Organometallic compound and organic electroluminescent device

Abstract

The application provides an organic metal compound and an organic electroluminescent device, and belongs to the field of organic photoelectric materials.The organic metal compound has a structure shown in formula I, the organic metal compound of the application introduces a suitable steric hindrance structure unit on Pt, links groups such as adamantane, trifluoromethyl and tert-butyl at specific positions to change the spatial configuration and stereoscopic structure among molecules, set the molecular orientation, adjust the steric hindrance, and match the device structure of the application, so that the obtained organic compound has the characteristics of long service life, high efficiency and low driving voltage when used in the organic electroluminescent device.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic optoelectronic materials, and particularly relates to an organic metal compound and an organic electroluminescent device. BACKGROUND

[0002] Organic semiconductor materials belong to a new type of optoelectronic materials, which originated from the discovery of doped polyacetylene with copper level conductivity by Shirakawa, A. Heeger and A. McDiamid in 1977. Subsequently, in 1987, C. Tang et al. of Kodak Company invented an organic small molecule light emitting diode (OLED). OLED uses an organic thin film which emits light when a voltage is applied to the device. OLED is becoming an increasingly popular technology for applications such as flat panel displays, lighting and backlights.

[0003] Optoelectronic devices that utilize organic materials are becoming increasingly important for a variety of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic optoelectronic devices have the potential to be lower cost than alternative inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, can make them well suited for particular applications, such as manufacturing on a flexible substrate. Examples of organic optoelectronic devices include organic light emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the active layers can have a small thickness of only two monolayers up to several hundred monolayers. As such, OLEDs can be used to realize full color displays. OLEDs utilizing organic materials are becoming an increasingly popular technology for a variety of applications, including full color displays. An OLED is typically fabricated by depositing a thin layer (typically less than 1,000 nm) of an organic material onto a substrate.

[0004] Therefore, how to provide a green phosphor organic electroluminescent material with long service life, high efficiency and low driving voltage is a problem to be solved by those skilled in the art. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide an organic metal compound and an organic electroluminescent device.

[0006] To achieve the purpose of the present application, the following technical solutions are adopted:

[0007] In one aspect, the present application provides an organic metal compound, which has the structure shown in formula I:

[0008]

[0009] wherein X is a metal, preferably Pt.

[0010] Ring A is selected from benzene, naphthalene, dibenzofuran, dibenzothiophene;

[0011] R1-R4 are each independently selected from hydrogen, deuterium, fluorine, trifluoromethyl, trimethylsilyl, trimethylgermyl, cyano, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heteroaryl, which heteroatom is one or a combination of at least two of O, S, N, Si, Ge or Se; R1-R3 are independently present or two adjacent substituents are connected to each other to form a ring;

[0012] R5 is each independently selected from trifluoromethyl or tert-butyl;

[0013] n, q, o are each independently selected from an integer from 0 to 4 (e.g., can be 0, 1, 2, 3, or 4);

[0014] p is an integer from 0 to 3 (e.g., can be 0, 1, 2, or 3);

[0015] m is an integer from 0 to the maximum number of substitutions possible for the A ring;

[0016] All hydrogens in formula I are independently substituted with deuterium or not substituted with deuterium.

[0017] Further, R1-R4 are each independently selected from hydrogen, deuterium, fluorine, trifluoromethyl, trimethylsilyl, trimethylgermyl, cyano, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C3-C15 heteroaryl, which heteroatom is one or a combination of at least two of O, S, N, Si, Ge or Se.

[0018] Still further, the organometallic compound has a structure according to any one of formulas I-1 to I-8:

[0019]

[0020] wherein R1-R4 are each independently selected from hydrogen, deuterium, fluorine, trifluoromethyl, trimethylsilyl, trimethylgermyl, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclopropanyl, substituted or unsubstituted cyclobutanyl, substituted or unsubstituted cyclopentanly, substituted or unsubstituted cyclohexanly;

[0021] n, q, o are independently selected from an integer of 0 to 4;

[0022] p, m are selected from an integer of 0 to 3;

[0023] and, all hydrogens in the above I-1 to I-3 are independently substituted with deuterium or are not substituted with deuterium;

[0024] wherein TMS represents a trimethylsilyl group.

[0025] Most preferably, R2 is selected from a tert-butyl group, and q is an integer of 1 or 2.

[0026] The number of carbon atoms in the term "substituted or unsubstituted C6-C30 aryl group", "substituted or unsubstituted C1-C30 alkyl group", "substituted or unsubstituted C3-C30 heteroaryl group", "substituted or unsubstituted C6-C18 aryl group", "substituted or unsubstituted C1-C15 alkyl group", "substituted or unsubstituted C3-C15 heteroaryl group", "substituted or unsubstituted C6-C15 aryl group", "substituted or unsubstituted C1-C6 alkyl group", "substituted or unsubstituted C3-C15 heteroaryl group", "substituted or unsubstituted C3-C30 cycloalkyl group", "substituted or unsubstituted C3-C15 cycloalkyl group", "substituted or unsubstituted C3-C10 cycloalkyl group" indicates the number of carbon atoms constituting the unsubstituted aryl group, unsubstituted alkyl group, unsubstituted cycloalkyl group, or the total number of heteroatoms and carbon atoms constituting the heteroaryl group, without considering the number of carbon atoms in the substituents.

[0027] The term "substituted" means substituted with one, two or more substituents selected from the group consisting of hydrogen, deuterium, a halogen group, a cyano group, a trifluoromethyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, a sec-butyl group, a 1-methylbutyl group, a 1-ethylbutyl group, an n-pentyl group, an iso-pentyl group, a neopentyl group, a tert-pentyl group, an n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a 1-methylhexyl group, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a thienyl group, a furanyl group, a pyrrolyl group, a benzothienyl group, a benzofuranyl group, a pyridyl group, an indolyl group, a cyclopentane group, a cyclohexane group, an adamantane group.

[0028] Preferably, the organometallic compound is any one of the following compounds, but is not limited thereto:

[0029] ;

[0030] ;

[0031] ;

[0032] ;

[0033] ;

[0034] ;

[0035] ;

[0036] ;

[0037] ;

[0038] Where D represents deuterium and TMS represents trimethylsilyl.

[0039] A second objective of this invention is to provide a method for preparing the above-mentioned organometallic platinum complex, which can be prepared by methods known to those skilled in the art.

[0040] The following are common knowledge references:

[0041] Organometallic Chemistry (6th Edition), Robert H. Crabtree, published by East China University of Science and Technology Press, Shanghai, September 00, 2017, ISBN: 978-7-5628-5111-0, page 388.

[0042] Organic Chemistry and Optoelectronic Materials Experiment Tutorial, Chen Runfeng, Publisher: Southeast University Press, Publication Date: 2019-11-00, ISBN: 9787564184230, Page 174.

[0043] Alternatively, the following reaction procedure is preferred for preparation, and the specific synthetic route is as follows:

[0044]

[0045] The limitations in the above formula are the same as those mentioned above, and will not be repeated here. Boc represents tert-butyloxycarbonyl.

[0046] The specific synthesis steps are as follows:

[0047] Step 1 specifically includes the following steps: under a nitrogen environment, the raw material A (1.0-1.1 eq) is dissolved in DCM, TEA (2.0-2.4 eq) is added, cooled to 0°C, (Boc)20 (1.5-1.8 eq) is slowly added, then warmed to room temperature, reacted at room temperature for 3-4 h, the reaction is detected by thin layer chromatography, after the reaction is completed, water is slowly added to quench, and it is left to stand until the layers separate, the organic phase is retained, then the aqueous phase is extracted with dichloromethane; after the organic phases are combined, they are concentrated, eluted with a mixture of dichloromethane and petroleum ether, and purified by column chromatography to obtain intermediate 1;

[0048] Step 2 specifically includes the following steps: under a nitrogen environment, the obtained intermediate 1 (1.0 eq) and raw material B (1.2 eq) are dissolved in tetrahydrofuran, S-phos (2-bicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl, 0.04-0.06 eq) and Pd2(dba)3 (tris(dibenzylideneacetone)dipalladium, 0.04-0.06 eq) are added, and the reaction is carried out at 50-60°C for 4-8 h, the reaction is detected by thin layer chromatography, after the reaction is completed, it is cooled to room temperature, water is slowly added to quench, and it is left to stand until the layers separate, the organic phase is retained, then the aqueous phase is extracted with dichloromethane; after the organic phases are combined, they are concentrated, eluted with a mixture of dichloromethane and petroleum ether, and purified by column chromatography to obtain intermediate 2;

[0049] Step 3 specifically includes the following steps: under a nitrogen environment, intermediate 2 (1.0 eq) is dissolved in DCM, triflic acid (1.0-1.2 eq) is added, and the reaction is carried out at room temperature for 4-8 h, the reaction is detected by thin layer chromatography, after the reaction is completed, water is slowly added to quench, and it is left to stand until the layers separate, the organic phase is retained, then the aqueous phase is extracted with dichloromethane; after the organic phases are combined, they are concentrated, eluted with a mixture of dichloromethane and petroleum ether, and purified by column chromatography to obtain intermediate 3;

[0050] Step 4 specifically includes the following steps: under a nitrogen environment, intermediate 3 (1.2 eq) is dissolved in THF, cooled to -78°C, and n-butyllithium (1.4-1.6 eq) is slowly added, stirred for two hours, then a THF (tetrahydrofuran) solution of raw material C (1.0 eq) is added while warming to -25°C, and stirring is continued for 2-4 h, the reaction is detected by thin layer chromatography, after the reaction is completed, it is warmed to room temperature, water is slowly added to separate the phases, the organic phase is collected, the remaining aqueous phase is extracted with DCM (dichloromethane), concentrated, dissolved in DCM, silica gel is added, and column chromatography is used for purification to obtain intermediate 4;

[0051] Step 5 specifically includes the following steps: under a nitrogen environment, intermediate 4 (1.0 eq) is dissolved in THF, Na2S2O4 (4.0-4.2 eq) is added, stirred uniformly, and reacted at room temperature for 40-48 h. The reaction is detected by thin layer chromatography. After the reaction is completed, saturated brine and EA (ethyl acetate) are added, and the organic phase is collected and concentrated. A mixed solution of dichloromethane and petroleum ether is used as an eluent, and column chromatography is used for purification to obtain intermediate 5;

[0052] Step 6 specifically includes the following steps: under a nitrogen environment, intermediate 5 (1.0 eq) and raw material D (1.0 eq) are dissolved in DMF (N,N-dimethylformamide), Na2S2O5 (2.0-2.2 eq) is added, stirred uniformly, and reacted at 110-120°C for 4-6 h. The reaction is detected by thin layer chromatography. After the reaction is completed, it is cooled to room temperature, water is slowly added, and a solid is precipitated. Filtration is performed to obtain intermediate 6;

[0053]

[0054] Step 7 specifically includes the following steps: under a nitrogen environment, raw material E (1.0 eq) and raw material F (1.3 eq) are dissolved in THF and water as solvents, NaOH (1.2-1.3 eq) and triphenylphosphine (0.03-0.05 eq) are added, and the reaction is performed at 45-60°C for 5-8 h. The reaction is detected by thin layer chromatography. After the reaction is completed, it is cooled to room temperature, and the organic phase is extracted with saturated brine and separated. The organic phase is dried and added to DCM silica gel for filtration to obtain intermediate 7;

[0055] Step 8 specifically includes the following steps: under a nitrogen environment, intermediate 7 (1.0 eq), raw material G (1.2-1.3 eq), potassium carbonate (1.1-1.2 eq), triphenylphosphine, palladium acetate, and n-BuNBr (n-butyl ammonium bromide) are dissolved in dioxane and water, stirred uniformly, and then heated to 50-60°C for 5-8 h. The reaction is detected by thin layer chromatography. After the reaction is completed, it is cooled to room temperature, extracted with DCM, and separated. The organic phase is collected and concentrated. A mixed solution of dichloromethane and petroleum ether is used as an eluent, and column chromatography is used for purification to obtain intermediate 8;

[0056] Step 8 specifically includes the following steps: under a nitrogen environment, intermediate 8 (1.0 eq), raw material H (1.3 eq) and potassium acetate (1.1-1.3 eq) are dissolved in dioxane and water, the mixed solution is bubbled with nitrogen for 5 minutes at room temperature, then Pd(dppf)Cl2 ([1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium, 0.08-0.12 eq) is added, nitrogen bubbling is continued for 5 minutes, then the temperature is raised to 80-90°C and the reaction is refluxed for 10-12 hours, the reaction is detected by thin layer chromatography, after the reaction is completed, it is cooled to room temperature, extracted with EA and saturated brine, the organic phase is collected and concentrated, a mixed solution of dichloromethane and petroleum ether is used as eluent, and intermediate 9 is obtained by column chromatography;

[0057]

[0058] Step 9 specifically includes the following steps: under a nitrogen environment, intermediate 6 (1.0 eq) and intermediate 9 (1.3 eq) and potassium acetate (2.0-2.2 eq) are dissolved in dioxane and water, the mixed solution is bubbled with nitrogen for 5 minutes at room temperature, then lead acetate (0.04-0.06 eq) and X-phos (2-dicyclohexylphosphino-2',4',6'-triisopropyl biphenyl, 0.04-0.06 eq) are added, nitrogen bubbling is continued for 5 minutes, then the temperature is raised to 80-90°C and the reaction is refluxed for 4-6 hours, the reaction is detected by thin layer chromatography, after the reaction is completed, it is cooled to room temperature, extracted with EA and saturated brine, the organic phase is collected and concentrated, a mixed solution of dichloromethane and petroleum ether is used as eluent, and intermediate 10 is obtained by column chromatography.

[0059] Step 10 specifically includes the following steps: under a nitrogen environment, intermediate 10 (1.0 eq) and K2PtCl4 (1.2-1.4 eq) are dissolved in a mixed solution of CHCl3 and HOAc (volume ratio 1:1), heated to reflux for 36-48 hours, the reaction is detected by thin layer chromatography, after the reaction is completed, it is cooled to room temperature, purified by column chromatography to obtain compound formula I.

[0060] In another aspect, the present application provides an organic electroluminescent device, which comprises an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a host material and a dopant material, and the dopant material comprises the organometallic compound as described above.

[0061] Preferably, the mass ratio of the host material and the dopant material is 90-99.5:0.5-10, for example 90:10, 92:8, 93:7, 94:6, 95:5, 96:4, 97:3, 98:2, 99:1 or 99.5:0.5.

[0062] Preferably, the organic layer further includes 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, a hole blocking layer, an electron transport layer, and an electron injection layer. However, the structure of the organic light emitting element is not limited thereto, and can include a smaller or greater number of organic layers.

[0063] The organic electroluminescent device can further include a cap layer.

[0064] As for the compound represented by the above Formula I, in the production of the organic electroluminescent device, the organic layer can be formed using a vacuum evaporation method, or a solution coating method. Among them, the solution coating method refers to a spin coating method, a dip coating method, a blade coating method, an inkjet printing method, a screen printing method, a spray method, a roll coating method, etc., but is not limited thereto.

[0065] The organic electroluminescent device of the present application can be a top emission type, a bottom emission type, or a bidirectional emission type, depending on the materials used.

[0066] The organic electroluminescent device of the present application can be used in an organic light emitting device, an organic solar cell, electronic paper, an organic photoreceptor, or an organic thin film transistor.

[0067] As an anode material, a material with a large work function is generally preferred in order to enable smooth injection of holes into the organic layer. As specific examples of the anode material that can be used in the present application, there are metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; combinations of a metal and an oxide such as ZnO:Al or SnO2:Sb.

[0068] The hole injection layer is preferably a p-doped hole injection layer, which means a hole injection layer doped with a p-dopant. The p-dopant is a material that imparts p-type semiconductor properties. The p-type semiconductor properties mean the property of injecting or transporting holes at the HOMO level, i.e., the property of a material having a high hole conductivity.

[0069] The hole transport material is a material that can receive holes from the anode or the hole injection layer and transport the holes to the light emitting layer, and has a high hole mobility. The hole transport material can be selected from arylamine derivatives, conductive polymers, and block copolymers having both a conjugated portion and a non-conjugated portion, etc.

[0070] An emission auxiliary layer (a multi-hole transport layer) is added between the hole transport layer and the light emitting layer. The emission auxiliary layer mainly functions as an auxiliary hole transport layer, and is sometimes referred to as a second hole transport layer. The emission auxiliary layer enables smooth movement of holes transferred from the anode to the light emitting layer, and can block electrons transferred from the cathode to confine the electrons within the light emitting layer, reduce the potential barrier between the hole transport layer and the light emitting layer, lower the driving voltage of the organic electroluminescent device, further increase the utilization rate of holes, and thus improve the light emitting efficiency and the lifetime of the device.

[0071] The light emitting substance of the light emitting layer is a substance capable of receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and causing the holes and the electrons to combine to emit light in the visible light region, and is preferably a substance having high quantum efficiency for fluorescence or phosphorescence.

[0072] The host material of the light emitting layer is an aromatic condensed ring derivative or a heterocyclic compound, etc. Specifically, as the aromatic condensed ring derivative, there are anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and as the heterocyclic compound, there are carbazole derivatives, diphenyl furan derivatives, pyrimidine derivatives, etc.

[0073] The electron transport layer can function to promote electron transport. The electron transport material is a material that advantageously receives electrons from the cathode and transports the electrons to the light emitting layer, and is preferably a material having high electron mobility. The electron transport layer can include at least one of an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and preferably at least one of the electron transport layer and the electron injection layer.

[0074] The electron injection layer can function to promote electron injection. It has the ability to transport electrons and prevents excitons generated in the light emitting layer from migrating to the hole injection layer. The material of the electron injection layer includes oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenyl methane, anthracene ketone, and derivatives thereof, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, ytterbium, and alloys thereof, metal complexes, nitrogen-containing 5-membered ring derivatives, etc., but is not limited thereto.

[0075] The cathode is generally preferably a material having a small work function to enable smooth injection of electrons into the organic material layer, and the layer thickness thereof is preferably between 0.5 and 5 nm. The cathode material is generally a material having a small work function to enable easy injection of electrons into the organic material layer. As specific examples of the cathode material, there are metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof: LiF / Al or LiO2 / Al, a multi-layered structure material such as Mg / Ag, etc.

[0076] Except for the doping material disclosed in the present application, there is no special limitation for other layer materials in the OLED device. The existing hole injection material, hole transport material, hole transport auxiliary material, dopant material, hole blocking layer material, electron transport layer material and electron injection material can be used.

[0077] Compared with the prior art, the present application has the following beneficial effects:

[0078] The organic metal compound of the present application introduces a suitable steric hindrance structural unit on Pt, links groups such as adamantane, trifluoromethyl and tert-butyl at a specific position to change the spatial configuration and stereoscopic structure between molecules, set the molecular orientation, adjust the steric hindrance, and match the device structure of the present application, so that the obtained organic compound has the characteristics of long service life, high efficiency and low driving voltage when used in an organic electroluminescent device. BRIEF DESCRIPTION OF DRAWINGS

[0079] Figure 1 The nuclear magnetic resonance hydrogen spectrum of compound 105. DETAILED DESCRIPTION

[0080] The technical solutions of the present application are further illustrated by the 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 a specific limitation on the present application.

[0081] Example 1: synthesis of compound 105

[0082]

[0083] Step 1 specifically includes the following steps: under a nitrogen environment, dissolving the raw material A-105 (1.0 eq, CAS number: 445-02-3) in DCM, adding TEA (2.0 eq) thereto, cooling to 0°C, slowly adding (Boc)2O (di-tert-butyl carbonate, 1.5 eq) thereto, then warming to room temperature, reacting at room temperature for 4 h, detecting the reaction by thin layer chromatography, after the reaction is completed, slowly adding water thereto for quenching, standing and waiting for phase separation, retaining the organic phase, then extracting the aqueous phase with dichloromethane; after the organic phases are combined, concentrating, using a mixed solution of dichloromethane and petroleum ether as an eluent, purifying by column chromatography to obtain the intermediate 1 (yield: 42.4%);

[0084] Step 2 specifically includes the following steps: the obtained intermediate 1 (1.0 eq) and raw material B-105 (1.2 eq, CAS No.: 312624-15-0) are dissolved in tetrahydrofuran under a nitrogen environment, S-phos (0.04 eq) and Pd2(dba)3 (0.04 eq) are added thereto, and reaction is carried out at 50°C for 4 h. After the reaction is completed, it is lowered to room temperature, water is slowly added thereto for quenching, and it is left to stand for layer separation. The organic phase is reserved, and then the aqueous phase is extracted with dichloromethane. After the organic phases are combined, they are concentrated, and a mixed solution of dichloromethane and petroleum ether is used as an eluent to purify the intermediate 2 by column chromatography (yield: 21.9%);

[0085] Step 3 specifically includes the following steps: intermediate 2 (1.0 eq) is dissolved in DCM under a nitrogen environment, trifluoromethanesulfonic acid (1.0 eq) is added thereto, and reaction is carried out at room temperature for 8 h. After the reaction is completed, water is slowly added thereto for quenching, and it is left to stand for layer separation. The organic phase is reserved, and then the aqueous phase is extracted with dichloromethane. After the organic phases are combined, they are concentrated, and a mixed solution of dichloromethane and petroleum ether is used as an eluent to purify the intermediate 3 by column chromatography (yield: 70.8%);

[0086] Step 4 specifically includes the following steps: intermediate 3 (1.2 eq) is dissolved in THF under a nitrogen environment, and it is cooled to -78°C. Normal butyl lithium (1.4 eq) is slowly added thereto, and it is stirred for two hours. Then, a THF solution of raw material C-105 (1.0 eq, CAS No.: 886762-70-5) is added thereto while being warmed to -25°C, and it is continuously stirred for 2 h. After the reaction is completed, it is warmed to room temperature, water is slowly added thereto for phase separation, the organic phase is collected, the remaining aqueous phase is extracted with DCM, and then it is concentrated and dissolved in DCM. Silica gel is added thereto, and column chromatography is used for purification to obtain the intermediate 4 (yield: 63.5%);

[0087] Step 5 specifically includes the following steps: intermediate 4 (1.0 eq) is dissolved in THF under a nitrogen environment, Na2S2O4 (4.0 eq) is added thereto, and it is stirred uniformly. Reaction is carried out at room temperature for 48 h. After the reaction is completed, saturated brine and EA are added thereto for extraction and phase separation. The organic phase is collected, concentrated, and a mixed solution of dichloromethane and petroleum ether is used as an eluent to purify the intermediate 5 by column chromatography (yield: 81.6%);

[0088] Step 6 comprises the following steps in particular: intermediate 5 (1.0 eq) and raw material D-105 (1.0 eq) (CAS No.: 37942-07-7) are dissolved in DMF under nitrogen atmosphere, Na2S2O5 (2.0 eq) is added thereto, stirring is uniform, reaction is carried out at 110°C for 4h, reaction is detected by thin layer chromatography, after reaction is completed, it is cooled to room temperature, water is slowly added thereto, solid is precipitated, filtration is extracted, and intermediate 6 (yield: 60.7%) is obtained;

[0089] ;

[0090] Step 7 comprises the following steps in particular: raw material E-105 (1.0 eq, CAS No.: 22918-01-0) and raw material F-105 (1.3 eq, CAS No.: 2235417-07-7) are dissolved in THF and water as solvents under nitrogen atmosphere, NaOH (1.2 eq) and triphenylphosphine (0.03 eq) are added thereto, reaction is carried out at 45°C for 5h, reaction is detected by thin layer chromatography, after reaction is completed, it is cooled to room temperature, liquid separation is carried out, the organic phase is extracted with saturated brine, liquid separation is carried out again, the organic phase is concentrated, DCM is added, silica gel is added, and the mixture is stirred, and intermediate 7 (yield: 71.1%) is obtained by passing through a filter funnel;

[0091] Step 8 comprises the following steps in particular: intermediate 7 (1.0 eq), raw material G-105 (1.3 eq, CAS No.: 950603-55-1), potassium carbonate (1.1 eq), triphenylphosphine, palladium acetate and n-BuNBr are dissolved in dioxane and water under nitrogen atmosphere, stirring is uniform, then the temperature is increased to 50°C, reaction is carried out for 5h, reaction is detected by thin layer chromatography, after reaction is completed, it is cooled to room temperature, DCM is added, liquid separation is carried out, the organic phase is concentrated, a mixed solution of dichloromethane and petroleum ether is used as an eluent, and intermediate 8 (yield: 83.2%) is obtained by column chromatography;

[0092] Step 9 comprises the following steps in particular: intermediate 8 (1.0 eq), raw material H-105 (1.3 eq) and potassium acetate (1.1 eq) are dissolved in dioxane and water under nitrogen atmosphere, the mixed solution is bubbled with nitrogen for 5 minutes at room temperature, Pd(dppf)Cl2 (0.08 eq) is added thereto, nitrogen bubbling is continued for 5 minutes, then the temperature is increased to 80°C, reaction is carried out for 10-12h, reaction is detected by thin layer chromatography, after reaction is completed, it is cooled to room temperature, EA and saturated brine are added, liquid separation is carried out, the organic phase is concentrated, a mixed solution of dichloromethane and petroleum ether is used as an eluent, and intermediate 9 (yield: 82.7%) is obtained by column chromatography;

[0093] ;

[0094] Step 10 specifically comprises the following steps: intermediate 6 (1.0 eq) and intermediate 9 (1.3 eq) and potassium acetate (2.0 eq) are dissolved in dioxane and water under a nitrogen atmosphere, the mixed solution is bubbled with nitrogen for 5 minutes at room temperature, then lead acetate (0.04 eq) and X-phos (0.04 eq) are added, nitrogen bubbling is continued for 5 minutes, then the temperature is raised to 80°C and the reaction is refluxed for 6 hours, the reaction is detected by thin layer chromatography, after the reaction is completed, the temperature is lowered to room temperature, extraction is performed with EA and saturated brine, the organic phase is collected and concentrated, a mixed solution of dichloromethane and petroleum ether is used as the eluent, and column chromatography is used for purification to obtain intermediate 10 (yield: 80.6%);

[0095] Step 11 specifically comprises the following steps: intermediate 10 (1.0 eq) and K2PtCl4 (1.2 eq) are dissolved in a mixed solution of CHCl3 and HOAc (volume ratio 1:1) under a nitrogen atmosphere, heated to reflux for 48 hours, the reaction is detected by thin layer chromatography, after the reaction is completed, the temperature is lowered to room temperature, and column chromatography is used for purification to obtain compound 105 (yield: 34.8%).

[0096] Compound 105 obtained is subjected to detection and analysis, the mass spectrometer is Waters XEVO TQD, low precision, ESI source test, and the results are as follows:

[0097] Test value ((ESI, m / Z): [M+H]+): 1124.51;

[0098] The nuclear magnetic resonance hydrogen spectrum of compound 105 is as shown in Figure 1 .

[0099] HPLC purity: >99.95%.

[0100] Elemental analysis: the test value is: C, 63.57; H, 5.94; F, 5.15; N, 3.82; O, 1.53; Si, 2.61.

[0101] Example 2: Synthesis of compound 264

[0102]

[0103] Step 1 comprises the following steps: dissolving raw material A-264 (1.0 eq, CAS No.: 103273-01-4) in DCM under a nitrogen atmosphere, adding TEA (triethanolamine, 2.0 eq) thereto, cooling to 0°C, slowly adding (Boc)20 (1.5 eq) thereto, then warming to room temperature, reacting at room temperature for 4 h, detecting the reaction using thin layer chromatography, after the reaction is completed, slowly adding water thereto to quench, allowing to stand until the layers separate, retaining the organic phase, then extracting the aqueous phase with dichloromethane; after the organic phases are combined, concentrating, using a mixture of dichloromethane and petroleum ether as an eluent, purifying by column chromatography to obtain intermediate 1 (yield: 41.6%);

[0104] Step 2 comprises the following steps: dissolving the obtained intermediate 1 (1.0 eq) and raw material B-264 (1.2 eq, CAS No.: 312624-15-0) in tetrahydrofuran under a nitrogen atmosphere, adding S-phos (0.04 eq) and Pd2(dba)3 (0.04 eq) thereto, reacting at 50°C for 4 h, detecting the reaction using thin layer chromatography, after the reaction is completed, cooling to room temperature, slowly adding water thereto to quench, allowing to stand until the layers separate, retaining the organic phase, then extracting the aqueous phase with dichloromethane; after the organic phases are combined, concentrating, using a mixture of dichloromethane and petroleum ether as an eluent, purifying by column chromatography to obtain intermediate 2 (yield: 22.3%);

[0105] Step 3 comprises the following steps: dissolving intermediate 2 (1.0 eq) in DCM under a nitrogen atmosphere, adding triflic acid (1.0 eq) thereto, reacting at room temperature for 8 h, detecting the reaction using thin layer chromatography, after the reaction is completed, slowly adding water thereto to quench, allowing to stand until the layers separate, retaining the organic phase, then extracting the aqueous phase with dichloromethane; after the organic phases are combined, concentrating, using a mixture of dichloromethane and petroleum ether as an eluent, purifying by column chromatography to obtain intermediate 3 (yield: 69.5%);

[0106] Step 4 comprises the following steps: dissolving intermediate 3 (1.2 eq) in THF under a nitrogen atmosphere, cooling to -78°C, slowly adding n-butyllithium (1.4 eq) thereto, stirring for two hours, then adding a THF solution of raw material C-264 (1.0 eq, CAS No.: 886762-70-5) thereto while warming to -25°C, continuing to stir for 2 h, detecting the reaction using thin layer chromatography, after the reaction is completed, warming to room temperature, slowly adding water to the solution, collecting the organic phase, extracting the remaining aqueous phase with DCM, dissolving after concentrating in DCM, adding silica gel to the solution, purifying by column chromatography to obtain intermediate 4 (yield: 64.4%);

[0107] Step 5 specifically includes the following steps: Under nitrogen atmosphere, intermediate 4 (1.0 eq) is dissolved in THF, and Na2S2O4 (4.0 eq) is added. The mixture is stirred evenly and reacted at room temperature for 48 h. The reaction is detected by thin-layer chromatography. After the reaction is completed, saturated saline and EA are added, and the mixture is extracted and separated. The collected organic phase is concentrated and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether as eluent to obtain intermediate 5 (yield: 80.7%).

[0108] Step 6 specifically includes the following steps: Under nitrogen atmosphere, intermediate 5 (1.0 eq) and raw material D-264 (1.0 eq) (CAS No.: 37942-07-7) are dissolved in DMF, and Na2S2O5 (2.0 eq) is added. The mixture is stirred evenly and reacted at 110℃ for 4 h. The reaction is detected by thin-layer chromatography. After the reaction is completed, the mixture is cooled to room temperature, and water is slowly added to precipitate the solid. The solid is then filtered to obtain intermediate 6 (yield: 61.2%).

[0109]

[0110] Step 7 specifically includes the following steps: Under nitrogen atmosphere, raw material E-264 (1.0 eq, CAS No.: 22918-01-0) and raw material F-264 (1.3 eq, CAS No.: 2235417-07-7) are dissolved in THF and water as solvents. NaOH (1.2 eq) and triphenylphosphine (0.03 eq) are added to the solution and reacted at 45°C for 5 h. The reaction is detected by thin-layer chromatography. After the reaction is completed, the mixture is cooled to room temperature and separated. The organic phase is extracted with saturated brine and separated again. The organic phase is evaporated to dryness, mixed with DCM silica gel, and passed through a funnel to obtain intermediate 7 (yield: 71.1%).

[0111] Step 8 specifically includes the following steps: Under nitrogen atmosphere, intermediate 7 (1.0 eq), raw material G-264 (1.3 eq, CAS No.: 950603-55-1), potassium carbonate (1.1 eq), triphenylphosphine, palladium acetate and n-BuNBr are dissolved in dioxane and water, stirred evenly, and then heated to 50℃ for 5 h. The reaction is detected by thin layer chromatography. After the reaction is completed, the mixture is cooled to room temperature, extracted and separated by DCM, the collected organic phase is concentrated, and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether as eluent to obtain intermediate 8 (yield: 82.9%).

[0112] Step 9 specifically includes the following steps: under the nitrogen environment, intermediate 8 (1.0 eq), raw material H-264 (1.3 eq) and potassium acetate (1.1 eq) are dissolved in dioxane and water, the mixed solution is bubbled with nitrogen for 5 minutes at room temperature, then Pd(dppf)Cl2(0.08 eq) is added, nitrogen bubbling is continued for 5 minutes, then the temperature is raised to 80°C and the reaction is refluxed for 10-12h, the reaction is detected by thin layer chromatography, after the reaction is completed, it is cooled to room temperature, extracted with EA and saturated brine, the organic phase is collected and concentrated, and purified by column chromatography with a mixed solution of dichloromethane and petroleum ether as eluent to obtain intermediate 9 (yield: 81.6%);

[0113]

[0114] Step 10 specifically includes the following steps: under the nitrogen environment, intermediate 6 (1.0 eq) and intermediate 9 (1.3 eq) and potassium acetate (2.0 eq) are dissolved in dioxane and water, the mixed solution is bubbled with nitrogen for 5 minutes at room temperature, then lead acetate (0.04 eq) and X-phos (0.04 eq) are added, nitrogen bubbling is continued for 5 minutes, then the temperature is raised to 80°C and the reaction is refluxed for 6h, the reaction is detected by thin layer chromatography, after the reaction is completed, it is cooled to room temperature, extracted with EA and saturated brine, the organic phase is collected and concentrated, and purified by column chromatography with a mixed solution of dichloromethane and petroleum ether as eluent to obtain intermediate 10 (yield: 82.0%);

[0115] Step 11 specifically includes the following steps: under the nitrogen environment, intermediate 10 (1.0 eq) and K2PtCl4(1.2 eq) are dissolved in a mixed solution of CHCl3and HOAc (volume ratio 1:1), heated to reflux for 48h, the reaction is detected by thin layer chromatography, after the reaction is completed, it is cooled to room temperature, purified by column chromatography to obtain compound 264 (yield: 33.9%).

[0116] The obtained compound 264 is detected and analyzed, the mass spectrometer is Waters XEVO TQD, low precision, ESI source test, and the results are as follows:

[0117] Test value ((ESI, m / Z): [M+H]+): 1124.51.

[0118] HPLC purity: >99.95%.

[0119] Elemental analysis: the test value is: C, 67.54; H, 7.12; N, 3.84; O, 1.52; Si, 2.60.

[0120] In addition, it should be noted that other compounds of the present application can be obtained by reference to the synthesis methods of the above-listed examples, and thus will not be listed here.

[0121] Device Preparation Example 1

[0122] Preparation of a green organic electroluminescent device:

[0123] a. ITO anode: ITO (indium tin oxide)-Ag-ITO (indium tin oxide) glass substrate with a coating thickness of 150 nm was cleaned in distilled water for 3 times, ultrasonic washing for 40 min, and then repeatedly 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, and then sent to an evaporation machine. The substrate was used as an anode, and other functional layers were sequentially evaporated on it. The organic layers specified below were sequentially evaporated on the ITO anode by thermal vacuum evaporation at a rate of 0.2-2 -8 / s under a vacuum degree of about 10 / s.

[0124] b. HIL (hole injection layer): HT-1 and HI-1 were vacuum evaporated as a hole injection layer at an evaporation rate of 1 / s, and the evaporation rate ratio of HT-1 and HI-1 was 98:2, and the thickness was 10 nm.

[0125] c. HTL (hole transport layer): HT-1 was vacuum evaporated as a hole transport layer on the hole injection layer at an evaporation rate of 1.5 / s, and the thickness was 130 nm.

[0126] d. EBL (electron blocking layer): EBM was vacuum evaporated as a hole blocking layer on the light-emitting layer at an evaporation rate of 0.5 / s, and the thickness was 5 nm.

[0127] e. EML (light-emitting layer): double-host materials (Host-1 and Host-2) and doped material compound 105 were vacuum evaporated as a light-emitting layer on the light-emitting auxiliary layer at an evaporation rate of 1 / s, and the thickness was 200 nm. The evaporation rate ratio of the host material to the doped material was 90:10, and the evaporation rate ratio of Host-1 to Host-2 in the host material was 4:6.

[0128] f. HBL (hole blocking layer): HB-1 was vacuum evaporated as a hole blocking layer on the light-emitting layer at an evaporation rate of 0.5 / s, and the thickness was 5 nm.

[0129] g. ETL (Electron Transport Layer): with 1 At a deposition rate of / s, ET-1 and 8-hydroxyquinoline-lithium (Liq) with a thickness of 30nm were vacuum-deposited on the hole blocking layer as an electron transport layer, wherein the deposition rate ratio of ET-1 to Liq was 50:50.

[0130] h, EIL (Electron Injection Layer): with 0.5 At a deposition rate of / s, a 1.0 nm 8-hydroxyquinoline-lithium (Liq) film was vacuum-deposited on the electron transport layer to form an electron injection layer.

[0131] i. Cathode: with 1 With a deposition rate ratio of / s, magnesium and silver were deposited at 13nm, with a deposition rate ratio of 1:9, resulting in an OLED device.

[0132] j. Optical extraction layer: with 1 At a evaporation rate of / s, a 65nm thick CPL-1 layer was vacuum-deposited on the cathode as a light extraction layer. The deposited substrate was then encapsulated. First, a UV adhesive was applied to the cleaned cover plate using a coating equipment. Then, the coated cover plate was moved to the lamination section, and the evaporated substrate was placed on top of the cover plate. Finally, the substrate and cover plate were bonded together using a bonding equipment, while simultaneously curing the UV adhesive under UV light.

[0133] The structures of HT-1, HI-1, Host-1, Host-1, HB-1, ET-1, and EBM used in Embodiment 1 of the above devices are shown below:

[0134]

[0135] Device Examples 2-93

[0136] The method described in Embodiment 1 of the above device is the same, except that the dopant compound 105 is replaced with 1, 5, 7, 9, 14, 19, 24, 25, 28, 29, 34, 37, 38, 40, 44, 45, 49, 53, 55, 57, 59, 64, 67, 70, 74, 76, 81, 86, 89, 98, 101, 104, 106, 109, 111, 119, 126, 129, 133, 145, 148, 149, 157, 166, 174, 17 8, 180, 189, 199, 202, 209, 214, 216, 220, 225, 228, 231, 234, 245, 248, 251, 254, 258, 261, 262, 263, 264, 276, 284, 277, 285, 287, 290, 294, 299, 304, 309, 315, 318, 324, 327, 330, 335, 340, 342, 347, 350, 355, 360, 361, 362, 363.

[0137] Device Comparison Examples 1-16

[0138] Organic electroluminescent devices were prepared according to the above-described method, except that compound 105 in device example 1 was replaced with compounds A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, and P. The structural formulas of compounds A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, and P are as follows:

[0139]

[0140] The driving voltage, luminous efficiency, and lifetime of the organic electroluminescent devices obtained in Examples 1-93 and Comparative Examples 1-16 were characterized at a brightness of 15000 nits. The test results are shown in Table 1 below.

[0141] Table 1. Results of luminous properties test (luminance value 15000 nits)

[0142]

[0143]

[0144]

[0145] As can be seen from Table 1, the organic electroluminescent device prepared by using the compound provided by the embodiment of the present application as the light-emitting layer dopant material has obvious advantages in the device lifetime and luminous efficiency compared with the organic electroluminescent device prepared by using the comparative example, and the device lifetime and luminous efficiency of the dopant material of the embodiment of the present application are increased by 10.8~26.6% and 5.4~13.0% respectively compared with the comparative example.

[0146] Meanwhile, the compound I and the compound 361, the compound 261 are parallel comparative examples, the comparative compound K and the compound 362, the compound 106 are parallel comparative examples, and the comparative compound N and the compound 363 are parallel comparative examples. As can be known from the comparison of the above three groups of parallel comparative examples, the introduction of adamantyl, trifluoromethyl and tert-butyl on Pt can fine-tune the electron, increase the mobility of the compound, thereby reduce the driving voltage and improve the luminous efficiency and the lifetime of the device, on the other hand, it also plays a role in increasing the steric hindrance to prevent light quenching, adjusting the molecular orientation to make the molecules effectively arranged horizontally, thereby effectively increasing the luminous efficiency, and the device lifetime is also greatly improved. On this basis, the introduction of TMS group can affect the electronic structure and energy level of the organic compound, and the driving voltage and luminous efficiency of the device are also improved to a certain extent.

[0147] The applicant declares that the organic metal compound and the organic electroluminescent device of the present application are illustrated by the above embodiments, but the present application is not limited to the above embodiments, that is, it does not mean that the present application must rely on the above embodiments 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 modes, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. An organometallic compound, characterized in that, The organometallic compound has the structure shown in Formula I: ； Where X is Pt; Ring A is selected from benzene; R1-R4 are independently selected from hydrogen, deuterium, fluorine, trimethylsilane, trimethylgermanium, cyano, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, and substituted or unsubstituted C3-C15 heteroaryl, with the heteroatom being one of O, S, and N. R1-R3 exist independently or two adjacent substituents are connected to each other to form a ring. "Substitution" means substitution by one, two or more substituents selected from the following: hydrogen, deuterium, halogen, cyano, 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, phenyl; R5 is independently selected from trifluoromethyl or tert-butyl; n, q, and o are each independently selected from integers between 0 and 4; p is an integer between 0 and 3; m is an integer from 0 to the maximum number of substitutions that can be achieved in the ring A. In Formula I, all hydrogen atoms are either substituted with deuterium or not substituted with deuterium.

2. The organometallic compound according to claim 1, characterized in that, The organometallic compound has a structure shown in any one of formulas I-1 to I-8: ； R1-R4 are independently selected from hydrogen, deuterium, fluorine, trifluoromethyl, trimethylsilyl, trimethylgermanyl, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazoyl, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted cyclopropane, substituted or unsubstituted cyclobutane, substituted or unsubstituted cyclopentane, and substituted or unsubstituted cyclohexane. n, q, and o are each independently selected from integers between 0 and 4; p and m are integers selected from 0 to 3; Furthermore, all hydrogen atoms in I-1 to I-3 above are independently substituted with or not substituted with deuterium; TMS stands for trimethylsilyl.

3. The organometallic compound according to claim 1 or 2, characterized in that, R2 is selected from tert-butyl groups, and q is an integer of 1 or 2.

4. An organometallic compound, characterized in that, The organometallic compound is any one of the following compounds: ； ； ； ； ； ； ； ； ； Where D represents deuterium and TMS represents trimethylsilyl.

5. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes an anode, a cathode, and an organic layer disposed between the anode and the cathode. The organic layer includes a host material and a dopant material, wherein the dopant material includes an organometallic compound as described in any one of claims 1-4.

6. The organic electroluminescent device according to claim 5, characterized in that, The mass ratio of the main material to the dopant material is 90-99.5:0.5-10.

7. The organic electroluminescent device according to claim 5, characterized in that, The organic layer further includes any one or a combination of at least two of the following: a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting auxiliary layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

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