Green phosphorescent doped material, preparation method thereof and organic electroluminescent device

Abstract

The invention provides a green phosphorescent doped material and a preparation method thereof, an organic electroluminescent device and an organic electroluminescent device, the structural general formula of the green phosphorescent doped material is chemical formula I. According to the green phosphorescent doped material provided by the invention, a platinum-containing ONCN tetradentate ligand structure is introduced, so that the stability of a compound can be effectively improved; a silane group is further connected to a parent nucleus, and the group has huge steric hindrance, so that close approaching between core planes of the Pt complex is hindered, the intermolecular pi-pi accumulation effect is effectively weakened, the concentration quenching effect is remarkably reduced, and the carrier capture efficiency and the device efficiency are improved. According to the material disclosed by the invention, a device with higher luminous efficiency and longer service life can be obtained while low driving voltage is maintained.

Description

TECHNICAL FIELD

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

[0002] It has been shown by research that transition metal complexes can be applied to phosphorescent OLEDs (phosphorescent OLEDs), and the phosphorescent material has a strong self-orbital coupling effect, which can utilize singlet and triplet excitons at the same time, so that the internal quantum efficiency of the phosphorescent electroluminescent device theoretically reaches 100%. Metal complex luminescent materials have been applied in the industry, and traditional industrialized phosphorescent OLED light-emitting layer dopant materials mainly use metal iridium complexes. However, metal platinum has a natural advantage over iridium in terms of price, and the complexes have excellent material stability due to their planarity, which has been greatly developed in recent years. In recent years, metal platinum complexes have shown properties that surpass iridium complexes. The synthesis steps of platinum complexes with ONCN tetradentate ligands are simple, and there are many modifiable sites, which can greatly improve the space. However, this structure is also prone to intermolecular π-π stacking interactions. This close packing can lead to exciton annihilation, and the excited states of adjacent molecules collide and deactivate, converting energy into heat or vibrational energy rather than emitting light (concentration quenching). It can also form excimers or excited state complexes, resulting in red shift and broadening of the emission spectrum, and reducing color purity. Therefore, it is an urgent need in the industry to develop a metal Pt complex as a green phosphorescent dopant material to achieve higher efficiency and longer service life of the device. SUMMARY

[0003] In view of the deficiencies of the prior art, the purpose of the present application is to provide a green phosphorescent dopant material, a preparation method thereof and an organic electroluminescent device. The green phosphorescent dopant material of the present application introduces an ONCN tetradentate ligand structure containing platinum, which can effectively improve the stability of the compound. Further, a silane group is connected to the parent nucleus. This group has a large steric hindrance, which prevents the close approach of the Pt complex core planes, effectively reduces the intermolecular π-π stacking interaction, significantly reduces the concentration quenching effect, and is more helpful to improve the carrier capture efficiency and improve the device efficiency. The material of the present application can maintain a low driving voltage while achieving a device with higher luminous efficiency and longer service life.

[0004] To achieve this purpose, the present application adopts the following technical solutions:

[0005] In one aspect, the present application provides a green phosphorescent dopant material, and the structure general formula of the green phosphorescent dopant material is chemical formula I:

[0006] ;

[0007] wherein,

[0008] Ring H is phenyl, naphthyl, dibenzofuranyl or dibenzothiophenyl;

[0009] Ar is selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0010] R1, R2 are independently selected from hydrogen, deuterium, halogen, cyano, TMS (trimethylsilyl), trifluoromethyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C24 aryl;

[0011] R3 is independently selected from hydrogen, deuterium, halogen, cyano, TMS, trifluoromethyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, which contains at least one of the heteroatoms O, S, N, Si or Se;

[0012] n1 is selected from an integer of 0, 1, 2 or 3;

[0013] n2 is selected from an integer of 0, 1, 2, 3 or 4;

[0014] n3 is selected from an integer of 0, 1, 2, 3 or 4;

[0015] R4-R6 are independently selected from deuterium, halogen, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfido, sulfinyl, sulfonyl, phosphino, selenoalkyl, amino, boroalkyl, germanoalkyl, silylalkyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C1-C10 heterocycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C1-C10 heteroalkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or combinations thereof;

[0016] R7, R8are independently selected from the group consisting of hydrogen, deuterium, fluorine, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;

[0017] m is selected from an integer of 0, 1 or 2;

[0018] In the chemical formula I, two of the four bonds connecting the central metal Pt are coordination bonds, and the other two are covalent bonds. The bond between the metal Pt and the two N is a coordination bond, the bond between Pt and the ring H is a covalent bond, and the bond between Pt and O is a covalent bond.

[0019] The hydrogen involved in the formula I is not deuterated, partially deuterated or fully deuterated.

[0020] Further preferably, the ring H is a phenyl group.

[0021] Ar is selected from substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted C5-C24 heteroaryl.

[0022] R1, R2are independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, TMS, trifluoromethyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C18 aryl.

[0023] R3is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, TMS, trifluoromethyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C5-C24 heteroaryl, which contains at least one of O, S, N, Si, Se as a heteroatom.

[0024] R4-R6are independently selected from the group consisting of deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C1-C6 heteroalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C5-C24 heteroaryl, or a combination thereof.

[0025] R7, R8are independently selected from the group consisting of hydrogen, deuterium, fluorine, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 heteroalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C2-C5 heterocycloalkyl, substituted or unsubstituted C6-C18 aryl, and substituted or unsubstituted C5-C24 heteroaryl.

[0026] The green phosphorescent dopant material further preferably has the general structure according to Formula I-A:

[0027] ;

[0028] wherein Ar1, Ar2are independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, TMS, trifluoromethyl, substituted or unsubstituted C1-C6alkyl, substituted or unsubstituted C3-C6cycloalkyl, substituted or unsubstituted C6-C18aryl, substituted or unsubstituted C5-C24heteroaryl;

[0029] n9, n 10 are independently selected from the group consisting of 0, 1, 2, 3, 4 or 5.

[0030] Further preferably, R1, R2are independently selected from the group consisting of hydrogen, deuterium, cyano, TMS, trifluoromethyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl, substituted or unsubstituted fluorenyl.

[0031] Further preferred, R3is independently selected from the group consisting of hydrogen, deuterium, cyano, TMS, trifluoromethyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted isobenzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzoisothiazolyl, substituted or unsubstituted benzoisoxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted isoindolyl, substituted or unsubstituted indolyl, substituted or unsubstituted benzoindolyl, substituted or unsubstituted benzothiadiazolyl.

[0032] Further preferred, R4-R6are independently selected from the group consisting of deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted isobenzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl.

[0033] Further preferred, R7, R8are independently selected from the group consisting of deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted isobenzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl.

[0034] Further preferred, the green phosphorescent dopant material has a general structure of:

[0035] ;

[0036] Further preferred, Ar1, Ar2are independently selected from the group consisting of deuterium, cyano, TMS, trifluoromethyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted isobenzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl.

[0037] In the present application, the "substituted" group in the substituted or unsubstituted is selected from one or at least two groups of substituents connected from the following groups: deuterium, halogen group, cyano group, TMS, trifluoromethyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, sec-butyl group, 1-methylbutyl group, 1-ethylbutyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 1-methylhexyl group, cyclopropane, cyclobutane, cyclopentane, cyclohexane, phenyl group, biphenyl group, naphthyl group, terphenyl group, fluorenyl group, dimethylfluorenyl group, phenanthryl group, anthryl group, indenyl group, triphenylene group, pyrenyl group, chrysenyl group, furanyl group, thienyl group, pyrrolyl group, pyridyl group, benzofuranyl group, benzothienyl group, isobenzofuranyl group, dibenzofuranyl group, dibenzothienyl group, benzimidazolyl group, benzothiazolyl group, benzoisothiazolyl group, benzoisoxazolyl group, benzoxazolyl group, isoindolyl group, indolyl group, benzoindolyl group, benzothiadiazolyl group, carbazolyl group, benzocarbazolyl group, adamantyl group.

[0038] In the above technical solution, further preferably, the green phosphorescent dopant material is any one of the following structures, but is not limited thereto:

[0039] ;

[0040] ;

[0041] ;

[0042] ;

[0043] ;

[0044] ;

[0045] ;

[0046] ;

[0047] ;

[0048] wherein D represents deuterium.

[0049] The green phosphorescent dopant material of the present application can be prepared by a synthetic method known to those skilled in the art. Alternatively, the following reaction scheme is preferably used for the preparation.

[0050]

[0051] In the above formula, R 1-R8, n1-n3, m are defined as in the above chemical formula I, X represents or The asterisk represents the connection site of the group.

[0052] In comparison with the complex raw materials not disclosed, the classical Suzuki coupling reaction, the Friedel-Crafts reaction, the Ullmann-type amination reaction, the displacement reaction and the application to the present application will be adopted.

[0053] The specific preparation method is as follows:

[0054] The step 1 specifically includes the following process:

[0055] The raw material A (1.0 eq), the raw material B (1.0 eq), Na2S2O3 (0.05-0.1 eq) and DMF (N, N-dimethylformamide) are added into a three-necked flask, replaced by N2, and reacted at 70-90°C for 1-12h. After the reaction is determined to be completed by thin layer chromatography, ethyl acetate and water are added for extraction and separation to obtain an organic layer which is concentrated, and the mixture solution of cyclohexane / ethyl acetate (V / V=12:1-8:1) is used for column chromatography to purify to obtain the intermediate 1.

[0056] The step 2 specifically includes the following process:

[0057] The intermediate 1 (1.0 eq), the 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 xylene are added into a three-necked flask, replaced by nitrogen, and reacted at 150-180°C for 8-40h in an oil bath, and then cooled to room temperature. After the reaction is directly filtered by using ethyl acetate as a washing agent to remove inorganic salts, the mixture solution of cyclohexane / ethyl acetate (V / V=12:1-8:1) is used for column chromatography to purify to obtain the intermediate 2.

[0058] The step 3 specifically includes the following process:

[0059] The raw material D (1.0-1.2 eq), the raw material E (1.0 eq), potassium carbonate (2.0-4.0 eq) and the mixed solution of toluene, ethanol and water (V:V:V:=3:1:1) are added into a three-necked flask, replaced by nitrogen, and then tetrakis(triphenylphosphine)palladium (0.01-0.03 eq) is added, and the temperature is increased to 70-95°C for reaction for 2-12h. After the reaction is detected by thin layer chromatography, the temperature is slightly reduced, water and dichloromethane are added for extraction and separation, and the organic phase is reserved for concentration. The mixture solution of dichloromethane and petroleum ether (V:V=1:3-1:12) is used for column chromatography to purify to obtain the intermediate 3.

[0060] The step 4 specifically includes the following process:

[0061] Intermediate 3 (1.0 eq), starting material F (1.0-2.0 eq), potassium acetate (2.0-4.0 eq) and 1,4-dioxane were added into a three-necked flask, and then the flask was purged with nitrogen. Then, tris(dibenzylideneacetone)dipalladium (0.01-0.03 eq) and X-Phos (0.1-0.2 eq) were added into the flask, and the flask was heated to 110-120 °C and stirred for 2-20 h. After the reaction was completed, water and dichloromethane were added into the flask to separate the organic phase. The organic phase was concentrated, and then purified by column chromatography using a mixture of dichloromethane and petroleum ether (V:V = 1:3-1:8) to obtain intermediate 4.

[0062] Step 5 specifically includes the following process:

[0063] Intermediate 4 (1.0-1.3 eq), intermediate 2 (1.0 eq) and a mixture of toluene, ethanol and water (V:V:V = 3:1:1) were added into a three-necked flask, and then the flask was purged with nitrogen. Then, tetrakis(triphenylphosphine)palladium (0.01-0.03 eq) and potassium carbonate (2.0-4.0 eq) were added into the flask, and the flask was heated to 70-95 °C and stirred for 2-10 h. After the reaction was completed, the temperature was slightly lowered, and water and dichloromethane were added into the flask to separate the organic phase. The organic phase was concentrated, and then purified by column chromatography using a mixture of dichloromethane and petroleum ether (V:V = 1:3-1:10) to obtain intermediate 5.

[0064] Step 6 specifically includes the following process:

[0065] Intermediate 5 (1.0 eq), K2PtCl4 (1.0-1.3 eq), acetic acid and H2O were added into a reaction flask, and the mixture was refluxed for 10-36 h. The refluxed mixture thus obtained was cooled to room temperature, and then filtered to obtain a precipitate. The precipitate was dissolved in dichloromethane and washed with water, and then the organic phase was concentrated. Finally, formula I was obtained by column chromatography using a mixture of dichloromethane and petroleum ether (V:V = 1:3-1:12).

[0066] Another object of the present application is to provide an organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises a light-emitting layer, and the light-emitting layer comprises the green phosphorescent dopant material as described above.

[0067] Preferably, the light-emitting layer comprises a host material and a dopant material, and the dopant material is the green phosphorescent dopant material as described above.

[0068] Preferably, the organic layer further comprises any one or a combination of at least two of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting auxiliary layer, an electron transport layer, an electron injection layer, or a hole blocking layer.

[0069] The organic 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 the organic layer contains 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 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 layers.

[0070] Except for the green phosphorescent dopant material of Formula I contained in the light emitting layer of the present application, there is no particular limitation on the materials for other layers in the OLED device.

[0071] The device described in the present application can be used in organic light emitting apparatuses, including but not limited to flat panel displays, computer monitors, medical monitors, televisions, billboards, lights 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, notebook computers, digital cameras, video cameras, viewfinders, micro-displays, three-dimensional displays, virtual reality or augmented reality displays, vehicles, video walls including multiple displays tiled together, theater or venue screens, light therapy devices, and signage.

[0072] Compared with the prior art, the present application has the following beneficial effects:

[0073] The compound of the present application is based on the ONCN tetradentate ligand containing platinum as the mother nucleus, and further connected with a trimethylsilane group. The device using the compound has high luminous efficiency, long service life, and at the same time maintains a low driving voltage. The ONCN tetradentate ligand structure containing platinum has strong rigidity. Such strong coordination bond not only inhibits ligand dissociation, but also effectively improves the stability of the overall structure, thereby improving the service life of the device. There are more modification sites, which further connect other structures, so that the phosphorescence quantum yield of the green light device is improved, and the electroluminescent performance of the compound is effectively improved. The sigma electron-donating property of the further introduced silane group can improve the electron density of the Pt metal center and enhance the MLCT transition. The huge steric hindrance hinders the close approach between the core planes of the Pt complex, effectively reduces the intermolecular π-π stacking effect, significantly reduces the concentration quenching effect, allows the use of higher doping concentration (usually can be increased to 10-20wt% or even higher) without loss of efficiency or color purity, and is more helpful to improve the carrier capture efficiency and improve the device efficiency. Moreover, the large steric hindance silane group can also inhibit the twisting vibration of the complex plane structure to a certain extent, reduce the non-radiative deactivation channel, inhibit the non-radiative d-d transition, and prevent efficiency loss. At the same time, the type and number of substituents connected to the left N of the benzimidazole are adjusted to control the material performance. The effect of connecting large steric hindance alkyl (such as tert-butyl) to the para position of the benzene ring connected to the left N of the benzimidazole and connecting aryl (such as phenyl) to the ortho position is the best. BRIEF DESCRIPTION OF DRAWINGS

[0074] Figure 1 The nuclear magnetic resonance hydrogen spectrum of compound 1 provided for example 1 of the present application. DETAILED DESCRIPTION

[0075] The technical solutions of the present application will be further described through specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application, and should not be regarded as specific limitations on the present application.

[0076] 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, rather than an absolutely accurate number.

[0077] Example 1

[0078]

[0079] Step 1 specifically includes the following process:

[0080] In a reaction flask, add raw material A-1 (1.0 eq, CAS No.: 1575-36-6), raw material B-1 (1.0 eq, CAS No.: 37942-07-7), Na2S2O3 (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 1-1 (yield: 29.7%).

[0081] Step 2 specifically includes the following process:

[0082] In a reaction flask, add intermediate 1-1 (1.0 eq), raw material C-1 (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 xylene, replace N2, and react at an oil bath temperature of 160°C for 14h, then cool to room temperature. After direct suction 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=7:1) to obtain intermediate 2-1 (yield: 58.4%).

[0083] Step 3 specifically includes the following process:

[0084] In a reaction flask, add raw material D-1 (1.0 eq, CAS No.: 2648406-99-7), raw material E-1 (1.0 eq, CAS No.: 1257879-78-9), potassium carbonate (2.0 eq), and a mixed solution of toluene, ethanol, and water (V:V:V:=3:1:1), replace N2, then add tetrakis(triphenylphosphine)palladium (0.01 eq), and react at 95°C for 3h. After detecting the reaction by thin layer chromatography and confirming the end of the reaction, slightly reduce the temperature, extract the solution with water and dichloromethane, 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 3-1 (yield: 78.2%).

[0085] Step 4 specifically includes the following process:

[0086] In a reaction bottle, intermediate 3-1 (1.0 eq), raw material F-1 (1.5 eq, CAS No.: 73183-34-3), potassium acetate (3.0 eq) and 1,4-dioxane were added, and after nitrogen was passed, tris(dibenzylideneacetone)dipalladium (0.02 eq) and X-Phos (0.1 eq) were added, and the reaction was stirred at 120°C for 17 h. After the reaction was determined to be completed by thin layer chromatography, 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 = 1:4) was used to purify by column chromatography to obtain intermediate 4-1 (yield: 82.1%).

[0087] Step 5 specifically includes the following process:

[0088] In a reaction bottle, intermediate 4-1 (1.0 eq), intermediate 2-1 (1.0 eq) and a mixed solution of toluene, ethanol and water (V:V:V = 3:1:1) were added, and after nitrogen was passed, tetrakis(triphenylphosphine)palladium (0.03 eq) and potassium carbonate (3.0 eq) were added, and the reaction was stirred at 95°C for 9 h. After the reaction was determined 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 5-1 (yield: 81.0%).

[0089] Step 6 specifically includes the following process:

[0090] In a reaction bottle, intermediate 5-1 (1.0 eq), K2PtCl4 (1.2 eq), acetic acid and H2O were added and refluxed for 21 h. 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 = 1:6) was used to purify by column chromatography to obtain compound 1 (yield: 57.4%).

[0091] The obtained compound 1 was detected and analyzed, and the results were as follows:

[0092] HPLC purity: >99.6%.

[0093] Mass spectrometry test: Waters XEVO TQD mass spectrometer, ESI source.

[0094] Test value MS (ESI, m / Z): [M+H] + = 1025.28

[0095] Elemental analysis:

[0096] Calculated: C, 66.77; H, 5.80; N, 4.10; O, 1.56; Pt, 19.03; Si, 2.74;

[0097] Test: C, 66.39; H, 5.90; N, 4.21; O, 1.66; Pt, 19.15; Si, 2.83.

[0098] The nuclear magnetic resonance hydrogen spectrum of compound 1 is shown in Figure 1 .

[0099] Example 2

[0100]

[0101] The synthesis process of intermediate 2-2 in this example is the same as that of intermediate 2-1 in Example 1.

[0102] Raw material E is not prior art and needs to be synthesized in advance (corresponding to step 1-2), and the corresponding intermediate B is obtained.

[0103] Step 1 specifically includes the following process:

[0104] In the reaction bottle, raw material a (1.0 eq, CAS number: 73583-37-6), raw material b (1.0 eq, CAS number: 1398503-82-6), potassium carbonate (2.0 eq) and a mixed solution of toluene, ethanol and water (V:V:V:=3:1:1) were added, and then tetrakis(triphenylphosphine)palladium (0.01 eq) was added after nitrogen was passed. The temperature was raised to 95°C and reacted for 3h; 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 then a mixed solution of dichloromethane and petroleum ether (V:V=1:5) was used to purify by column chromatography to obtain intermediate A (yield: 78.8%).

[0105] Step 2 specifically includes the following process:

[0106] In the reaction bottle, intermediate A (1.0 eq), raw material c (1.5 eq, CAS number: 73183-34-3), potassium acetate (3.0 eq) and 1,4-dioxane were added, and then tris(dibenzylideneacetone)dipalladium (0.02 eq) and X-Phos (2-bis(cyclohexylphosphino)-2',4',6'-triisopropylbiphenyl, 0.1 eq) were added after nitrogen was passed. The temperature was raised to 120°C and stirred for 16h; after the reaction was confirmed to be completed by thin layer chromatography, water and dichloromethane were added to separate the liquid, the organic phase was retained and concentrated, and then a mixed solution of dichloromethane and petroleum ether (V:V=1:5) was used to purify by column chromatography to obtain intermediate B (yield: 81.7%).

[0107] Step 3 specifically includes the following process:

[0108] In a reaction bottle, raw material D-2 (1.0 eq, CAS No.: 2648406-99-7), intermediate B (1.0 eq, CAS No.: 1257879-78-9), potassium carbonate (2.0 eq), and a mixed solution of toluene, ethanol, and water (V:V:V = 3:1:1) were added, and after nitrogen was passed, tetrakis(triphenylphosphine)palladium (0.01 eq) was added, and the temperature was raised to 95°C for 4h of reaction; 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 3-2 (yield: 77.9%).

[0109] Step 4 specifically includes the following process:

[0110] In a reaction bottle, intermediate 3-2 (1.0 eq), raw material F-2 (1.5 eq, CAS No.: 73183-34-3), potassium acetate (3.0 eq), and 1,4-dioxane were added, and after nitrogen was passed, tris(dibenzylideneacetone)dipalladium (0.02 eq) and X-Phos (0.1 eq) were added, and the temperature was raised to 120°C for 18h of stirring reaction; after the reaction was confirmed to be completed by thin layer chromatography, 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 = 1:6) was used to purify by column chromatography to obtain intermediate 4-2 (yield: 80.6%).

[0111] Step 5 specifically includes the following process:

[0112] In a reaction bottle, intermediate 4-2 (1.0 eq), intermediate 2-2 (1.0 eq), and a mixed solution of toluene, ethanol, and water (V:V:V = 3:1:1) were added, and after nitrogen was passed, tetrakis(triphenylphosphine)palladium (0.03 eq) and potassium carbonate (3.0 eq) were added, and the temperature was raised to 95°C for 10h of reaction; 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 5-2 (yield: 81.4%).

[0113] Step 6 specifically includes the following process:

[0114] In a reaction bottle, intermediate 5-2 (1.0 eq), K2PtCl4 (1.2 eq), acetic acid and H2O were added and refluxed for 23 hours. The refluxed mixture thus obtained was cooled to room temperature, filtered to obtain a precipitate, the precipitate was dissolved in dichloromethane and washed by water, then the organic phase was reserved and concentrated, purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V:V=1:6) to obtain compound 2 (yield: 57.1%).

[0115] The obtained compound 2 was detected and analyzed, and the results were as follows:

[0116] HPLC purity: >99.4%.

[0117] Mass spectrometry test: mass spectrometer of Waters XEVO TQD type, using ESI source.

[0118] Test value MS (ESI, m / Z): [M+H] + =1042.19

[0119] Elemental analysis:

[0120] Calculated value: C, 66.83; H, 6.19; N, 4.03; O, 1.53; Pt, 18.72; Si, 2.69;

[0121] Test value: C, 66.43; H, 6.30; N, 4.13; O, 1.65; Pt, 18.83; Si, 2.79.

[0122] In addition, it should be noted that other compounds of the present application can be obtained by referring to the synthesis methods of the above-mentioned examples, so they will not be listed one by one here.

[0123] The following will specifically describe the organic electroluminescent composition and the organic electroluminescent device provided by the present application in combination with specific examples.

[0124] Device Example 1: Preparation of a green organic electroluminescent device

[0125] The structure of the prepared OLED device is: ITO anode / HIL / HTL / Prime / EML / HBL / ETL / EIL / cathode / CPL.

[0126] a. ITO anode: ITO (indium tin oxide)-Ag-ITO glass substrate with a coating thickness of 1500 angstroms was cleaned in distilled water for 3 times, ultrasonic washing for 40 min, and then cleaned in distilled water for 3 times, ultrasonic washing for 20 min. After washing, the substrate was dried, and then transferred to a plasma cleaning machine for washing for 5 min. Then, the substrate was sent to an evaporation machine, and other functional layers were evaporated on the substrate as an anode.

[0127] b. HIL (hole injection layer): HT and P-dopant were vacuum evaporated at an evaporation rate of 1 angstrom / s. The chemical formula of the HT and P-dopant is shown below. The evaporation rate ratio of the HT and P-dopant was 97:3, and the thickness was 10 nm.

[0128] c. HTL (hole transport layer): HT was vacuum evaporated on the hole injection layer at an evaporation rate of 1.5 angstrom / s, and the thickness was 130 nm, serving as a hole transport layer.

[0129] d. Prime (light-emitting auxiliary layer): Prime was vacuum evaporated on the hole transport layer at an evaporation rate of 0.5 angstrom / s, and the thickness was 100 nm, serving as a light-emitting auxiliary layer.

[0130] e. EML (light-emitting layer): Then, a double-host material (Host-1 and Host-2) and a doping material (Compound 1 provided in the above embodiment) were vacuum evaporated on the light-emitting auxiliary layer at an evaporation rate of 1 angstrom / s, and the thickness was 30 nm, serving as a light-emitting layer. The ratio of Host-1 and Host-2 was 50:50, and the evaporation rate ratio of the double-host material and the doping material was 90:10.

[0131] f. HBL (hole blocking layer): A hole blocking layer HB was vacuum evaporated at an evaporation rate of 0.5 angstrom / s, and the thickness was 5 nm.

[0132] g. ETL (electron transport layer): ET and Liq were vacuum evaporated at an evaporation rate of 1 angstrom / s, and the thickness was 30 nm, serving as an electron transport layer. The chemical formula of the ET is shown below. The evaporation rate ratio of the ET and Liq was 50:50.

[0133] h. EIL (electron injection layer): Yb was evaporated at an evaporation rate of 0.5 angstrom / s, and the thickness was 1 nm, forming an electron injection layer.

[0134] i. Cathode: Magnesium and silver were evaporated at an evaporation rate of 1 angstrom / s, and the thickness was 13 nm. The evaporation rate ratio of magnesium and silver was 1:9, and an OLED device was obtained.

[0135] j. CPL (light out-coupling layer): CPL was vacuum deposited on the cathode as a light out-coupling layer with a thickness of 65 nm at a deposition rate of 1 A / s.

[0136] k. Subsequently, the substrate on which the deposition was completed was encapsulated. First, the cleaned cover plate was coated with UV glue using a coating device, and then the coated cover plate was moved to a pressing section, the substrate on which the deposition was completed was placed on the end of the cover plate, and finally the substrate and the cover plate were laminated under the action of a laminating device, and the UV glue was simultaneously cured by light.

[0137] The structures of HT, P-dopant, Host-1, Host-2, Prime, HB, ET, and CPL used in the above device embodiment 1 are shown below:

[0138] .

[0139] Referring to the method provided in the above device embodiment 1, the corresponding compounds in Table 1 were respectively selected to replace compound 1 to perform the deposition of the doped material layer, and the corresponding organic electroluminescent devices were prepared and were respectively recorded as device embodiments 2-102.

[0140] Device comparative examples 1-14:

[0141] This comparative example provides an organic electroluminescent device, and the only difference between the preparation method of the organic electroluminescent device and device embodiment 1 is that the organic electroluminescent device is deposited by using existing comparative compounds a-n to replace the doped material (compound 1) in the above device embodiment 1. The chemical structural formulas of the comparative compounds a-n are as follows:

[0142] .

[0143] Under the current density test condition of 20 mA / cm 2 The driving voltage, luminous efficiency, and lifetime of the organic electroluminescent devices obtained from the above device embodiments 1-102 and device comparative examples 1-14 were characterized, and the test results are shown in Table 1 below.

[0144] Table 1

[0145]

[0146]

[0147]

[0148] As can be seen from Table 1, 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.

[0149] Generally, the device lifespan can be improved by 10%, and in the art, it can be considered that the compound has achieved significant performance improvement, the efficiency is improved by more than 5%, and it can be considered that the efficiency has been significantly improved.

[0150] At a current density of 20 mA / cm 2 Hereinafter, the efficiency of the compound of the present application is 172.5-178.5 cd / A, the luminous efficiency of the comparative compound is 157.5-162.6 cd / A, the efficiency is improved by 6.09%-13.33%, the lifespan of the compound of the present application is 225-263 h, and the lifespan of the comparative compound is 162-185 h, and the lifespan is improved by at least 21.62%. It can be seen that the compound of the present application has made significant progress in luminous efficiency and lifespan compared with the prior art.

[0151]

[0152] The comparative compound a and the compound 1 are parallel comparative examples, the difference between them is that in the comparative compound a, a tert-butyl group is connected to the benzene ring at the upper right corner of the right parent nucleus as a substituent, while in the compound 1 of the present application, a trimethylsilyl group (TMS) is connected to the benzene ring at the corresponding position as a substituent. The Pt complex parent nucleus has a planar tetragonal structure, which is prone to intermolecular π-π stacking interaction leading to concentration quenching, and the electronegativity of silicon atom is lower than that of carbon atom, which makes the methyl group on the silicon atom more inclined to push the electron density to the silicon atom through hyperconjugation (σ-hyperconjugation). Since the bonding orbital energy level of silicon and the directly connected atom (aromatic ring carbon) is high, these electrons are more likely to be donated to the metal center or the conjugated system. In addition, the Si-C bond is longer than the C-C bond, which makes the three methyl groups more separated in space. The huge steric hindrance of TMS prevents the close approach of the Pt complex core plane, effectively reducing the intermolecular π-π stacking interaction. The concentration quenching effect is significantly reduced, allowing higher doping concentration to be used without losing efficiency or color purity. It is more helpful to improve the carrier capture efficiency and improve the device efficiency. Moreover, the large steric hindrance TMS group can also inhibit the twisting vibration of the complex planar structure to some extent, reduce the non-radiative deactivation channel, inhibit the non-radiative d-d transition, and prevent efficiency loss.

[0153] In addition, compared with the comparative compound a having a tert-butyl group at the substitution site, in compound 1 having a trimethylsilyl (TMS) group, it is confirmed that it has a short wavelength shift (blue shift) suitable for high color purity, high glass transition temperature (Tg) and high melting temperature (Tm) characteristics caused by improved thermal stability, and the π-π stacking interaction is effectively regulated, and has a lower sublimation purification temperature under the same conditions (as shown in Table 2 below). The improved thermal characteristics and lower deposition temperature can fully explain that the deposition material not only has excellent processability, but also can realize the long service life of the device.

[0154] Table 2

[0155]

[0156] (1) The related test instruments are as follows:

[0157] Ø 80 sublimation instrument: Model CM:ON-80.

[0158] Differential scanning calorimeter: Model DSC3500.

[0159] (2) The PL test conditions are as follows:

[0160] Emission starting wavelength: 350 nm.

[0161] Emission ending wavelength: 650 nm.

[0162] Excitation wavelength: 375 nm.

[0163] Sample concentration: 0.5 mg / mL diluted 100 times.

[0164] Solvent: Tetrahydrofuran.

[0165] The applicant declares that the green phosphor dopant material, the preparation method thereof, the organic electroluminescent device and the organic electroluminescent apparatus of the present application are illustrated by the above-mentioned examples, but the present application is not limited to the above-mentioned examples, that is, it does not mean that the present application must rely on the above-mentioned examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of the selected raw materials of the present application, addition of auxiliary ingredients, selection of specific methods, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A green phosphorescent doping material, characterized in that: The general structural formula of the green phosphorescent doping material is Chemical Formula I: ； in, Ring H is phenyl, naphthyl, dibenzofuranyl or dibenzothienyl; Ar is selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl; R1 and R2 are independently selected from hydrogen, deuterium, halogen, cyano, trimethylsilyl, trifluoromethyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C24 aryl; R3 is independently selected from hydrogen, deuterium, halogen, cyano, trimethylsilyl, trifluoromethyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, wherein the heteroatom contains at least one of O, S, N, Si or Se; n1 is an integer selected from 0, 1, 2 or 3; n2 is an integer selected from 0, 1, 2, 3 or 4; n3 is an integer selected from 0, 1, 2, 3 or 4; R4-R6 are independently selected from deuterium, halogen, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, selenanyl, amino, boryl, germanyl, silanyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C1-C10 heterocycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C1-C10 heteroalkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or a combination thereof; R7 and R8 are independently selected from hydrogen, deuterium, fluorine, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl; m is an integer selected from 0, 1 or 2; In chemical formula I, two of the four bonds connecting to the intermediate metal Pt are coordination bonds and two are covalent bonds. The bonds between the metal Pt and the two N atoms are coordination bonds, the bond between Pt and the ring H atoms is a covalent bond, and the bond between Pt and O atoms is a covalent bond. The hydrogen involved in formula I is undeuterated, partially deuterated or fully deuterated.

2. The green phosphorescent doping material according to claim 1, characterized in that: Ring H is phenyl; Ar is selected from substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted C5-C24 heteroaryl; R1 and R2 are independently selected from hydrogen, deuterium, halogen, cyano, trimethylsilyl, trifluoromethyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C18 aryl; R3 is independently selected from hydrogen, deuterium, halogen, cyano, trimethylsilyl, trifluoromethyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C5-C24 heteroaryl, wherein the heteroatom contains at least one of O, S, N, Si and Se; R4-R6 are independently selected from deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C1-C6 heteroalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C5-C24 heteroaryl, or a combination thereof; R7 and R8 are independently selected from hydrogen, deuterium, fluorine, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 heteroalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C2-C5 heterocycloalkyl, substituted or unsubstituted C6-C18 aryl and substituted or unsubstituted C5-C24 heteroaryl.

3. The green phosphorescent doping material according to claim 1, characterized in that: The general structural formula of the green phosphorescent doping material is the following chemical formula IA: ； wherein Ar1 and Ar2 are independently selected from hydrogen, deuterium, halogen, cyano, trimethylsilyl, trifluoromethyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C5-C24 heteroaryl; n9、n 10 An integer independently selected from 0, 1, 2, 3, 4 or 5; R1 and R2 are independently selected from hydrogen, deuterium, cyano, trimethylsilyl, trifluoromethyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl; R3 is independently selected from hydrogen, deuterium, cyano, trimethylsilyl, trifluoromethyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted furanyl, substituted or unsubstituted substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted isobenzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzisothiazolyl, substituted or unsubstituted benzisoxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted isoindole, substituted or unsubstituted indolyl, substituted or unsubstituted benzindolyl, substituted or unsubstituted benzothiadiazolyl; R4-R6 are independently selected from deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted cyclohexane, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane ... substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted isobenzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl; R7, R8 are independently selected from deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted cyclohexane, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane ... substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted isobenzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl.

4. The green phosphorescent doping material according to claim 1, characterized in that: The general structural formula of the green phosphorescent doping material is: ； ； Ar1 and Ar2 are independently selected from deuterium, cyano, trimethylsilyl, trifluoromethyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane, substituted or unsubstituted cyclohexane, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted phenyl groups ... substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted isobenzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl.

5. The green phosphorescent doping material according to any one of claims 1 to 4, characterized in that: The "substituted" group in the substituted or unsubstituted group is selected from the following groups, one or at least two of which are connected: deuterium, halogen, cyano, trimethylsilyl, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, 1-methylhexyl, cyclopentyl ... Propane, cyclobutane, cyclopentane, cyclohexane, phenyl, biphenyl, naphthyl, terphenyl, fluorenyl, dimethylfluorenyl, phenanthryl, anthracenyl, indenyl, triphenylene, pyrenyl, chrysyl, furyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzindolyl, benzothiadiazolyl, carbazolyl, benzocarbazolyl, and adamantyl.

6. The green phosphorescent doping material according to claim 1, characterized in that: The green phosphorescent doping material is any one of the following compounds: ； ； ； ； ； ； ； ； ； Where D stands for deuterium.

7. An organic electroluminescent device, characterized in that: The organic electroluminescent device includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode. The organic layer includes a light-emitting layer. The light-emitting layer includes the green phosphorescent doping material according to any one of claims 1 to 6.

8. The organic electroluminescent device according to claim 7, characterized in that: The light-emitting layer includes a host material and a doping material, and the doping material is the green phosphorescent doping material according to any one of claims 1 to 6.

9. The organic electroluminescent device according to claim 7, characterized in that: The organic layer further includes any one of a hole injection layer, a hole transport layer, an electron blocking layer, a luminescence auxiliary layer, an electron transport layer, an electron injection layer or a hole blocking layer, or a combination of at least two of them.

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