reaction bottle, a mixed solution of toluene, ethanol and water (V 甲苯 :V 乙醇 :V 水 = 3:1:1), intermediate 2 (1.0 eq), raw material D (1.0-1.2 eq), potassium carbonate (2.0-4.0 eq), after passing nitrogen, add tetrakis(triphenylphosphine)palladium (0.01-0.03 eq), and heat to 70-95°C for 2-14h; after confirming the end of the reaction by thin layer chromatography, slightly reduce the temperature, add water and dichloromethane to extract and separate, retain the organic phase and concentrate, and purify by column chromatography using a mixed solution of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1:4-1:12).

[0059] Step 4 specifically includes the following process:

[0060] In a reaction bottle, add intermediate 3 (1.0 eq), raw material E (1.0-2.0 eq), potassium acetate (2.0-4.0 eq) and 1,4-dioxane, pass nitrogen, then add tris(dibenzylideneacetone)dipalladium (0.01-0.03 eq) and X-Phos (0.1-0.2 eq), heat to 110-120°C and stir for 3-18h; after confirming the end of the reaction by thin layer chromatography, add water and dichloromethane to extract and separate, retain the organic phase and concentrate, and purify by column chromatography using a mixed solution of dichloromethane and petroleum ether (V 二氯甲烷 :V 石油醚 = 1:4-1:8).

[0061] Step 5 specifically includes the following process:

[0062] In a reaction bottle, add a mixed solution of toluene, ethanol and water (V 甲苯 :V 乙醇 :V 水 = 3:1:1), intermediate 4 (1.0 eq), raw material F (1.0-1.3 eq), potassium carbonate (2.0-4.0 eq), pass nitrogen, then add tetrakis(triphenylphosphine)palladium (0.01-0.03 eq), heat to 70-95°C for 2-10h; after confirming the end of the reaction by thin layer chromatography, slightly reduce the temperature, add water and dichloromethane to extract and separate, retain the organic phase and concentrate, and purify by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V = 1:4-1:10) to obtain intermediate 5.

[0063] Note: In this reaction step, the raw material F has two halogens. On the one hand, it takes advantage of the characteristics of the Suzuki coupling reaction, that is, the reactivity Br>Cl. On the other hand, by controlling the reaction conditions, the reaction site is controlled to achieve the preparation of the intermediate of the target structure. The reaction is purified by column chromatography or silica gel funnel to remove the by-products to obtain the target compound. The reaction mechanism is described in: Transition Metal Organic Chemistry (6th edition), Robert. H. Crabtree, Publisher: Shanghai East China University of Technology Press, Publication Date: 2017-09-00, ISBN: 978-7-5628-5111-0, page 388; and Organic Chemistry and Optoelectronic Materials Experiment Course, Chen Runfeng, Publisher: Southeast University Press, Publication Date: 2019-11-00, ISBN: 9787564184230, page 174.

[0064] Step 6 specifically includes the following process:

[0065] A mixture solution of toluene, ethanol and water (V:V:V: = 3:1:1), intermediate 5 (1.0 eq), raw material G (1.0-1.2 eq), cesium carbonate (2.0-4.0 eq) is added to the reaction bottle, and then palladium acetate (0.01-0.05 eq) and X-Phos (0.1-0.2 eq) are added after nitrogen is passed. The temperature is raised to 80-95℃ and reacted for 3-20h; after the reaction is confirmed to be completed by thin layer chromatography, the temperature is slightly lowered, water and dichloromethane are added for separation, the organic phase is retained and concentrated, and then purified by column chromatography using a mixture of dichloromethane and petroleum ether (V:V = 1:4-1:10) to obtain intermediate 6.

[0066] Step 7 specifically includes the following process:

[0067] Acetic acid and H2O, intermediate 6 (1.0 eq), K2PtCl4 (1.0-1.3 eq) are added to the reaction bottle and refluxed for 10-36 hours. The refluxed mixture thus obtained is cooled to room temperature, and the precipitate is filtered to obtain a precipitate, which is dissolved in dichloromethane and washed with water, and then the organic phase is retained and concentrated. Purified by column chromatography using a mixture of dichloromethane and petroleum ether (V:V = 1:4-1:12) to obtain chemical formula I.

[0068] The application also provides an organic electroluminescent device, which comprises an anode, a cathode, and a multilayer organic film layer between the anode and the cathode, the multilayer organic film layer comprising at least a light-emitting layer, wherein the light-emitting layer comprises any of the green phosphorescent dopant materials described above.

[0069] The application also provides a display device comprising the aforementioned organic electroluminescent device. The display device is particularly a mobile phone, computer, television, smart watch, smart car, VR or AR helmet.

[0070] Advantages of the application:

[0071] The compound of the application is based on a platinum-containing ONCN tetradentate ligand as a mother nucleus, combined with a tetramethyl-substituted cyclohexane-benzene structure. The platinum-containing ONCN tetradentate ligand structure has strong rigidity, which can effectively improve the stability of the overall structure, and further improve the service life of the device. In addition, there are more modification sites, which can further connect other substituent structures, effectively balance the molecular weight of the whole molecule, regulate the overall structure of the molecule, and further improve the electroluminescent performance of the compound.

[0072] In addition, the tetramethyl-substituted cycloalkyl-benzene structure has a hyperconjugation effect, and its structure is more three-dimensional in space, which can have a certain adjusting effect on the spatial structure of the compound. As a steric hindrance structure, it can reduce aggregation quenching, enhance the electron mobility of the whole structure, on the other hand, it can significantly improve the resonance factor of the compound, effectively prevent the close packing between molecules and reduce the concentration of excitons, and realize more efficient energy transmission, thereby improving the luminous efficiency and service life of the organic electroluminescent device, while maintaining a lower driving voltage. BRIEF DESCRIPTION OF DRAWINGS

[0073] Figure 1 is the nuclear magnetic resonance hydrogen spectrum of compound 1 provided in Example 1 of the application. DETAILED DESCRIPTION

[0074] The technical solutions in the embodiments of the application will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the application, not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the application.

[0075] In addition, it should be noted that the numerical values given in the following examples are as accurate as possible, but those skilled in the art understand that due to unavoidable measurement errors and experimental operation problems, each number should be understood as an approximate number, not an absolutely accurate number.

[0076] Wherein D-1, E-76, D-185, E-197 are the same raw material, the CAS number is: 73183-34-3; A-1, D-84, A-185 are prior art, which can be directly used in the synthesis route.

[0077] Example 1

[0078]

[0079] In a reaction flask, raw material A-1 (1.0 eq, CAS No.: 3008260-44-1), raw material B-1 (3.0 eq, CAS No.: 166322-31-2), Cu (0.5 eq), CuI (0.5 eq), 1,10-phenanthroline (1.0 eq), cesium carbonate (3.0 eq), and anhydrous dimethyl ether were added, and the mixture was stirred at 160°C for 20 hours under nitrogen atmosphere. After the reaction mixture was cooled to room temperature, the inorganic salt was removed by filtration, and the filtrate was purified by column chromatography using a mixture of cyclohexane / ethyl acetate (V / V = 9:1) to obtain intermediate 1 (yield: 50%).

[0080] In a reaction flask, a mixture of toluene, ethanol, and water (V:V:V = 3:1:1), intermediate 1 (1.0 eq), raw material C-1 (1.1 eq, CAS No.: 2095254-96-7), and potassium carbonate (3.0 eq) were added, and the mixture was stirred at 95°C for 7 hours under nitrogen atmosphere. After the reaction was confirmed to be completed by thin layer chromatography, the temperature was slightly lowered, and the reaction mixture was extracted with water and dichloromethane. The organic layer was concentrated, and the residue was purified by column chromatography using a mixture of dichloromethane and petroleum ether (V:V = 1:7) to obtain intermediate 2 (yield: 78.5%).

[0081] In a reaction flask, intermediate 2 (1.0 eq), raw material D-1 (1.5 eq, CAS No.: 73183-34-3), potassium acetate (3.0 eq), and 1,4-dioxane were added, and the mixture was stirred at 120°C for 14 hours under nitrogen atmosphere. After the reaction was confirmed to be completed by thin layer chromatography, the temperature was slightly lowered, and the reaction mixture was extracted with water and dichloromethane. The organic layer was concentrated, and the residue was purified by column chromatography using a mixture of dichloromethane and petroleum ether (V:V = 1:4) to obtain intermediate 3 (yield: 74.5%).

[0082] In a reaction flask, a mixture of toluene, ethanol, and water (V:V:V = 3:1:1), intermediate 3 (1.0 eq), raw material E-1 (1.1 eq, CAS No.: 22918-01-0), and potassium carbonate (3.0 eq) were added, and the mixture was stirred at 85°C for 4 hours under nitrogen atmosphere. After the reaction was confirmed to be completed by thin layer chromatography, the temperature was slightly lowered, and the reaction mixture was extracted with water and dichloromethane. The organic layer was concentrated, and the residue was purified by column chromatography using a mixture of dichloromethane and petroleum ether (V:V = 1:8) to obtain intermediate 4 (yield: 71.7%).

[0083] In a reaction flask, a mixture solution of toluene, ethanol and water (V:V:V: = 3:1:1), intermediate 4 (1.0 eq) raw material F-1 (1.1 eq, CAS No: 169126-63-0), cesium carbonate (3.0 eq), after nitrogen was introduced, palladium (0) acetate (0.05 eq) and X-Phos (0.1 eq) were added, and the temperature was raised to 95°C for 15h; after the reaction was confirmed by thin layer chromatography, the temperature was slightly lowered, water and dichloromethane were added to separate the liquid, the organic phase was retained and concentrated, and a mixture of dichloromethane and petroleum ether (V:V = 1:6) was used to purify by column chromatography to obtain intermediate 5 (yield: 83.6%).

[0084] In a reaction flask, acetic acid and H2O, intermediate 5 (1.0 eq), K2PtCl4 (1.2 eq) were added and refluxed for 18h. The refluxed mixture thus obtained was cooled to room temperature, and the precipitate was filtered, dissolved in dichloromethane and washed with water, and then the organic phase was retained and concentrated, and a mixture of dichloromethane and petroleum ether (V:V = 1:6) was used to purify by column chromatography to obtain compound 1 (yield: 61.1%).

[0085] The obtained compound 1 was subjected to detection analysis, and the results were as follows:

[0086] HPLC purity: >99.2%.

[0087] Mass spectrometry: Waters XEVO TQD mass spectrometer, ESI source.

[0088] Test value MS (ESI, m / Z): [M+H]+ = 1096.8.

[0089] Elemental analysis:

[0090] Calculated value: C, 70.05; H, 6.89; N, 3.83; O, 1.46; Pt, 17.78;

[0091] Test value: C, 69.69; H, 7.02; N, 3.98; O, 1.60; Pt, 17.89.

[0092] Nuclear magnetic resonance hydrogen spectrum: as shown in Figure 1 (compound 1).

[0093] Example 2

[0094]

[0095] In a reaction flask, add raw material A-76 (1.0 eq, CAS No.: 1575-36-6), raw material B-76 (1.0 eq, CAS No.: 66232-34-6), Na2S2O3 (0.05-0.1 eq) and DMF (N,N-dimethylformamide), replace N2, and react at 80°C for 4h. After determining the end of the reaction by thin layer chromatography, extract the solution with ethyl acetate and water to obtain an organic layer, concentrate, and purify by column chromatography using a mixed solution of cyclohexane / ethyl acetate (V / V=8:1) to obtain intermediate 1 (yield: 22.0%).

[0096] In a reaction flask, add intermediate 1 (1.0 eq), raw material C-76 (3.0 eq, CAS No.: 166322-31-2), Cu (0.5 eq), CuI (0.5 eq), 1,10-phenanthroline (1.0 eq), cesium carbonate (3.0 eq), and anhydrous dimethyl, replace N2, and react at 160°C for 18h in an oil bath, then cool to room temperature. After direct filtration of the reaction with ethyl acetate as the eluent to remove inorganic salts, purify by column chromatography using a mixed solution of cyclohexane / ethyl acetate (V / V=8:1) to obtain intermediate 2 (yield: 52.0%).

[0097] In a reaction flask, add a mixed solution of toluene, ethanol, and water (V:V:V:=3:1:1), intermediate 2 (1.0 eq), raw material D-76 (1.1 eq, CAS No.: 2750016-14-7), potassium carbonate (3.0 eq), replace N2, then add tetrakis(triphenylphosphine)palladium (0.01 eq), and react at 95°C for 9h. After confirming the end of the reaction by thin layer chromatography, add water and dichloromethane to extract the solution, retain the organic phase, concentrate, and purify by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V=1:8) to obtain intermediate 3 (yield: 79.8%).

[0098] In a reaction flask, add intermediate 3 (1.0 eq), raw material E-76 (1.5 eq, CAS No.: 73183-34-3), potassium acetate (3.0 eq), and 1,4-dioxane, replace N2, then add tris(dibenzylideneacetone)dipalladium (0.02 eq) and X-Phos (0.1 eq), and react at 120°C for 16h with stirring. After confirming the end of the reaction by thin layer chromatography, add water and dichloromethane to extract the solution, retain the organic phase, concentrate, and purify by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V=1:5) to obtain intermediate 4 (yield: 74.0%).

[0099] In a reaction flask, a mixed solution of toluene, ethanol and water (V:V:V: = 3:1:1), intermediate 4 (1.0 eq), raw material F-76 (1.1 eq, CAS No.: 22918-01-0), potassium carbonate (3.0 eq) were added, and after nitrogen was passed, tetrakis(triphenylphosphine)palladium (0.01 eq) was added, and the temperature was raised to 85°C for 6h. After the reaction was confirmed to be completed by thin layer chromatography, the temperature was slightly lowered, water and dichloromethane were added to separate the liquid, the organic phase was retained, and then concentrated. A mixed solution of dichloromethane and petroleum ether (V:V = 1:9) was used to purify by column chromatography to obtain intermediate 5 (yield: 70.6%).

[0100] In a reaction flask, a mixed solution of toluene, ethanol and water (V:V:V: = 3:1:1), intermediate 5 (1.0 eq), raw material G-76 (1.1 eq, CAS No.: 2411321-84-9), cesium carbonate (3.0 eq) were added, and after nitrogen was passed, palladium acetate (0.05 eq) and X-Phos (0.1 eq) were added, and the temperature was raised to 95°C for 18h. After the reaction was confirmed to be completed by thin layer chromatography, the temperature was slightly lowered, water and dichloromethane were added to separate the liquid, the organic phase was retained, and then concentrated. A mixed solution of dichloromethane and petroleum ether (V:V = 1:5) was used to purify by column chromatography to obtain intermediate 6 (yield: 80.8%).

[0101] In a reaction flask, acetic acid and H2O, intermediate 6 (1.0 eq), K2PtCl4 (1.2 eq) were added, and refluxed for 24h. The refluxed mixture thus obtained was cooled to room temperature, and the precipitate was filtered, dissolved in dichloromethane and washed with water, and then the organic phase was retained and concentrated. A mixed solution of dichloromethane and petroleum ether (V:V = 1:8) was used to purify by column chromatography to obtain compound 76 (yield: 57.6%).

[0102] The obtained compound 76 was subjected to detection analysis, and the results were as follows:

[0103] HPLC purity: >99.0%.

[0104] Mass spectrometry: Waters XEVO TQD mass spectrometer, ESI source.

[0105] Test value MS (ESI, m / Z): [M+H] + = 1096.67.

[0106] Elemental analysis:

[0107] Calculated value: C, 70.06; H, 5.42; N, 3.83; O, 2.92; Pt, 17.78;

[0108] Test values: C, 69.68; H, 5.56; N, 3.96; O, 3.04; Pt, 17.91.

[0109] Example 3

[0110]

[0111] In a reaction flask, intermediate 1 (1.0 eq), starting material C-84 (3.0 eq, CAS No.: 166322-31-2), Cu (0.5 eq), CuI (0.5 eq), 1,10-phenanthroline (1.0 eq), cesium carbonate (3.0 eq), and anhydrous dimethylformamide were added. After the reaction was carried out at 160°C for 22 h in an oil bath with nitrogen, it was cooled to room temperature. After the reaction was directly filtered to remove inorganic salts with ethyl acetate as the eluent, intermediate 2 (yield: 48.0%) was obtained by column chromatography using a mixture of cyclohexane / ethyl acetate (V / V = 10:1).

[0112] In a reaction flask, intermediate 1 (1.0 eq), starting material C-84 (3.0 eq, CAS No.: 166322-31-2), Cu (0.5 eq), CuI (0.5 eq), 1,10-phenanthroline (1.0 eq), cesium carbonate (3.0 eq), and anhydrous dimethylformamide were added. After the reaction was carried out at 160°C for 22 h in an oil bath with nitrogen, it was cooled to room temperature. After the reaction was directly filtered to remove inorganic salts with ethyl acetate as the eluent, intermediate 2 (yield: 48.0%) was obtained by column chromatography using a mixture of cyclohexane / ethyl acetate (V / V = 10:1).

[0113] In a reaction flask, intermediate 1 (1.0 eq), starting material C-84 (3.0 eq, CAS No.: 166322-31-2), Cu (0.5 eq), CuI (0.5 eq), 1,10-phenanthroline (1.0 eq), cesium carbonate (3.0 eq), and anhydrous dimethylformamide were added. After the reaction was carried out at 160°C for 22 h in an oil bath with nitrogen, it was cooled to room temperature. After the reaction was directly filtered to remove inorganic salts with ethyl acetate as the eluent, intermediate 2 (yield: 48.0%) was obtained by column chromatography using a mixture of cyclohexane / ethyl acetate (V / V = 10:1).

[0114] To a reaction flask, acetic acid and H2O, intermediate 3 (1.0 eq), K2PtCl4(1.2 eq) were added, and the reaction was refluxed for 20 h. The refluxed mixture thus obtained was cooled to room temperature, filtered to obtain a precipitate, the precipitate was dissolved in dichloromethane and washed with water, then the organic phase was reserved after concentration, purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V = 1:7) to obtain compound 84 (yield: 59.9%).

[0115] The obtained compound 84 was subjected to detection analysis, and the results were as follows:

[0116] HPLC purity: >99.1%.

[0117] Mass spectrometry: Waters XEVO TQD mass spectrometer, ESI source.

[0118] Test value MS (ESI, m / Z): [M+H] + = 1042.75.

[0119] Elemental analysis:

[0120] Calculated value: C, 69.07; H, 6.67; N, 4.03; O, 1.53; Pt, 18.70;

[0121] Test value: C, 68.72; H, 6.79; N, 4.14; O, 1.68; Pt, 18.84.

[0122] Example 4

[0123]

[0124] To a reaction flask, raw material A-185 (1.0 eq, CAS No.: 1770-32-7), raw material B-185 (3.0 eq, CAS No.: 2490476-18-9), Cu (0.5 eq), CuI (0.5 eq), 1,10-phenanthroline (1.0 eq), cesium carbonate (3.0 eq) and anhydrous dimethyl were added, nitrogen was passed, and the reaction was carried out at an oil bath temperature of 160°C for 21 h after cooling to room temperature. The reaction was directly filtered to remove inorganic salts with ethyl acetate as the eluent, and then purified by column chromatography using a mixed solution of cyclohexane / ethyl acetate (V / V = 9:1) to obtain intermediate 1 (yield: 55.0%).

[0125] In a reaction flask, add a mixture solution of toluene, ethanol and water (V:V:V: = 3:1:1), intermediate 1 (1.0 eq), raw material C-185 (1.1 eq, CAS No.: 2919766-20-2), potassium carbonate (3.0 eq), and then add tetrakis(triphenylphosphine)palladium (0.01 eq) after passing nitrogen, and then heat to 95°C for 5h; after confirming the end of the reaction by thin layer chromatography, slightly lower the temperature, add water and dichloromethane to extract and separate, retain the organic phase and then concentrate, purify by column chromatography using a mixture solution of dichloromethane and petroleum ether (V:V = 1:7) to obtain intermediate 2 (yield: 78.6%).

[0126] In a reaction flask, add intermediate 2 (1.0 eq), raw material D-185 (1.5 eq, CAS No.: 73183-34-3), potassium acetate (3.0 eq), and 1,4-dioxane, and then add tris(dibenzylideneacetone)dipalladium (0.02 eq) and X-Phos (0.1 eq) after passing nitrogen, and then heat to 120°C and stir for 13h; after confirming the end of the reaction by thin layer chromatography, add water and dichloromethane to extract and separate, retain the organic phase and then concentrate, purify by column chromatography using a mixture solution of dichloromethane and petroleum ether (V:V = 1:4) to obtain intermediate 3 (yield: 74.9%).

[0127] In a reaction flask, add a mixture solution of toluene, ethanol and water (V:V:V: = 3:1:1), intermediate 3 (1.0 eq), raw material E-185 (1.1 eq, CAS No.: 22918-01-0), potassium carbonate (3.0 eq), and then add tetrakis(triphenylphosphine)palladium (0.01 eq) after passing nitrogen, and then heat to 85°C for 3h; after confirming the end of the reaction by thin layer chromatography, slightly lower the temperature, add water and dichloromethane to extract and separate, retain the organic phase and then concentrate, purify by column chromatography using a mixture solution of dichloromethane and petroleum ether (V:V = 1:8) to obtain intermediate 4 (yield: 72.3%).

[0128] In a reaction flask, add a mixture solution of toluene, ethanol and water (V:V:V: = 3:1:1), intermediate 4 (1.0 eq), raw material F-185 (1.1 eq, CAS No.: 2816974-76-0), cesium carbonate (3.0 eq), and then add palladium acetate (0.05 eq) and X-Phos (0.1 eq) after passing nitrogen, and then heat to 95°C for 16h; after confirming the end of the reaction by thin layer chromatography, slightly lower the temperature, add water and dichloromethane to extract and separate, retain the organic phase and then concentrate, purify by column chromatography using a mixture solution of dichloromethane and petroleum ether (V:V = 1:6) to obtain intermediate 5 (yield: 82.2%).

[0129] In a reaction flask, acetic acid and H2O, intermediate 5 (1.0 eq), K2PtCl4(1.2 eq) were added and the reaction was refluxed for 21 h. The refluxed mixture thus obtained was cooled to room temperature, filtered to obtain the precipitate, which was dissolved in dichloromethane and washed with water, then the organic phase was retained after concentration, purified by column chromatography using a mixture of dichloromethane and petroleum ether (V:V = 1:7) to obtain compound 185 (yield: 59.2%).

[0130] The compound 185 thus obtained was subjected to analytical testing, with the following results:

[0131] HPLC purity: >99.1%.

[0132] Mass spectrometry test: mass spectrometer of Waters XEVO TQD type, with ESI source.

[0133] Test value MS (ESI, m / Z): [M+H]+= 992.64.

[0134] Elemental analysis:

[0135] Calculated: C, 68.93; H, 5.58; N, 4.23; O, 1.61; Pt, 19.64;

[0136] Test value: C, 68.56; H, 5.71; N, 4.36; O, 1.73; Pt, 19.79.

[0137] Example 5

[0138]

[0139] In a reaction flask, raw material A-197 (1.0 eq, CAS No: 1575-36-6), raw material B-197 (1.0 eq, CAS No: 17887-65-9), Na2S2O3(0.05-0.1 eq) and DMF (N,N-dimethylformamide) were added, replaced with N2, and reacted at 80°C for 7 h. After determining the end of the reaction by thin layer chromatography, ethyl acetate and water were added to extract the solution, and the organic layer was concentrated, purified by column chromatography using a mixture of cyclohexane / ethyl acetate (V / V = 10:1) to obtain intermediate 1 (yield: 78.0%).

[0140] In a reaction flask, add intermediate 1 (1.0 eq), raw material C-197 (3.0 eq, CAS No.: 1612853-56-1), Cu (0.5 eq), CuI (0.5 eq), 1,10-phenanthroline (1.0 eq), cesium carbonate (3.0 eq) and anhydrous dimethyl, nitrogen, oil bath temperature 160℃ reaction 28h after cooling to room temperature, reaction with ethyl acetate as eluent directly filter out the inorganic salt, using cyclohexane / ethyl acetate (V / V = 12:1) mixed solution, purified by column chromatography to obtain intermediate 2 (yield: 45.0%).

[0141] In a reaction flask, add a mixture of toluene, ethanol and water (V:V:V: = 3:1:1), intermediate 2 (1.0 eq), raw material D-197 (1.1 eq, CAS No.: 2095254-96-7), potassium carbonate (3.0 eq), and then add tetrakis(triphenylphosphine)palladium (0.01 eq) after nitrogen, and then heat to 95℃ for 8h; use thin layer chromatography to detect the reaction, confirm the end of the reaction, slightly lower the temperature, add water and dichloromethane to extract and separate, retain the organic phase, concentrate, use a mixture of dichloromethane and petroleum ether (V:V = 1:9) to purify by column chromatography to obtain intermediate 3 (yield: 77.5%).

[0142] In a reaction flask, add intermediate 3 (1.0 eq), raw material E-197 (1.5 eq, CAS No.: 73183-34-3), potassium acetate (3.0 eq) and 1,4-dioxane, then add tris(dibenzylideneacetone)dipalladium (0.02 eq) and X-Phos (0.1 eq) after nitrogen, and then heat to 120℃ and stir for 18h; use thin layer chromatography to detect the reaction, determine the end of the reaction, add water and dichloromethane to extract and separate, retain the organic phase, concentrate, use a mixture of dichloromethane and petroleum ether (V:V = 1:6) to purify by column chromatography to obtain intermediate 4 (yield: 73.7%).

[0143] In a reaction flask, add a mixture of toluene, ethanol and water (V:V:V: = 3:1:1), intermediate 4 (1.0 eq), raw material F-197 (1.1 eq, CAS No.: 22918-01-0), potassium carbonate (3.0 eq), and then add tetrakis(triphenylphosphine)palladium (0.01 eq) after nitrogen, and then heat to 85℃ for 8h; use thin layer chromatography to detect the reaction, confirm the end of the reaction, slightly lower the temperature, add water and dichloromethane to extract and separate, retain the organic phase, concentrate, use a mixture of dichloromethane and petroleum ether (V:V = 1:10) to purify by column chromatography to obtain intermediate 5 (yield: 69.5%).

[0144] In a reaction flask, a mixed solution of toluene, ethanol and water (V:V:V: = 3:1:1), intermediate 5 (1.0 eq), raw material G-197 (1.1 eq, CAS No.: 2816974-76-0), cesium carbonate (3.0 eq), after nitrogen was introduced, palladium (0) acetate (0.05 eq) and X-Phos (0.1 eq) were added, and the temperature was raised to 95°C for 20h; after the reaction was confirmed to be completed by thin layer chromatography, the temperature was slightly lowered, water and dichloromethane were added to separate the liquid, the organic phase was retained and concentrated, and a mixed solution of dichloromethane and petroleum ether (V:V = 1:5) was used to purify by column chromatography to obtain intermediate 6 (yield: 81.9%).

[0145] In a reaction flask, acetic acid and H2O, intermediate 6 (1.0 eq), K2PtCl4 (1.2 eq) were added and refluxed for 25h. The refluxed mixture thus obtained was cooled to room temperature, and the precipitate was filtered, dissolved in dichloromethane and washed with water, and then the organic phase was retained and concentrated, and a mixed solution of dichloromethane and petroleum ether (V:V = 1:8) was used to purify by column chromatography to obtain compound 197 (yield: 55.8%).

[0146] The obtained compound 197 was subjected to detection analysis, and the results were as follows:

[0147] HPLC purity: >99.0%.

[0148] Mass spectrometry: Waters XEVO TQD mass spectrometer, ESI source.

[0149] Test value MS (ESI, m / Z): [M+H] + = 1128.62.

[0150] Elemental analysis:

[0151] Calculated value: C, 67.00; H, 5.27; N, 3.72; O, 1.42; Pt, 17.27; S, 2.84; Si, 2.49;

[0152] Test value: C, 66.54; H, 5.38; N, 3.84; O, 1.56; Pt, 17.39; S, 2.97; Si, 2.60.

[0153] Example 6-30

[0154] The synthesis of the following compounds was completed according to the synthesis method of Reference Example 1-5, and the mass spectrometer was tested by Waters XEVO TQD, which had low accuracy, and the mass spectrometer was tested by ESI source, and the mass spectrometer test values were shown in Table 1.

[0155] Table 1 Mass spectrometry test values for Examples 6-30

[0156]

[0157]

[0158] In addition, it should be noted that other compounds of the present application can be obtained by reference to the synthetic methods of the examples listed above, and therefore are not individually listed here.

[0159] Another object of the present application is to provide an organic electroluminescent device including a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode.

[0160] The organic material layer of the organic light emitting device of the present application can be formed as a single layer structure, but can also be formed as a multi-layer structure in which layers and two or more organic material layers. For example, the organic light emitting device of the present application can have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, etc. as the organic material layer. However, the structure of the organic light emitting device is not limited thereto, and can include a smaller number of organic material layers or a larger number of organic material layers.

[0161] In addition to the green dopant material layer disclosed herein containing Formula I, there is no particular restriction on the material of other layers in the OLED device.

[0162] The devices described herein can be used in organic light emitting devices, including but not limited to flat panel displays, computer monitors, medical monitors, televisions, billboards, lamps for interior or exterior illumination and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, laser printers, telephones, cell phones, photo albums, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, three-dimensional displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or venue screens, light therapy devices, and signage.

[0163] The organic electroluminescent composition and the organic electroluminescent device provided by the present application are specifically described below in conjunction with specific examples.

[0164] Device Example 1: Preparation of an organic electroluminescent device

[0165] The structure of the prepared OLED device is: ITO anode / HIL / HTL / Prime / EML / HBL / ETL / EIL / cathode / CPL.

[0166] a. ITO anode: The coating thickness is... The ITO (indium tin oxide)-Ag-ITO (indium tin oxide) glass substrate was cleaned three times with distilled water, ultrasonically washed for 40 minutes, then repeatedly cleaned three times with distilled water, ultrasonically washed for 20 minutes. After washing, it was ultrasonically washed sequentially with methanol, acetone, and isopropanol (5 minutes each time), dried, and then transferred to a plasma cleaner for 5 minutes. Finally, it was sent to an evaporation machine, where other functional layers were sequentially deposited on the substrate as the anode.

[0167] b. HIL (Hole Injection Layer): The evaporation rate of the hole injection layer material HT and P-dopant was vacuum evaporated, and their chemical formulas are shown below. The evaporation rate ratio of HT and P-dopant was 97:3, and the thickness was 10 nm.

[0168] c. HTL (Hole Transport Layer): At a certain evaporation rate, a 130nm HT layer was vacuum-deposited on top of the hole injection layer as a hole transport layer.

[0169] d. Prime (Emitting Assist Layer): with At a certain evaporation rate, a 100 nm Prime layer was vacuum-deposited on the hole transport layer as a light-emitting auxiliary layer.

[0170] e. EML (Emitting Layer): Then, on the above-mentioned emitting auxiliary layer, with... The evaporation rate is such that a dual host material (Host-1 and Host-2) and a doped material (compound 1 provided in the above embodiment) with a vacuum evaporation thickness of 30 nm are used as the light-emitting layer, wherein the ratio of Host-2 to Host-3 is 50:50, and the evaporation rate ratio of the dual host material to the doped material is 90:10.

[0171] f. HBL (Hole Blocking Layer): The evaporation rate was high, and a hole blocking layer HB with a thickness of 5 nm was vacuum-deposited.

[0172] g. ETL (Electron Transport Layer): The evaporation rate was determined, and ET and Liq were vacuum-deposited to a thickness of 30 nm as electron transport layers. The chemical formula of ET is shown below. The evaporation rate ratio of ET to Liq is 50:50.

[0173] h, EIL (Electron Injection Layer): with The evaporation rate was such that a 1 nm Yb film was deposited to form an electron injection layer.

[0174] i. Cathode: with The OLED device was prepared by vacuum evaporation of 13 nm of Mg and 13 nm of Ag at a rate ratio of 1:9 on the cathode.

[0175] j. CPL (light extraction layer): 65 nm of CPL was vacuum evaporated on the cathode as a light extraction layer at a rate ratio of 1:9. The OLED device was prepared by vacuum evaporation of 13 nm of Mg and 13 nm of Ag at a rate ratio of 1:9 on the cathode.

[0176] k. The substrate on which the evaporation was completed was then encapsulated. First, the cleaned cover plate was coated with UV glue using a glue coating device, then the coated cover plate was moved to the pressing section, the substrate on which the evaporation was completed was placed on the end of the cover plate, and finally the substrate and the cover plate were bonded under the action of the bonding device, and the UV glue was simultaneously cured by light.

[0177] The structures of the HT, P-dopant, Host-1, Host-2, Prime, HB, ET, and CPL used in the above device embodiment 1 are shown below:

[0178]

[0179] Referring to the method provided in the above device embodiment 1, the corresponding compounds in Table 2 were respectively selected to replace compound 1 to perform evaporation of the doping material, and the corresponding organic electroluminescent devices were prepared and were respectively recorded as device embodiments 2-30.

[0180] Device comparative examples 1-6:

[0181] This comparative example provides an organic electroluminescent device, and the preparation method of the organic electroluminescent device is different from that of device embodiment 1 in that the organic electroluminescent device is prepared by replacing the above-mentioned doping material (compound 1) in device embodiment 1 with existing comparative compounds a-f for evaporation. The chemical structural formulas of the comparative compounds a-f are as follows:

[0182]

[0183] The driving voltage, luminous efficiency, and lifetime of the organic electroluminescent devices obtained from the above device embodiments 1-30 and device comparative examples 1-6 were characterized at a brightness of 15000 (nits), and the test results are shown in Table 2 (the test results are normalized with respect to comparative example 1).

[0184] Table 2

[0185]

[0186]

[0187] As can be seen from Table 2, the metal compound in the present application has excellent phosphorescent light emitting properties, and the organic electroluminescent device prepared therefrom has more excellent driving voltage, luminous efficiency and lifespan, and the performance is obviously improved compared with the organic electroluminescent device prepared from the comparative compound.

[0188]

[0189] The comparative compounds a, c, f and the compounds 16, 133, 62 are parallel comparative examples, and the difference is that the comparative compounds do not contain the tetramethyl-substituted cyclohexanophenyl structure However, the compound 16, 133, 62 of the present application contains at least one tetramethyl-substituted cyclohexanophenyl structure on the N on the left side or the N-containing benzene ring on the right side, which is more three-dimensional in space, can have certain adjustment effect on the spatial structure of the compound, can reduce the aggregation quenching as a steric hindrance structure, enhance the electron flow in the whole structure, on the other hand, can significantly improve the resonance factor of the compound, can effectively prevent the close packing between molecules and reduce the concentration of excitons, and can realize more efficient energy transmission, thereby improving the luminous efficiency and service life of the organic electroluminescent device, while maintaining a lower driving voltage.

[0190] In addition, further, the NPT method in molecular dynamics is used to simulate the disordered packing density of the thin film, to verify whether the existence of the tetramethyl-substituted cyclohexanophenyl structure affects the packing density of the thin film obtained after evaporation. The comparative compounds a, b, c and the compounds 16, 133, 62 of the present application are tested, and the test results are 1.631 g / cm 3 , 1.219 g / cm 3 , 1.290 g / cm 3 , 1.265 g / cm 3 , 1.152 g / cm 3 , 1.246 g / cm 3 The thin film packing density of the compound of the present application containing the tetramethyl-substituted cyclohexanophenyl structure is lower than that of the corresponding comparative compound (not containing the tetramethyl-substituted cyclohexanophenyl structure), so that the intermolecular stacking is reduced when prepared into a device, the carrier accumulation trap is avoided, which is beneficial to the carrier transmission, improves the carrier balance of the device, optimizes the device performance, and further verifies the test results above.

[0191] The foregoing description of the disclosed embodiments enables a person skilled in the art to carry out or use the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein can be applied to other embodiments without departing from the spirit or scope of the application. Therefore, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

[0192] Finally, it should be noted that the above detailed description of the specific embodiments is not to be taken in a limiting sense, but is only for describing the principal of the present application. Although the present application has been described in detail with reference to the examples, it will be appreciated that various modifications can be made without departing from the spirit and scope of the application, and such modifications are intended to be included within the scope of the claims.

Claims

1. A green phosphorescent doped material, wherein the general structural formula of the phosphorescent doped material is chemical formula I: in, R1 is independently selected from hydrogen, deuterium, halogen group, cyano group, TMS, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C6-C 18 aryl; R2 is independently selected from hydrogen, deuterium, halogen group, cyano group, TMS, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C6-C 18 aryl; R3 is independently selected from hydrogen, deuterium, halogen group, cyano group, TMS, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C6-C 18 aryl; A is independently selected from hydrogen, deuterium, halogen group, cyano group, TMS, substituted or unsubstituted C1-C20 alkyl group, substituted or unsubstituted C6-C group. 30 aryl, substituted or unsubstituted C6-C 30 One of the heteroaryl groups, wherein the heteroatom contains at least one of O, S, N, Si, or Se, and the structure... B is independently selected from substituted or unsubstituted C6-C. 30 aryl, substituted or unsubstituted C6-C 30 One of the heteroaryl groups, wherein the heteroatom contains at least one of O, S, N, Si, or Se, and the structure... And at least one of A and B contains a structure n1 and n2 are integers independently selected from 0, 1, 2, and 3, respectively; n3 is an integer independently selected from 0, 1, 2, 3, and 4.

2. The green phosphorescent doped material as described in claim 1, characterized in that, The general structural formula of the phosphorescent doped material is chemical formula I-1, I-2, or I-3:

3. The green phosphorescent doped material as described in any one of claims 1 to 2, characterized in that, R1 is independently selected from hydrogen, substituted or unsubstituted C1-C6 alkyl groups; substituted or unsubstituted phenyl groups, substituted or unsubstituted biphenyl groups; R2 is independently selected from hydrogen, deuterium, halogen group, cyano group, TMS, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl; R3 is independently selected from hydrogen, deuterium, halogen group, cyano group, TMS, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl; A is independently selected from hydrogen, deuterium, halogen group, cyano group, TMS, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted 9,9-dimethylfluorene group, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted dibenzothiophene group, and structure B is independently selected from substituted or unsubstituted phenyl groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted terphenyl groups, substituted or unsubstituted naphthyl groups, substituted or unsubstituted 9,9-dimethylfluorene groups, substituted or unsubstituted furan groups, substituted or unsubstituted thiophene groups, and structurally...

4. The green phosphorescent doped material as described in claim 3, characterized in that, R1, R2, and R3 are independently selected from hydrogen and the following structures: R4-R9 can be selected from F, CF3, CN, TMS, and one of the following alkyl groups: Where n4, n5, n7, and n9 are independently selected from integers of 0, 1, 2, 3, 4, and 5, respectively; Where n6 and n8 are independently selected from integers 0, 1, 2, 3, and 4, respectively.

5. The green phosphorescent doped material as described in any one of claims 1 to 2, characterized in that, A is independently selected from hydrogen, deuterium, halogen group, cyano group, TMS, and one of the following structures: B is independently selected from the following structures: R10 and R11 can be selected from F, CF3, CN, TMS, and one of the following alkyl groups: Where n10 is an integer independently selected from 0, 1, 2, 3, 4, 5, 6, and 7; where n11 is an integer independently selected from 0, 1, 2, 3, and 4; And at least one of A and B contains a structure 6. The green phosphorescent doped material as described in claim 1, characterized in that, The doped material is any one of the following structures:

7. A method for preparing a green phosphorescent doped material according to any one of claims 1 to 6, characterized in that, The reaction process is as follows: In the above formula, A, B, R1-R3, and n1-n3 are as defined in the above chemical formula I, and X represents... Or *-B(OH)2.

8. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes an anode, a cathode, and a multilayer organic film layer located between the anode and the cathode. The multilayer organic film layer includes at least a light-emitting layer, which includes the green phosphorescent doping material as described in any one of claims 1 to 6.

9. A display device, characterized in that, Including the organic electroluminescent device as described in claim 8.

10. The display device according to claim 9, characterized in that, The display device can be a mobile phone, computer, television, smartwatch, smart car, or VR or AR headset.

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