Blue phosphorescent divalent platinum complexes, methods of making and using the same, and organic optoelectronic devices

Abstract

The present invention relates to the technical field of luminescent materials, and discloses a blue phosphorescent divalent platinum complex, a preparation method and application thereof, and an organic photoelectric device. The blue phosphorescent divalent platinum complex has a structure shown in formula (I): R a 、R b 、R c 、R f 、R d and R e The single-atom substitution or polyatomic substitution group independently exists or does not exist; the blue phosphorescent divalent platinum complex has a narrow blue phosphorescent emission spectrum, which can promote the emission color and improve the performance of the blue phosphorescent device;

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and in particular to a blue phosphorescent divalent platinum complex, a preparation method and application thereof, and an organic photoelectric device. Background Art

[0002] Compounds capable of absorbing or emitting light are suitable for use in a variety of optical and optoelectronic devices, including but not limited to light-absorbing devices such as solar cells and photosensors, organic light-emitting diodes (OLEDs), light-emitting devices, or devices with both light-absorbing and light-emitting capabilities, as well as applications related to biomarkers. Much research has been devoted to discovering organic and organometallic materials for use in optical and electroluminescent devices. Significant progress has been made in the research of optoelectronic materials for use in light-emitting and illumination devices (red and green organometallic materials are used as phosphorescent materials, and blue organometallic materials are used as fluorescent materials), and they have been successfully applied in organic light-emitting diode lighting and advanced displays. However, current applications in large-scale display devices still suffer from shortcomings such as short luminescence lifetime, high heat generation, and low practical efficiency.

[0003] It is generally believed that short-wavelength blue light (high-energy blue light) between 400 and 450 nm is the most harmful to the eyes, causing digital visual fatigue and disrupting sleep, ultimately leading to myopia, cataracts, and macular degeneration, which can harm eye pathologies and human rhythms. Designing a blue light source with a wavelength between 450 and 500 nm and applying it to related electronic products can fundamentally address the harmful effects of high-energy blue light in today's electronic devices, and such research has significant practical significance.

[0004] However, compared to red and green emitting materials, excellent blue light-emitting materials are more scarce. In particular, there is a great demand for high-efficiency phosphorescent blue light-emitting material molecules with both stable structures and suitable emission spectra. Compared with the lowest triplet excited state energies of red and green phosphors, the lowest triplet excited state energy of blue phosphors is very high, which means that the lowest triplet excited state energy of the host material of blue devices must be even higher.

[0005] Therefore, the types of organic optoelectronic devices that can reach the blue light emission range are relatively limited. Correspondingly, it is more difficult to control the appropriate blue light spectrum so that the blue light-emitting device can exhibit excellent performance during the light emission process. Summary of the Invention

[0006] The purpose of the present invention is to overcome the deficiency of OLED devices in the prior art in that they lack complex luminescent materials that can emit stable and efficient blue light, and to provide a blue phosphorescent divalent platinum complex, a preparation method and application thereof, and an organic optoelectronic device. The blue phosphorescent divalent platinum complex has a narrow blue phosphorescent emission spectrum, which can promote the emission color and improve the performance of blue phosphorescent devices.

[0007] In order to achieve the above object, the first aspect of the present invention provides a blue phosphorescent divalent platinum complex, wherein the blue phosphorescent divalent platinum complex has a structure shown in formula (I):

[0008]

[0009] Wherein, in formula (I):

[0010] R a 、R b 、R c 、R f 、R d and R e monoatomic or polyatomic substituents, each independently present or absent;

[0011] The monoatomic substituent includes a hydrogen atom, a hydrogen isotope atom or a halogen atom;

[0012] The polyatomic substituents include alkyl, aryl-substituted alkyl, fluorine-substituted alkyl, aryl, alkyl-substituted aryl, aryl-substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, dialkylamino, diarylamino, alkoxy, aryloxy, haloalkyl, ester, alkoxycarbonyl, silyl, or the above substituents containing isotopic atoms.

[0013] The second aspect of the present invention provides a method for preparing the aforementioned blue phosphorescent divalent platinum complex, wherein the method comprises:

[0014] (1) Under protective gas, a first coupling reaction is performed on the compound represented by formula (II) and a boronic acid having a substituent to obtain a compound represented by formula (III);

[0015] (2) Under protective gas, the compound represented by formula (III) is subjected to a second coupling reaction with trifluoroacetamide to obtain the compound represented by formula (IV);

[0016] (3) Under protective gas, the compound represented by formula (IV) is subjected to a third coupling reaction with substituted o-bromoaniline to obtain a compound represented by formula (V);

[0017] (4) Under protective gas, the compound represented by formula (V) is subjected to a ring-closure reaction with ammonium hexafluorophosphonate to obtain a compound represented by formula (VI);

[0018] (5) subjecting the compound represented by formula (VI) to a cyclometallation reaction to obtain a divalent platinum complex represented by formula (I);

[0019]

[0020] The definitions of the groups in formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI) are the same as those described above.

[0021] The third aspect of the present invention provides a use of the aforementioned blue phosphorescent divalent platinum complex in an organic photoelectric device.

[0022] A fourth aspect of the present invention provides an organic photoelectric device, wherein the device comprises a substrate, an anode layer, a hole transport layer, a light-emitting layer, an electron transport layer and a metal cathode layer, and at least one of the light-emitting layer, the electron transport layer and the hole transport layer comprises the aforementioned blue phosphorescent divalent platinum complex.

[0023] Through the above technical solution, the blue-phosphorescent divalent platinum complex of the present invention is a blue-light emitting material or a phosphorescent material, and can be used as an electroluminescent material or a photoluminescent material. The divalent platinum complex provided in embodiments of the present invention has a peak blue light wavelength within the range of 450-470 nm. Furthermore, the blue light spectrum of the divalent platinum complex provided in embodiments of the present invention falls within the range of 450-500 nm for more than 50%. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is a blue phosphorescent divalent platinum complex 40 according to an embodiment of the present invention. 1 H NMR spectrum;

[0025] Figure 2 is a mass spectrum of a blue phosphorescent divalent platinum complex 40 according to one embodiment of the present invention;

[0026] Figure 3 1 is a luminescence spectrum diagram of a blue phosphorescent divalent platinum complex 40 in solution and film according to an embodiment of the present invention;

[0027] Figure 4 1 is a luminescence spectrum diagram of a blue phosphorescent divalent platinum complex 148 in solution and thin film according to an embodiment of the present invention;

[0028] Figure 5 is a luminescence spectrum of a blue phosphorescent divalent platinum complex 29 in solution according to one embodiment of the present invention;

[0029] Figure 6is a UV-Vis absorption spectrum of blue phosphorescent divalent platinum complex 40 and complex 148 according to an embodiment of the present application;

[0030] Figure 7 is a cross-sectional view of an OLED device according to an embodiment of the present application;

[0031] Figure 8 is a device structure diagram of blue phosphorescent divalent platinum complex 40 according to an embodiment of the present application;

[0032] Figure 9 is an emission spectrum of a device of blue phosphorescent divalent platinum complex 40 according to an embodiment of the present application;

[0033] Figure 10 is a power efficiency of photoelectric conversion of a device of blue phosphorescent divalent platinum complex 40 according to an embodiment of the present application;

[0034] Figure 11 is a power efficiency of photoelectric conversion of a device of blue phosphorescent divalent platinum complex 40 according to an embodiment of the present application;

[0035] Figure 12 is a power efficiency of photoelectric conversion of a device of blue phosphorescent divalent platinum complex 40 according to an embodiment of the present application;

[0036] Figure 13 is a power efficiency of photoelectric conversion of a device of blue phosphorescent divalent platinum complex 40 according to an embodiment of the present application.

[0037] BRIEF DESCRIPTION OF DRAWINGS

[0038] 1000 organic optoelectronic device 1002 substrate 1004 anode layer

[0039] 1006 hole transport layer 1008 light emitting layer 1010 electron transport layer

[0040] 1012 metal cathode layer DETAILED DESCRIPTION

[0041] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are understood to be approximate values. The endpoints of the ranges and any values should be considered to be open-ended ranges, unless expressly stated otherwise. Ranges involving endpoints are to be understood to include the endpoint values themselves. The endpoints of the ranges and any values are understood to be approximate values. The endpoints of the ranges and any values should be considered to be open-ended ranges, unless expressly stated otherwise. Ranges involving endpoints are to be understood to include the endpoint values themselves.

[0042] To achieve the above object, the present application provides a blue phosphorescent divalent platinum complex, wherein the blue phosphorescent divalent platinum complex has a structure shown in formula (I):

[0043]

[0044] Wherein, in formula (I):

[0045] R a 、R b 、R c 、R f , single-atom or multi-atom substituents that are independently present or absent;

[0046] The monoatomic substituent includes a hydrogen atom, a hydrogen isotope atom or a halogen atom;

[0047] The polyatomic substituents include alkyl, aryl-substituted alkyl, fluorine-substituted alkyl, aryl, alkyl-substituted aryl, aryl-substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, dialkylamino, diarylamino, alkoxy, aryloxy, haloalkyl, ester, alkoxycarbonyl, silyl, or the above substituents containing isotopic atoms.

[0048] The inventors of the present invention have discovered that by introducing a pyridine carbon-platinum coordination structure into a divalent platinum complex, the present invention provides a new blue phosphorescent luminescent material with a more stable frontier orbital (FBO, including HOMO and LUMO). This reduces the HOMO and LUMO orbital energies, thereby increasing the charge (including hole and electron) capture efficiency, and ultimately improving the luminous efficiency and stability of the molecule in the device. Furthermore, the ligand structure of the present invention contains a benzimidazole carbene coordination structure and a pyridine carbazole coordination structure. These two structures have suitable triplet state energies suitable for blue light emission and have narrow-band emission properties. This gives this new compound the effect of a narrow blue phosphorescent emission spectrum, which will be able to promote the emission color and improve the performance of blue phosphorescent devices, making it suitable as a healthy organic blue light emitter in OLED-related products.

[0049] In addition, in the embodiment of the present invention, the disclosed divalent platinum complex molecule coordinated by a neutral tetradentate ligand containing a C-Pt carbene coordination structure can emit blue light as a phosphorescent material, and has good stability, high efficiency, and a narrow luminescence range within the long-wavelength blue light range. It is suitable as a healthy organic blue light emitter in OLED-related products.

[0050] Furthermore, the compounds provided by embodiments of the present invention are easy to prepare and purify by sublimation, are soluble in common organic solvents, and are suitable for both vapor deposition and solution-based device fabrication processes. These materials exhibit low-energy, high-color purity luminescence, while simultaneously emitting blue light and improving device performance.

[0051] In addition, the stable complex luminescent material provided by the embodiment of the present application is suitable for industrial production and can be used in OLED display related applications, and the device has high luminescent efficiency and the luminescent color is in the CIE coordinate and more in line with the demand of healthy blue light required by flat panel display.

[0052] According to a preferred embodiment of the present application, in formula (I):

[0053] R a , R b , R c and R f are each independently selected from a hydrogen, deuterium, tritium, fluorine, chlorine, bromine or iodine atom; R d and R e are each independently selected from an alkyl, aryl-substituted alkyl, fluorine-substituted alkyl, aryl, alkyl-substituted aryl, aryl-substituted aryl or cycloalkyl group.

[0054] According to a preferred embodiment of the present application, in formula (I):

[0055] R a , R b , R c , R d , R e and R f are each independently selected from -CDH2, -CD2H, -CD3, -CDR1R2 or -CD2R1, wherein R1 and R2 are each independently selected from an alkyl, aryl-substituted alkyl, aryl, alkyl-substituted aryl, aryl-substituted aryl, cycloalkyl, cycloalkenyl, heteroaryl, alkenyl, alkynyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, alkoxy, aryloxy, haloalkyl, ester, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamide, carbamoyl, alkylthio, ureido, phosphonamidate or silyl group.

[0056] In the present application, it is necessary to point out that, for example, in the "-CDH2" group, "C" refers to carbon, and "D" refers to deuterium (D), an isotope of hydrogen, also called heavy hydrogen.

[0057] According to a preferred embodiment of the present application, in formula (I):

[0058] R a , R b , R c , R d , R e and R fEach independently selected from methyl, deuterated methyl, benzyl, diphenylmethyl, triphenylmethyl; ethyl, 2-phenylethyl, 2,2-phenylethyl, 2,2,2-trifluoroethyl; propyl, isopropyl, 3,3,3-trifluoropropyl, 1,1,1,3,3,3-hexafluoro-2-propyl; butyl, isobutyl, hexafluoroisobutyl, tert-butyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl; phenyl, 2-methylphenyl, 2-isopropylphenyl, 2-ethylphenyl, 4- Methylphenyl, 4-isopropylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 2,3-dimethylphenyl, 2,3-diethylphenyl, 2,3-diisopropylphenyl, 2,3-diisobutylphenyl, 2,3-dicyclohexylphenyl, 2,3-dicyclopropylphenyl, 2,3-dicyclobutylphenyl, 2,3-dicyclopentylphenyl, 2,4-dimethylphenyl, 2,4-diethylphenyl, 2,4-diisopropylphenyl, 2,4-diisobutylphenyl, 2,4-dicyclohexylphenyl phenyl, 2,4-dicyclopropylphenyl, 2,4-dicyclobutylphenyl, 2,4-dicyclopentylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,6-diisobutylphenyl, 2,6-dicyclohexylphenyl, 2,6-dicyclopropylphenyl, 2,6-dicyclobutylphenyl, 2,6-dicyclopentylphenyl, 3,5-dimethylphenyl, 3,5-diethylphenyl, 3,5-diisopropylphenyl, 3,5-diisobutylphenyl phenyl, 3,5-dicyclohexylphenyl, 3,5-dicyclopropylphenyl, 3,5-dicyclobutylphenyl, 3,5-dicyclopentylphenyl, 2,3,5,6-tetramethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 2,4,6-triisopropylphenyl, 2,4,6-triisobutylphenyl, 2,4,6-tricyclohexylphenyl, 2,4,6-tricyclopropylphenyl, 2,4,6-tricyclobutylphenyl or 2,4,6-tricyclopentylphenyl.

[0059] According to a preferred embodiment of the present invention, the blue phosphorescent divalent platinum complex is selected from at least one of the following:

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070] According to a preferred embodiment of the present invention, the blue phosphorescent divalent platinum complex is selected from at least one of the following:

[0071]

[0072] The present invention has no particular limitation on the method for preparing the divalent platinum complex containing blue phosphorescence. Those skilled in the art can obtain appropriate steps to synthesize the complex described in the present invention based on the structural formula provided by the present invention in combination with known synthesis methods in the field of organic synthesis. The preparation methods of several specific compounds are exemplified below in the present invention, which should not be construed by those skilled in the art as limiting the present invention.

[0073] However, in order to increase the yield and purity of the blue phosphorescent divalent platinum complex of the present invention, as mentioned above, the second aspect of the present invention provides a method for preparing the aforementioned blue phosphorescent divalent platinum complex, wherein the method comprises:

[0074] (1) Under protective gas, a first coupling reaction is performed on the compound represented by formula (II) and a boronic acid having a substituent to obtain a compound represented by formula (III);

[0075] (2) Under protective gas, the compound represented by formula (III) is subjected to a second coupling reaction with trifluoroacetamide to obtain the compound represented by formula (IV);

[0076] (3) Under protective gas, the compound represented by formula (IV) is subjected to a third coupling reaction with substituted o-bromoaniline to obtain a compound represented by formula (V);

[0077] (4) Under protective gas, the compound represented by formula (V) is subjected to a ring-closure reaction with ammonium hexafluorophosphonate to obtain a compound represented by formula (VI);

[0078] (5) subjecting the compound represented by formula (VI) to a cyclometallation reaction to obtain a divalent platinum complex represented by formula (I);

[0079]

[0080] The definitions of the groups in formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI) are the same as those described above.

[0081] According to the present invention, the synthesis flow diagram of the blue phosphorescent divalent platinum complex is as follows:

[0082]

[0083] According to the present invention, the reaction conditions of the first coupling reaction include: adding the compound represented by formula (II) and various substituted boronic acids into a sealed tube, and in addition, adding a catalyst, a ligand, a base and a solvent. The reaction is Suzuki coupling.

[0084] In the present invention, the catalyst is a palladium catalyst system. Preferably, the palladium catalyst is selected from one or more of tris(dibenzylideneacetone)dipalladium, tetrakistriphenylphosphine palladium and palladium acetate.

[0085] In the present invention, the ligand is a phosphine ligand. Preferably, the ligand is selected from one or more of 2-(di-tert-butylphosphino)biphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxy-biphenyl and 1,1'-binaphthyl-2,2'-bisdiphenylphosphine.

[0086] In the present invention, the base is an inorganic base. Preferably, the base is selected from one or more of potassium carbonate, potassium hydroxide and cesium carbonate.

[0087] In the present invention, the solvent is selected from 1,4-dioxane or ethylene glycol dimethyl ether.

[0088] In the present invention, the molar ratio of the compound represented by formula (II), the catalyst, the ligand and the base is 1:(0.05-2):(0.1-5):(2.5-10).

[0089] In the present invention, the reaction conditions of the first coupling reaction include: temperature of 90-110° C., time of 11-13 h, preferably, temperature of 100° C., time of 12 h.

[0090] According to the present invention, the reaction conditions of the second coupling reaction include: adding the compound shown as the raw material and trifluoroacetamide into a sealed tube, and in addition, adding a catalyst, a ligand, a base and a solvent. A copper catalyst is usually selected for the reaction of converting halogen to amino group. Preferably, the copper catalyst is selected from one or more of cuprous iodide, cuprous bromide and cuprous chloride.

[0091] In the present invention, the ligand is selected from N 1 ,N 2 -dimethylethane-1,2-diamine, 2,2,6,6-tetramethylheptanedione, N 1 ,N 2one or more of bis(5-methyl-[1,1'-biphenyl]-2-yl)oxal amide, trans-cyclohexanediamine, 1-methylimidazole and L-Proline.

[0092] In the present application, the base is selected from one or more of cesium carbonate, potassium carbonate, potassium phosphate, cesium fluoride and potassium hydroxide.

[0093] In the present application, the solvent is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, ethylene glycol dimethyl ether, deionized water and toluene.

[0094] In the present application, the molar ratio of the compound of formula (III), trifluoroacetamide, catalyst, ligand and base in the raw material is 1:(2-10):(0.1-3):(0.5-5):(2-10).

[0095] In the present application, the conditions of the second coupling reaction include a temperature of 110-130℃ and a time of 23-25h; preferably, the temperature is 120℃ and the time is 24h.

[0096] According to the present application, the reaction conditions of the third coupling reaction include putting the raw material compound of formula (IV) and various substituted o-bromoanilines into a sealed tube, in addition to putting catalyst, ligand, base and solvent, the reaction can select copper catalyst or palladium catalyst, the catalyst can be selected from one or more of cuprous iodide, cuprous bromide and cuprous chloride and other copper catalysts, or selected from one or more of tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium and palladium acetate and other palladium catalysts.

[0097] In the present application, the ligand is selected from phosphine ligands, N 1 ,N 2 - dimethyl ethane-1,2-diamine, 2,2,6,6-tetramethylheptanedione, N 1 ,N 2 - one or more of bis(5-methyl-[1,1'-biphenyl]-2-yl)oxal amide, trans-cyclohexanediamine, 1-methylimidazole and L-Proline; wherein the phosphine ligand is selected from one or more of 2-(di-tert-butylphosphino)biphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxy-biphenyl and 1,1'-binaphthalene-2,2'-bisdiphenylphosphine.

[0098] In the present application, the base is an inorganic base or an organic base; wherein the inorganic base is selected from one or more of cesium carbonate, potassium carbonate, potassium phosphate, cesium fluoride and potassium hydroxide, and the organic base is selected from one or more of sodium tert-butoxide, potassium tert-butoxide and lithium tert-butoxide.

[0099] In the present application, the solvent is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, ethylene glycol dimethyl ether, deionized water and toluene.

[0100] In the present application, the molar ratio of the compound of formula (IV), o-bromoaniline, catalyst, ligand and base is 1:(2-10):(0.1-5):(0.5-5):(2-10).

[0101] In the present application, the conditions of the third coupling reaction include: temperature of 90-110℃, time of 23-25h; preferably, temperature of 100℃, time of 24h.

[0102] According to the present application, the ring-closing reaction includes: putting the raw material compound of formula (V) and ammonium hexafluorophosphate into a sealed tube, in addition to which triethyl orthoformate is also needed as a solvent; the molar ratio of formula (V), ammonium hexafluorophosphate and the solvent triethyl orthoformate is 1:(1.2-5):(0.25-3), preferably 1:1.2:0.25.

[0103] In the present application, the conditions of the ring-closing reaction include: temperature of 110-130℃, time of 23-25h; preferably, temperature of 120℃, time of 24h.

[0104] According to the present application, the step of the cyclometallation reaction includes: mixing the compound of formula (VI), platinum dichloride and N,N-dimethylformamide uniformly, the molar ratio of the compound of formula (VI) and platinum dichloride is 1:(1.1-5), preferably 1:1.1; the concentration of N,N-dimethylformamide is 0.01mmol / ml, in the presence of a protective gas, for example in a nitrogen environment, heating to a temperature of 120-140℃ and stirring for 71-73h; preferably, heating to a temperature of 130℃ and stirring for 72h.

[0105] As previously described, the third aspect of the present application provides a use of the aforementioned blue-phosphorescent divalent platinum complex in an organic optoelectronic device.

[0106] As previously described, the fourth aspect of the present application provides an organic optoelectronic device, wherein the device contains a substrate, an anode layer, a hole transport layer, a light-emitting layer, an electron transport layer and a metal cathode layer, at least one of the light-emitting layer, the electron transport layer and the hole transport layer contains the aforementioned blue-phosphorescent divalent platinum complex.

[0107] Figure 7 is a cross-sectional view of an OLED device according to an embodiment of the present application; Figure 8is a device structure diagram prepared according to a blue phosphorescent divalent platinum complex 40 of an embodiment of the present application; in a preferred embodiment of the present application, as shown in Figure 7 and Figure 8 The organic optoelectronic device (OLED) 1000 includes a substrate 1002, an anode layer 1004, a hole transport layer 1006, a light-emitting layer 1008, an electron transport layer 1010, and a metal cathode layer 1012, wherein the anode layer 1004 is generally made of a transparent material, such as indium tin oxide; the light-emitting layer 1008 can include a light-emitting material of an emitter and a host. In addition, an EIL (electron injection layer) can be considered as part of the electron transport layer 1010, an HIL (hole injection layer) can be considered as part of the hole transport layer 1006, and a CPL is a cathode cover layer.

[0108] According to a particularly preferred specific embodiment, the blue phosphorescent divalent platinum complex is contained in the light-emitting layer.

[0109] More preferably, the blue phosphorescent divalent platinum complex is a light-emitting material, a host material, or a guest material in the light-emitting layer.

[0110] In a preferred embodiment of the present application, the material of the light-emitting layer is a mixture of 3,3'-di(9H-carbazol-9-yl)-1,1'-biphenyl or 2,6-di(9-carbazolyl)pyridine and the blue phosphorescent divalent platinum complex according to the present application, with a weight ratio of 10:1.

[0111] In the present application, the anode material in the anode layer can be a conventional material in the art, for example, it can be ITO (indium tin oxide).

[0112] In the present application, the hole transport layer is a conventional material in the art, for example, it can be PEDOT:PSS (poly 3,4-ethylenedioxythiophene / polystyrene sulfonate), preferably, the thickness of the hole transport layer is 20-60 nm, preferably 40 nm.

[0113] In the present application, in order to improve the light-emitting efficiency of the organic optoelectronic device, preferably, a hole blocking layer is further provided in the hole transport layer, and the material of the hole blocking layer can be a conventional material in the art, for example, it can be DPEPO (di[2-((oxo)diphenylphosphino)phenyl] ether), preferably, the thickness of the hole blocking layer is 5-20 nm, preferably 10 nm.

[0114] In the present application, the material of the electron transport layer can be a conventional material in the art, for example, it can be TmPyPB (3,3'-[5'-[3-(3-pyridyl)phenyl][1,1':3',1"-terphenyl]-3,3"-diyl]dipyridine), preferably, the thickness of the electron transport layer is 30-80 nm, preferably 50 nm.

[0115] In the present application, the material of the metal cathode layer can be conventional material in the art, for example, can be Al / Liq (aluminum and 8-hydroxyquinoline lithium), wherein the thickness of the Al layer can be 50-150 nm, preferably 100 nm, and the thickness of the Liq can be 0.5-2 nm, preferably 1 nm.

[0116] In the present application, in order to improve the light-emitting efficiency of the organic optoelectronic device, preferably, a hole blocking layer is further arranged in the hole transport layer, and the material of the hole blocking layer can be conventional material in the art, for example, can be DPEPO (di[2-((oxo)diphenylphosphanyl)phenyl] ether), preferably, the thickness of the hole blocking layer is 30-60 nm, preferably 40 nm.

[0117] The present application will be described in detail below through examples.

[0118] In the following examples:

[0119] Nuclear magnetic resonance spectrum analysis: in CDCl3 or DMSO-d6 solution, recorded by Bruker liquid nuclear magnetic resonance instrument 1 HNMR (hydrogen nuclear magnetic resonance) and 13C NMR (carbon nuclear magnetic resonance) with a frequency of 300, 400 or 500 MHz, and the chemical shift is based on the residual protonated solvent. If CDCl3 is used as the solvent, tetramethylsilane (δ = 0.00 ppm) is used as the internal reference to record 1 H NMR (hydrogen nuclear magnetic resonance) spectrum; CDCl3 (δ = 77.00 ppm) is used as the internal reference to record 13 C NMR (carbon nuclear magnetic resonance) spectrum. If DMSO-d6 is used as the solvent, residual H2O (δ = 3.33 ppm) is used as the internal reference to record 1 H NMR spectrum; DMSO-d6 (δ = 39.52 ppm) is used as the internal reference to record 13 C NMR spectrum.

[0120] Mass spectrum analysis: some compounds were tested by Waters Aquity Qda ultra-high pressure liquid chromatography-mass spectrometry (ESI-MS) mass spectrometry or high-resolution mass spectrometry by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) instrument.

[0121] Material purification: after the final product platinum complex is separated by column chromatography and preparative HPLC, it is subjected to sublimation purification by ultra-high vacuum (10 -4 ~ 10 -5 Pa) sublimation purification equipment to the purity requirement for device production.

[0122] High performance liquid chromatography analysis: using methanol / water (1 / 9) as the mobile phase, the purity of the platinum complex sample was analyzed.

[0123] Cyclic voltammetry and energy level calculation: A three-electrode system was used, with a platinum column as the working electrode, a platinum wire as the counter electrode, and a silver / silver chloride (Ag / AgCl) reference electrode. The samples were tested under a nitrogen atmosphere using 0.1M tetrabutylammonium hexafluorophosphate in N,N-dimethylformamide as the solvent. Ferrocene was used as the internal standard at a scan rate of 100 mV / s. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the platinum complex molecule can be calculated based on Equations 5-1 and 5-2 and the CV test results. Since the measured potential of ferrocene in DMF solution relative to the reference electrode is not a fixed value but varies slightly among different platinum complex solutions, the ferrocene redox potential measured in that test was used for the calculation.

[0124] HOMO=-[E ox -E Fc / Fc+ox +4.8]eV 5-1

[0125] LUMO=-[E red -E Fc / Fc+red +4.8]eV 5-2

[0126] Where: E ox 、E red are the oxidation peak onset potential and reduction peak onset potential of the sample, E Fc / Fc+ox 、E Fc / Fc+red are the onset potential of the oxidation peak and the reduction peak of ferrocene, respectively, and 4.8 is the vacuum energy level of ferrocene.

[0127] UV-visible absorption spectrum test: The absorption spectrum of the platinum complex in dichloromethane solution at room temperature was tested, with a scanning range of 250 to 500 nm and an interval of 1 nm.

[0128] Steady-state spectral measurements were performed on the platinum complex's room-temperature dichloromethane solution, the luminescence / excitation spectra of 2-methyltetrahydrofuran at 77K, and the spectra of a 5wt% doped polymethyl methacrylate (PMMA) film. The dichloromethane solution spectra were measured after the solvent was thoroughly purged with nitrogen. Polymer-doped films were prepared by spin coating in a glove box using chloroform as the solvent and a quartz wafer as the film support. Film samples were tested in a glove box or vacuum chamber to minimize oxygen quenching of the complex's luminescence. The photoluminescence quantum yield (PLQY) of the platinum complex solution and film was also measured using an integrating sphere.

[0129] Transient spectrum and phosphorescence lifetime tests: Time-resolved spectrum tests and luminescence lifetime half-life tests were performed on room temperature dichloromethane solutions of platinum complexes using the Fluorolog-3 full-spectrum optical platform. Life tests were also performed on 5wt% doped PMMA films. All tests were performed under nitrogen or vacuum conditions.

[0130] Example 1

[0131] This example is intended to illustrate the preparation of blue phosphorescent divalent platinum complex 6.

[0132] (1) Intermediate 2-((2-chloro-6-(2,6-diisopropylphenyl)pyridin-4-yl)oxy)-7-methyl-9-(pyridin- Synthesis of 2-methyl-9H-carbazole :

[0133]

[0134] To a 15 mL sealed tube, 2-((2,6-dichloropyridin-4-yl)oxy)-7-methyl-9-(pyridin-2-yl)-9H-carbazole (1 mmol), 2-(2,6-diisopropylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.2 mmol), tris(dibenzylideneacetone)dipalladium (0.05 mmol), tricyclohexylphosphine (0.4 mmol), cesium carbonate (1.25 mmol), 1,4-dioxane (2 mL) were added. The obtained mixture was bubbled with nitrogen and then heated with stirring; cooled to room temperature, water was added to quench the reaction, extracted with ethyl acetate, the organic phases were combined, washed with an appropriate amount of saturated sodium chloride aqueous solution, and then dried over anhydrous sodium sulfate; the solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography with petroleum ether:ethyl acetate = 25:1 as eluent to obtain 2-((2-chloro-6-(2,6-diisopropylphenyl)pyridin-4-yl)oxy)-7-methyl-9-(pyridin-2-yl)-9H-carbazole as a white solid.

[0135] (2) Intermediate 2-((2-(1H-benzo[d]imidazol-1-yl]-6-(2,6-diisopropylphenyl)pyridin-4-yl)oxy Synthesis of 7-methyl-9-(pyridin-2-yl)-9H-carbazole :

[0136]

[0137] To a 75 mL sealed tube were added 2-((2-chloro-6-(2,6-diisopropylphenyl)pyridin-4-yl)oxy)-7-methyl-9-(pyridin-2-yl)-9H-carbazole (1 mmol), benzimidazole (2 mmol), cuprous iodide (0.1 mmol), N 1 ,N 2- Bis(5-methyl-[l,l'-biphenyl]-2-yl)oxalamide (0.2 mmol), potassium phosphate (1.5 mL), dimethyl sulfoxide (10 mL), the resulting mixture was bubbled with nitrogen and heated with stirring; cooled to room temperature, the reaction was quenched with water, extracted with ethyl acetate, combined organic phase was washed with an appropriate amount of saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate; the solvent was removed under reduced pressure, the resulting crude product was purified by column chromatography on silica gel, eluent was petroleum ether: ethyl acetate = 10: 1, to obtain a white solid 2-((2-(lH-benzo[d]imidazol-l-yl]-6-(2,6-diisopropylphenyl)pyridin-4-yl)oxy)-7-methyl-9-(pyridin-2-yl)-9H-carbazole.

[0138] (3) Intermediate 2-(2-(2,6-diisopropylphenyl)-6-(3-methyl-2,3-dihydro-1H-benzo[d]imidazole- Synthesis of 9-(1-yl)pyridin-4-yl)oxy)-7-methyl-9-(pyridin-2-yl)-9H-carbazole :

[0139]

[0140] Into a 100 mL round bottom flask was added 2-((2-(lH-benzo[d]imidazol-l-yl]-6-(2,6-diisopropylphenyl)pyridin-4-yl)oxy)-7-methyl-9-(pyridin-2-yl)-9H-carbazole (5 mmol), acetone (30 mL), the resulting mixture was stirred at room temperature under nitrogen protection, iodomethane (1 mL) was added dropwise, the reaction was detected by TLC, the reaction was quenched with water, extracted with ethyl acetate, combined organic phase was washed with an appropriate amount of saturated aqueous sodium chloride solution and dried over anhydrous sodium sulfate; the solvent was removed under reduced pressure, the resulting crude product was purified by column chromatography on silica gel, eluent was petroleum ether: ethyl acetate = 10: 1, to obtain a white solid 2-((2-(2,6-diisopropylphenyl)-6-(3-methyl-2,3-dihydro-lH-benzo[d]imidazol-l-yl)pyridin-4-yl)oxy)-7-methyl-9-(pyridin-2-yl)-9H-carbazole.

[0141] (4) Synthesis of ligand precursor L6 :

[0142]

[0143] Into a 45 mL sealed tube was added 2-((2-(2,6-diisopropylphenyl)-6-(3-methyl-2,3-dihydro-lH-benzo[d]imidazol-l-yl)pyridin-4-yl)oxy)-7-methyl-9-(pyridin-2-yl)-9H-carbazole (2 mmol), ammonium hexafluorophosphate (2.2 mmol), methanol (10 mL) and water (10 mL). Heated overnight. After cooling to room temperature, add ethyl acetate to precipitate a yellow precipitate, filter to obtain ligand L6.

[0144] (5) Synthesis of complex 6 :

[0145]

[0146] Ligand L6 (0.2 mmol), platinum dichloride (0.22 mmol), and N,N-dimethylformamide (20 mL) were added to a 75 mL sealed tube. The mixture was stirred at room temperature for one day and heated at 130°C for two days. After cooling to room temperature, the mixture was spin-dried and purified by silica gel chromatography using dichloromethane:petroleum ether = 1:1 as the eluent to obtain complex 6 (yellow-green powder); MS (ESI): 836.4 [M+H] + .

[0147] Example 2

[0148] This example is intended to illustrate the preparation of blue phosphorescent divalent platinum complex 29.

[0149] (1) Intermediate 9-(4-bromopyridin-2-yl)-2-((2-chloro-6-(2,6-dimethylphenyl)pyridin-4-yl)oxy Synthesis of 2-(2-methyl-1-oxo-2-nitropropene)-9H-carbazole:

[0150]

[0151] To a 15 mL sealed tube were added 9-(4-bromopyridin-2-yl)-2-((2,6-dichloropyridin-4-yl)oxy)-9H-carbazole (1 mmol), (2,6-dimethylphenyl)boronic acid (1.2 mmol), tris(dibenzylideneacetone)dipalladium (0.05 mmol), tricyclohexylphosphine (0.4 mmol), cesium carbonate (1.5 mmol), 1,4-dioxane (2 mL), and the resulting mixture was bubbling with nitrogen. The reaction mixture was heated with stirring; cooled to room temperature, water was added to quench the reaction, and the mixture was extracted with ethyl acetate. The organic phases were combined, washed with an appropriate amount of saturated sodium chloride aqueous solution, and dried over anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography with petroleum ether:ethyl acetate = 25:1 as eluent to obtain 9-(4-bromopyridin-2-yl)-2-((2-chloro-6-(2,6-dimethylphenyl)pyridin-4-yl)oxy)-9H-carbazole as a white solid.

[0152] (2) Intermediate 2-((2-(1H-benzo[d]imidazol-1-yl)-6-(2,6-dimethylphenyl)pyridin-4-yl)oxy Synthesis of 9-(4-bromopyridin-2-yl)-9H-carbazole:

[0153]

[0154] To a 45 mL sealed tube were added 9-(4-bromopyridin-2-yl)-2-((2-chloro-6-(2,6-dimethylphenyl)pyridin-4-yl)oxy)-9H-carbazole (1 mmol), benzimidazole (2 mmol), cuprous iodide (0.1 mmol), N 1 ,N 2-bis(5-methyl-[1,1'-biphenyl]-2-yl)oxamide (0.2 mmol), potassium phosphate (1.5 mL), dimethyl sulfoxide (10 mL), the resulting mixture was bubbling with nitrogen and then heated with stirring; cooled to room temperature, water was added to quench the reaction, extracted with ethyl acetate, the organic phases were combined, washed with an appropriate amount of saturated sodium chloride aqueous solution, and dried over anhydrous sodium sulfate; the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography with petroleum ether: ethyl acetate = 10:1 as eluent to obtain 2-((2-(1H-benzo[d]imidazol-1-yl)-6-(2,6-dimethylphenyl)pyridin-4-yl)oxy)-9-(4-bromopyridin-2-yl)-9H-carbazole as a white solid.

[0155] (3) Intermediate 9-(4-bromopyridin-2-yl)-2-((2-(2,6-dimethylphenyl)-6-(3-methyl-2,3-dihydro- Synthesis of (1H-benzo[d]imidazol-1-yl)pyridin-4-yl)oxy)-9H-carbazole:

[0156]

[0157] To a 100 mL round-bottom flask was added 2-((2-(1H-benzo[d]imidazol-1-yl)-6-(2,6-dimethylphenyl)pyridin-4-yl)oxy)-9-(4-bromopyridin-2-yl)-9H-carbazole (3 mmol) and acetone (30 mL). The resulting mixture was stirred at room temperature under nitrogen protection. Iodomethane (0.5 mL) was added dropwise. The reaction was complete as determined by TLC. The reaction was quenched by adding water and extracted with ethyl acetate. The organic phases were combined. , washed with an appropriate amount of saturated sodium chloride aqueous solution and then dried over anhydrous sodium sulfate; the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography with petroleum ether: ethyl acetate = 10:1 as eluent to obtain 2-((2-(2,6-diisopropylphenyl)-6-(3-methyl-2,3-dihydro-1H-benzo[d]imidazol-1-yl)pyridin-4-yl)oxy)-7-methyl-9-(pyridin-2-yl)-9H-carbazole as a white solid.

[0158] (4) Intermediate 9-(4-bromopyridin-2-yl)-2-((2-(2,6-dimethylphenyl)-6-(3-methyl-2,3-dihydro- Synthesis of 1H-benzo[d]imidazol-1-yl)pyridin-4-yl)oxy)-9H-carbazole hexafluorophosphate:

[0159]

[0160] To a 75 mL sealed tube, add 2-((2-(2,6-diisopropylphenyl)-6-(3-methyl-2,3-dihydro-1H-benzo[d]imidazol-1-yl)pyridin-4-yl)oxy)-7-methyl-9-(pyridin-2-yl)-9H-carbazole (2 mmol), ammonium hexafluorophosphate (2.2 mmol), methanol (20 mL), and water (20 mL). Heat overnight. After cooling to room temperature, add ethyl acetate to precipitate a yellow precipitate, which is filtered to obtain the hexafluorophosphate ligand.

[0161] (5) Synthesis of ligand precursor L29:

[0162]

[0163] To a 45 mL sealed tube, 9-(4-bromopyridin-2-yl)-2-((2-(2,6-dimethylphenyl)-6-(3-methyl-2,3-dihydro-1H-benzo[d]imidazol-1-yl)pyridin-4-yl)oxy)-9H-carbazole (1 mmol), sodium deuterated formate (2 mmol), palladium acetate (0.2 mmol), tri-o-tolylphosphine (0.8 mmol), and dimethyl sulfoxide (5 mL) were added. The reaction system was heated to 80°C and stirred for 12 hours under a nitrogen atmosphere. After cooling to room temperature, water and ethyl acetate were added for extraction. The organic phases were combined, washed, dried over anhydrous sodium sulfate, and distilled under reduced pressure to obtain a crude product. The crude product was purified by column chromatography to obtain ligand L29 as a white solid.

[0164] (6) Synthesis of complex 29:

[0165]

[0166] Ligand L29 (0.2 mmol), platinum dichloride (0.22 mmol), and N,N-dimethylformamide (20 mL) were added to a 75 mL sealed tube. The mixture was stirred at room temperature for one day and heated at 130°C for two days. After cooling to room temperature, the mixture was spin-dried and purified by silica gel chromatography using dichloromethane:petroleum ether = 1:1 as the eluent to obtain the target complex 29 (yellow-green powder); MS (ESI): 767.4 [M+H] + .

[0167] Example 3

[0168] This example is intended to illustrate the preparation of a blue phosphorescent divalent platinum complex 40.

[0169] (1) Synthesis of the intermediate 6-methylsulfonyl-4-((9-(pyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-amine become:

[0170]

[0171] To a 15 mL sealed tube were added 2-((2-chloro-6-methylphenylpyridin-4-yl)oxy)-9-(pyridin-2-yl)-9H-carbazole (2 mmol), 2,2,2-trifluoroacetamide (2.4 mmol), cuprous iodide (0.1 mmol), N 1 ,N 2-dimethylethane-1,2-diamine (0.2 mmol), potassium carbonate (4 mmol), 1,4-dioxane (2 mL), the resulting mixture was bubbling with nitrogen and then heated with stirring; cooled to room temperature, water was added to quench the reaction, extracted with ethyl acetate, the organic phases were combined, washed with an appropriate amount of saturated sodium chloride aqueous solution, and then dried over anhydrous sodium sulfate; the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography with petroleum ether: ethyl acetate = 3:1 as eluent to obtain 6-methylsulfonyl-4-((9-(pyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-amine as a white solid.

[0172] (2) Intermediate N1-isopropyl-N2-(6-methylsulfonyl-4-((9-(pyridin-2-yl)-9H-carbazol-2-yl)oxy) Synthesis of 2-(2-yl)pyridin-2-yl)benzene-1,2-diamine:

[0173]

[0174] To a 45 mL sealed tube were added 6-methylsulfonyl-4-((9-(pyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-amine (1 mmol), 2-bromo-N-isopropylaniline (1.5 mmol), tris(dibenzylideneacetone)dipalladium (0.05 mmol), 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (0.1 mmol), sodium tert-butoxide (1.5 mmol), and toluene (4 mmol). The resulting mixture was bubbled with nitrogen and then added. The mixture was stirred hot; cooled to room temperature, water was added to quench the reaction, and the mixture was extracted with ethyl acetate. The organic phases were combined, washed with an appropriate amount of saturated sodium chloride aqueous solution, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography with petroleum ether:ethyl acetate = 5:1 as eluent to obtain N1-isopropyl-N2-(6-methylsulfonyl-4-((9-(pyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-yl)benzene-1,2-diamine as a white solid.

[0175] (3) Synthesis of ligand precursor L40:

[0176]

[0177] To a 15 mL sealed tube, add N1-isopropyl-N2-(6-methylsulfonyl-4-((9-(pyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-yl)benzene-1,2-diamine (0.1 mmol), ammonium hexafluorophosphate (0.12 mmol), and triethyl orthoformate (0.4 mmol). Heat at 120°C overnight. After cooling to room temperature, add ethyl acetate to precipitate a yellow precipitate, which is filtered to obtain ligand L40.

[0178] (4) Synthesis of complex 40:

[0179]

[0180] Ligand L40 (0.5 mmol), platinum dichloride (0.55 mmol), and N,N-dimethylformamide (50 mL) were added to a 150 mL sealed tube. Stir at room temperature for one day and heat at 120°C for two days. After cooling to room temperature, the mixture was spin-dried and purified by silica gel chromatography using dichloromethane:petroleum ether = 1:1 as the eluent to obtain the desired product: complex 40 (yellow-green powder). 1 NMR(400MHz,DMSO)δ9.51(d,J=8.0Hz,1H),8.55–8.50(m,1H),8.26–8.14(m,3H),8.09( d,J=8.0Hz,1H),7.98(m,1H),7.92(d,J=8.0Hz,1H),7.71–7.62(m,1H),7.50–7.44(m,1 H),7.42–7.35(m,3H),7.30(m,2H),6.95(s,1H),6.72(s,1H),4.18(t,1H),2.28(s,3H) ,2.10(d,J=28.0Hz,6H),1.92–1.89(m,3H),1.51(d,J=8.0Hz,3H).MS(ESI):808.2[M+H] + .Emission peak in DCM at 450nm, FWHM=38nm, peak in PMMA at 447nm, FWHM=20nm.

[0181] In addition, if Figure 1 As shown, the complex 40 1 H NMR spectrum; the H NMR spectrum demonstrates that the complex can exist independently and stably, and can be isolated, purified, and characterized. The NMR spectrum shows that, in addition to the stable structure of the divalent platinum complex, the divalent platinum complex does not show any signs of aggregation, indicating that the divalent platinum complex exists as a single isolated molecule in solution.

[0182] Figure 2 The figure is a mass spectrometry characterization diagram of the molecule of complex 40. The mass spectrometry molecular signal shows that the M / C peak is 808.2, which is consistent with the molecular ion peak of compound 40, indicating that the structure of the complex is the designed structure.

[0183] Example 4

[0184] This example is intended to illustrate the preparation of the blue phosphorescent divalent platinum complex 143.

[0185] (1) Intermediate 2-((2-chloro-6-(2,6-dimethylphenyl)pyridin-4-yl)oxy)-9-(4-methylpyridine-2- Synthesis of 2-(2-methyl-1-oxo-2-nitropropene)-9H-carbazole:

[0186]

[0187] To a 15 mL sealed tube were added 2-((2,6-dichloropyridin-4-yl)oxy)-9-(4-methylpyridin-2-yl)-9H-carbazole (1 mmol), (2,6-dimethylphenyl)boronic acid (1.2 mmol), tris(dibenzylideneacetone)dipalladium (0.05 mmol), tricyclohexylphosphine (0.4 mmol), cesium carbonate (1.25 mmol), 1,4-dioxane (2 ml), and the resulting mixture was bubbled with nitrogen. The reaction mixture was heated with stirring; cooled to room temperature, water was added to quench the reaction, and the mixture was extracted with ethyl acetate. The organic phases were combined, washed with an appropriate amount of saturated sodium chloride aqueous solution, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography using petroleum ether:ethyl acetate = 25:1 as eluent to obtain 2-((2-chloro-6-(2,6-dimethylphenyl)pyridin-4-yl)oxy)-9-(4-methylpyridin-2-yl)-9H-carbazole as a white solid.

[0188] (2) Intermediate 6-(2,6-dimethylphenyl)-4-((9-(4-methylpyridin-2-yl)-9H-carbazol-2-yl)oxy Synthesis of (4-amino)pyridin-2-amine:

[0189]

[0190] To a 15 mL sealed tube were added 2-((2-chloro-6-(2,6-dimethylphenyl)pyridin-4-yl)oxy)-9-(4-methylpyridin-2-yl)-9H-carbazole (2 mmol), 2,2,2-trifluoroacetamide (2.2 mmol), cuprous iodide (0.1 mmol), N 1 ,N 2 -dimethylethane-1,2-diamine (0.2 mmol), potassium carbonate (4 mmol), 1,4-dioxane (2 ml), the resulting mixture was bubbling with nitrogen and then heated with stirring; cooled to room temperature, water was added to quench the reaction, extracted with ethyl acetate, the organic phases were combined, washed with an appropriate amount of saturated sodium chloride aqueous solution, and then dried over anhydrous sodium sulfate; the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography with petroleum ether: ethyl acetate = 3:1 as eluent to obtain 6-(2,6-dimethylphenyl)-4-((9-(4-methylpyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-amine as a white solid.

[0191] (3) Intermediate N 1 -(6-(2,6-dimethylphenyl)-4-((9-(4-methylpyridin-2-yl)-9H-carbazol-2-yl) Synthesis of (2-(2-oxy)pyridin-2-yl)benzene-1,2-diamine:

[0192]

[0193] To a 45 mL sealed tube were added 6-(2,6-dimethylphenyl)-4-((9-(4-methylpyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-amine (2 mmol), o-bromoaniline (2.2 mmol), tris(dibenzylideneacetone)dipalladium (0.16 mmol), J-Phos (0.32 mmol), sodium tert-butoxide (3 mmol), and toluene (8 ml). The resulting mixture was bubbling with nitrogen and then heated with stirring; cooled to room temperature, the reaction was quenched by adding water, extracted with ethyl acetate, the organic phases were combined, washed with an appropriate amount of saturated sodium chloride aqueous solution, and dried over anhydrous sodium sulfate; the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography with petroleum ether: ethyl acetate = 5:1 as the eluent to obtain N 1 -(6-(2,6-dimethylphenyl)-4-((9-(4-methylpyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-yl)benzene-1,2-diamine.

[0194] (4) Intermediate N 1 -(6-(2,6-dimethylphenyl)-4-((9-(4-methylpyridin-2-yl)-9H-carbazol-2-yl) Oxy)pyridin-2-yl)-N 2 -Synthesis of resorcinol-1,2-diamine:

[0195]

[0196] Add N to the 15 mL sealed tube. 1 -(6-(2,6-dimethylphenyl)-4-((9-(4-methylpyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-yl)benzene-1,2-diamine (1 mmol), 2-bromo-1,3,5-trimethylbenzene (2 mmol), tris(dibenzylideneacetone)dipalladium (0.1 mmol), J-Phos (0.2 mmol), sodium tert-butoxide (1.5 mmol), toluene (4 ml), the resulting mixture was bubbling with nitrogen and then heated with stirring; cooled to room temperature, the reaction was quenched by adding water, extracted with ethyl acetate, the organic phases were combined, washed with an appropriate amount of saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate; the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography with petroleum ether:ethyl acetate = 5:1 as the eluent to obtain white solid N 1 -(6-(2,6-dimethylphenyl)-4-((9-(4-methylpyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-yl)-N 2 -resorcinol-1,2-diamine.

[0197] (5) Synthesis of ligand L143:

[0198]

[0199] Add N to the 15 mL sealed tube. 1-(6-(2,6-dimethylphenyl)-4-((9-(4-methylpyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-yl)-N 2 Resorcinol-1,2-diamine (1 mmol), ammonium hexafluorophosphate (1.2 mmol), and triethyl orthoformate (0.4 mmol) were heated at 120°C overnight. After cooling to room temperature, ethyl acetate was added to precipitate a yellow precipitate, which was filtered to obtain ligand L143.

[0200] (6) Synthesis of complex 143:

[0201]

[0202] Ligand L143 (0.2 mmol), platinum dichloride (0.22 mmol), and DMF (20 ml) were added to a 757 mL sealed tube. The mixture was stirred at room temperature for one day and heated at 120°C for two days. After cooling to room temperature, the mixture was spin-dried and purified by silica gel chromatography using dichloromethane:petroleum ether = 1:1 as the eluent to obtain the desired product, complex 143 (yellow-green powder); MS (ESI): 884.2 [M+H] + .

[0203] Example 5

[0204] This example is intended to illustrate the preparation of the blue phosphorescent divalent platinum complex 148.

[0205] (1) N-(2-bromophenyl)-6-methanesulfonyl-4-((9-(pyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridine-2- Synthesis of amines:

[0206]

[0207] To a 45 mL sealed tube were added 6-methylsulfonyl-4-((9-(pyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-amine (1 mmol), o-dibromobenzene (1.5 mmol), tris(dibenzylideneacetone)dipalladium (0.05 mmol), J-Phos (0.1 mmol), sodium tert-butoxide (1.5 mmol), and toluene (4 ml). The resulting mixture was sparged with nitrogen and then heated with stirring. The mixture was cooled to room temperature, quenched with water, and extracted with ethyl acetate. The organic phases were combined, washed with an appropriate amount of saturated sodium chloride aqueous solution, and dried over anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was separated and purified by silica gel column chromatography with petroleum ether:ethyl acetate = 5:1 as eluent to obtain N-(2-bromophenyl)-6-methylsulfonyl-4-((9-(pyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-amine as a white solid.

[0208] (2)N 1 -(2,6-diisopropylphenyl)-N 2 -(6-methanesulfonyl-4-((9-(pyridin-2-yl)-9H-carbazole-2- Synthesis of 2-(4-(2-yl)oxy)pyridin-2-yl)benzene-1,2-diamine:

[0209]

[0210] To a 15 mL sealed tube were added N-(2-bromophenyl)-6-methanesulfonyl-4-((9-(pyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-amine (0.5 mmol), 2,6-diisopropylaniline (1 mmol), tris(dibenzylideneacetone)dipalladium (0.08 mmol), 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (0.16 mmol), sodium tert-butoxide (0.75 mmol), and toluene (2 ml). The resulting mixture was bubbling with nitrogen and then heated with stirring; cooled to room temperature, the reaction was quenched by adding water, extracted with ethyl acetate, the organic phases were combined, washed with an appropriate amount of saturated sodium chloride aqueous solution, and dried over anhydrous sodium sulfate; the solvent was distilled off under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography with petroleum ether: ethyl acetate = 3:1 as the eluent to obtain N as a white solid. 1 -(2,6-diisopropylphenyl)-N 2 -(6-methanesulfonyl-4-((9-(pyridin-2-yl)-9H-carbazol-2-yl)oxy)pyridin-2-yl)benzene-1,2-diamine.

[0211] (3) Synthesis of ligand precursor L148:

[0212]

[0213] Add N to the 15 mL sealed tube. 1 -(2,6-diisopropylphenyl)-N 2 1,2-diamine (0.1 mmol), ammonium hexafluorophosphate (0.11 mmol), and triethyl orthoformate (0.4 mmol) were added. Heat at 120°C overnight. After cooling to room temperature, ethyl acetate was added to precipitate a yellow precipitate, which was filtered to obtain ligand L148.

[0214] (4) Synthesis of complex 148:

[0215]

[0216] Ligand precursor L148 (0.2 mmol), platinum dichloride (0.22 mmol), and N,N-dimethylformamide (20 ml) were added to a 75 mL sealed tube. Stir at room temperature for one day and then heat at 120°C for two days. After cooling to room temperature, the mixture was spin-dried and purified by silica gel chromatography using dichloromethane:petroleum ether = 1:1 as the eluent to obtain the desired product, complex 148 (yellow-green powder).

[0217] Test Example 1

[0218] Luminescence Properties of Platinum Complexes 29, 40, and 148

[0219] Attachment Figure 3-4 The luminescence spectra of divalent platinum complexes 40 and 148 in solution and film are shown in sequence. Under 340nm ultraviolet light excitation, the luminescence wavelengths of the three complexes in dichloromethane solution are between 450-470nm, and the luminescence wavelengths in polymethyl methacrylate are between 440-470nm. The wavelengths of all complexes are in the deep blue light region, and the half-peak width of the spectrum is narrow, indicating that this series of complexes are good blue luminescent materials. Among them, Figure 3 This is a luminescence spectrum diagram of the complex 40 in a specific embodiment of the present invention in a solution and a film. The film emission peak wavelength is 447nm, which has a blue shift effect compared to the solution emission wavelength of 450nm. Both show good blue light emission spectra, indicating that the complex 40 is suitable for applications in blue light luminescence. Figure 4 The following are the luminescence spectra of complex 148 in solution and film according to a specific embodiment of the present invention. The peak wavelength of the film emission spectrum is 468nm, and the peak wavelength of the solution emission spectrum is 470nm. The luminescence spectrum of complex 148 is 20nm red-shifted compared with complex 148, and its vibrational structure peaks are broader. This indicates that the main energy level of complex 148 is affected by the substituents on the carbene, and the overall structure of complex 148 is rigid, but the local 800cm -1 The following vibrations have weaker coupling effects in the luminescence process. Complex 5 is a blue phosphorescent luminescent material; Figure 5 This is a luminescence spectrum of complex 29 in solution, according to a specific embodiment of the present invention. The peak wavelength of the solution emission spectrum is 470 nm, indicating that complex 29 is a blue phosphorescent material. This indicates that the complex represented by general formula I exhibits blue phosphorescence, and its emission peak and emission waveform in the blue light band can be manipulated by substituents.

[0220] Figure 6The UV-visible absorption spectra of complexes 40 and 148 according to a specific embodiment of the present invention are shown below. Complexes 40 and 148 exhibit nearly identical absorption bands, but the relative intensities within each band vary significantly, indicating that the substituents significantly influence the distribution of excited-state charges. The absorption spectrum exhibits very strong absorption in the long-wavelength region of 280-420 nm, a region distinct from that of the ligand precursor. The absorption peaks between 280 and 330 nm can be attributed to π-π* transitions centered around carbazole in the complex, while the absorption peaks beyond 330 nm can be attributed to valence transfer transitions between the complex's central metal ion and the ligand, as well as charge transitions within different ligand moieties. This demonstrates that these molecules possess complex excitation transition characteristics, resulting in highly efficient energy absorption and a preferred molecular structure for doping material molecules. The absorption peak between 400 and 430 is associated with the metal-to-ligand charge transfer transition, and the absorption band is also strong, indicating that this series of compounds has a strong metal-to-ligand charge transfer effect. According to relevant theory (Yersin, H.; Finkenzeller, WJ Triplet Emitters for Organic Light-Emitting Diodes: Basic Properties; 2008.), this effect can increase the phosphorescent luminescence efficiency of the molecules. This type of complex molecule can be used as a preferred molecule for doping materials in phosphorescent devices.

[0221] Test Example 2

[0222] Characterization of photophysical properties of the complex

[0223] Representative data on the color purity of the emitter can be obtained from the emission spectra of thin films prepared using a 5% polymethyl methacrylate dichloromethane solution. Table 1 shows the emission spectrum data of the complexes. In Table 1 below, λ is the peak wavelength, FWHM is the half-maximum width, 450-700nm is the integral ratio of the emission spectrum within the 450-500nm range, and CIE (x, y) is the chromaticity coordinate parameter based on the International Commission on Illumination standard. The five complexes prepared in the examples of the present invention have peak wavelengths between 440-470nm and half-maximum widths between 19-30nm, and all are blue light emitting materials.

[0224] Table 1

[0225]

[0226] The above data show that the blue light wavelength peak of the divalent platinum complex provided by the embodiment of the present invention is in the range of 440-470 nm, and more than 50% of the blue light spectrum is in the range of 450-490 nm. Therefore, it can be used as a blue light electroluminescent material or photoluminescent material.

[0227] Test Example 3

[0228] Characterization of the band gap and related optical properties of the complexes

[0229] The band gaps and related optical properties of the five complexes are shown in Table 2 below:

[0230] The band gap value of the material (E g ), LUMO and HOMO values ​​were measured by cyclic voltammetry. The entire test process was carried out on a CHI600D electrochemical workstation (Shanghai Chenhua Instrument Co., Ltd.) in a glove box (Lab2000, Etelux). A three-electrode system was formed with a Pt column as the working electrode, Ag / AgCl as the reference electrode, and a Pt wire as the auxiliary electrode. The medium used in the test process was a 0.1M dimethylformamide solution of tetrabutylammonium hexafluorophosphate. The measured potentials were all based on the added ferrocene as the internal standard. In the table below, λ is the peak wavelength of the divalent platinum complex dissolved in dichloromethane, FWHM is its half-peak width, and the triplet photon energy of the material (E T1 ) is calculated from the formula 1240 / λ 0→1 Calculated (λ 0→1 is the first vibration peak at 77K), and its unit is electron volt (eV).

[0231] Table 2

[0232] Complex <![CDATA[E HOMO / eV]]> <![CDATA[E LUMO / eV]]> Eg / eV <![CDATA[E S1 / eV]]> <![CDATA[E T1 / eV]]> 6 -5.09 -2.17 2.92 2.91 2.75 29 -5.10 -2.19 2.91 2.95 2.79 40 -5.17 -2.33 2.84 2.99 2.82 143 -5.12 -2.18 2.94 2.93 2.76 148 -5.11 -2.20 2.91 2.95 2.77

[0233] Test Example 4

[0234] Application of the divalent platinum complex of the present invention in OLED light-emitting devices

[0235] Figure 7A cross-sectional view of an OLED light-emitting device 1000 is shown, which can use the divalent platinum complex described herein as a light-emitting material. The OLED device 1000 includes a substrate 1002, an anode layer 1004, a hole transport layer 1006, a light-emitting layer 1008, an electron transport layer 1010, and a metal cathode layer 1012. The anode 1004 is generally a transparent material, such as indium tin oxide. The light-emitting layer 1008 can be a light-emitting material including an emitter and a host. The EIL refers to the electron injection layer, which can be regarded as part of the electron transport layer 1010. The HIL is the hole injection layer, which can be regarded as part of the hole transport layer 1006. The CPL is a cathode capping layer. The divalent platinum complex described in the present invention is used as a blue light-emitting doping material in the light-emitting layer 1008. When a divalent platinum complex is used as a doping material in an OLED device, the device is prepared by spin coating, and the structure is ITO / PEDOT:PSS (70nm) / main material: divalent platinum complex (1000-x:x, 40nm) / DPEPO (10nm) / TmPyPB (50nm) / Liq (1nm) / Al (100nm).

[0236] The light-emitting layer 1008 may comprise one or more divalent platinum complexes as described herein, optionally in combination with a host material. The ETL layer 1010 and the HTL 1006 may also comprise one or more divalent platinum complexes and another injection layer close to the electrode. The materials of the injection layer may include an EIL (electron injection layer), a HIL (hole injection layer) and a CPL (cathode capping layer), which may be in the form of a single layer or dispersed in an electron or hole transport material. The host material may be any suitable host material known in the art. The luminescent color of the OLED is determined by the luminescent energy (optical energy gap) of the light-emitting layer 1008 material, which can be tuned by tuning the electronic structure of the emitting platinum complex and / or the host material as described above. The hole transport material in the HTL layer 1006 and the electron transport material in the ETL layer 1010 may include any suitable hole transporter known in the art.

[0237] The complex 40 is doped into the host material as a light-emitting material to prepare a device OLED. The OLED device structure can be Figure 7 On the basis of the charge blocking layer, such as the hole blocking layer HBL and the electron blocking layer EBL, the device efficiency is improved. Figure 8As shown: ITO / P-doping HT / HTL / EBL / host material: platinum complex / HBL / N-doping ET / metal electrode. P-doping and N-doping refer to doping P-type and N-type materials, respectively, and these materials can be either organic or inorganic. BD refers to the blue-light doping material, namely the platinum complex of the present invention. In addition, the complex of the present invention can also be used in the following common device structures: ITO / HATCN (10nm) / NPD (40nm) / TAPC (10nm) / 2,6-mCPy: platinum complex / DPPS (40nm) / LiF / Al; ITO / HATCN (10nm) / NPD (40nm) / TAPC (10nm) / TAPC: PO15: platinum complex (25nm) / PO15 (10nm) / BmPyPB / LiF / Al; ITO / HATCN (10nm) / NPD (40nm) / mCBP: platinum complex / BAlq (10nm) / Alq (30nm) / LiF / Al; ITO / HATCN (10nm) / NPD (40nm) / TAPC (10nm) / host material: platinum complex / DPPS (40nm) / BmPyPB or TmPyPB / LiF / Al; ITO / HATCN(10nm) / HTL / EBL / bipolar host material: divalent platinum complex / bipolar host material / BmPyPB or TmPyPB / LiF / Al; platinum complex / DPPS(40nm) / BmPyPB or TmPyPB / LiF / Al; ITO / HATCN(10nm) / NPD(40nm) / TrisPCz(10nm) / mCBP: platinum complex (25nm) / Balq(10nm)or mCBT(8nm) / BPyTP(40nm) / LiF / Al, etc. Figure 8 In the schematic diagram of the OLED structure containing EBL and HBL layers in which the complex 40 is used as the electroluminescent material, the addition of a blocking layer can improve the charge utilization rate and luminous efficiency, and also increase the stability of the device.

[0238] Test Example 5

[0239] Function of complex 40 in light-emitting devices

[0240] Figure 9The luminescence spectrum of a device using platinum complex 40 is shown. The structure used is ITO / HATCN (10nm) / NPD (40nm) / TAPC (10nm) / 2,6-mCPy: 5% complex 4 (25nm) / 2,6-mCPy (10nm) / TmPyPB (30nm) / LiF (1nm) / Al (100nm). The electroluminescence spectrum of a device with a 5% doped light-emitting layer shows that the luminescence peak is red-shifted by 5nm relative to the photoluminescence peak in PMMA, with a comparable full width at half maximum (WFHM), preserving the inherent luminescence properties of complex 40. The calculated chromaticity coordinates are CIE (0.14, 0.16), indicating that this device is suitable for deep-blue light emitting devices. The normalized integral shows that only 13.4% of the irritating blue light is below 450nm, and 73.6% of the photon energy is above 500nm. According to traditional blue light attribution, blue light photons between 450-500 nm account for 60.2% of the number of all emitted photons.

[0241] Test Example 6

[0242] Determination of photoelectric conversion current efficiency of devices prepared with complex 40

[0243] Figure 10 is the photoelectric conversion current efficiency of the device using the complex 40 in the specific embodiment of the present invention, Figure 10 It can be seen that the current efficiency of the device prepared using complex 40 is higher. The device structure is ITO / HATCN (10nm) / ET301 (70nm) / OH006 (10nm) / 26mCPy:mCBP: complex 4 (47%:47%:4%, 30nm) / 26mcpy (10nm) / TmPyPb (30nm) / Liq / Al (120nm). Figure 10 The photoelectric conversion current efficiency of the device using complex 40 was very stable, ranging from 5 mA / cm 2 Up to 20mA / cm 2 Under the change of current density, the current roll-off is less than 5%, and the device of the doped material has a high efficiency, among which the 4% doped device has a high efficiency at 5mA / cm 2 The current efficiency is 14.2 cd / A, indicating that complex 40 has efficient and stable luminescent light conversion performance as a blue light emitting doping material.

[0244] Test Example 7

[0245] Power efficiency of devices using complex 40 in photoelectric conversion

[0246] Figure 11The power efficiency of photoelectric conversion of the device using complex 40 in the embodiment of the present application is shown, and the device structure is ITO / HATCN (10 nm) / ET301 (70 nm) / OH006 (10 nm) / 26mCPy:mCBP:complex 40 (47%:47%:4%, 30 nm) / 26mcpy (10 nm) / TmPyPb (30 nm) / Liq / Al (120 nm), and the proportion of complex 40 in the light-emitting layer material is 4%, the power efficiency of the 4% doped device is 352.91 cd / m 2 The luminance is 6.78 lm / W, and the complex 4 as a blue light-emitting dopant material has high and stable light conversion performance.

[0247] Test Example 8

[0248] External quantum efficiency of the device using complex 40 in photoelectric conversion

[0249] Figure 12 is the external quantum efficiency curve of the device using complex 40 in the embodiment of the present application; the device structure is ITO / HATCN (10 nm) / ET301 (70 nm) / OH006 (10 nm) / 26mCPy:mCBP:complex 4 (47%:47%:4%, 30 nm) / 26mcpy (10 nm) / TmPyPb (30 nm) / Liq / Al (120 nm), Figure 12 The curve of the external quantum efficiency of the device using complex 40 with the change of luminance is shown, and the external quantum efficiency is 9.35% at 711 cd / cm 2 to 5000 cd / cm 2 The external quantum efficiency roll-off is less than 5% with the change of luminance, and the device of the dopant material has high efficiency, and the external quantum efficiency of the 4% doped device is 9.35% at 711 cd / cm 2 The external quantum efficiency is 9.35%, which shows that the complex 40 as a blue light-emitting dopant material has high and stable light conversion performance.

[0250] Test Example 9

[0251] Time decay of electroluminescence of the device prepared by complex 40

[0252] Figure 13 is the time decay curve of the electroluminescence of the device prepared by the complex 40 in the present application. The device structure is ITO / HATCN (10 nm) / ET301 (70 nm) / OH006 (10 nm) / 26mCPy:mCBP:complex 40 (47%:47%:4%, 30 nm) / 26mcpy (10 nm) / TmPyPb (30 nm) / Liq / Al (120 nm), and the proportion of complex 40 in the light-emitting layer material is 4%, the power efficiency of the 4% doped device is 352.91 cd / m Figure 13It can be seen that the electroluminescence decay of the device prepared by complex 40 is slower and has better device stability. LT97@40mA / cm 2 The lifespan is 75min respectively.

[0253] Performance comparison experiment of light-emitting devices prepared using five complexes in Examples 1-5 The performance data of the light-emitting devices prepared using the above platinum complexes are shown in Table 3.

[0254] Table 3

[0255]

[0256] Table 3 shows a comparison of the luminescence performance data of the light-emitting devices prepared from various platinum complexes. The electroluminescence wavelength of the light-emitting device is mainly determined by the photoluminescence of the platinum complex itself, and the purity of the photoluminescence spectrum of the platinum complex itself is directly related to the spectral purity of the electroluminescence. Under the same conditions, the efficiency of the light-emitting device is also consistent with the trend of the luminescence quantum efficiency of the platinum complex itself, and the color purity of the light-emitting device is directly related to the spectral color purity of the light emitted under the light excitation of the doping material itself. Comparison of the electroluminescence spectrum of the platinum complex light-emitting device with the photoluminescent device in the thin film shows that the electroluminescence spectrum of the light-emitting device is slightly red-shifted compared to the photoluminescence spectrum of the thin film, but the peak wavelength is still in the blue light region (450-475nm), and most of the spectrum is also in the blue light range. The calculated chromaticity coordinates show that the light-emitting device is a pure blue light-emitting device. Since most of the light is in the blue light range, only a small amount of long-wavelength light needs to be filtered out, indicating that the platinum complex material provided by the embodiment of the present invention can fully meet the chromaticity requirements of high-efficiency pure blue light devices in displays.

[0257] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A blue phosphorescent divalent platinum complex, characterized in that: The blue phosphorescent divalent platinum complex has a structure shown in Formula I: Among them, R a 、R b 、R c 、R d 、R e and R f Each is independently selected from methyl, deuterated methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, 2-methylphenyl, 2-isopropylphenyl, 2-ethylphenyl, 4-methylphenyl, 4-isopropylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 2,3-dimethylphenyl, 2,3-diethylphenyl, 2,3-diisopropylphenyl, 2 ,3-diisobutylphenyl, 2,3-dicyclohexylphenyl, 2,3-dicyclopropylphenyl, 2,3-dicyclobutylphenyl, 2,3-dicyclopentylphenyl, 2,4-dimethylphenyl, 2,4-diethylphenyl, 2,4-diisopropylphenyl, 2,4-diisobutylphenyl, 2,4-dicyclohexylphenyl, 2,4-dicyclopropylphenyl, 2,4-dicyclobutylphenyl, 2,4-dicyclopentylphenyl, 2,6 -dimethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,6-diisobutylphenyl, 2,6-dicyclohexylphenyl, 2,6-dicyclopropylphenyl, 2,6-dicyclobutylphenyl, 2,6-dicyclopentylphenyl, 3,5-dimethylphenyl, 3,5-diethylphenyl, 3,5-diisopropylphenyl, 3,5-diisobutylphenyl, 3,5-dicyclohexylphenyl, 3,5-dicyclopropylphenyl, propylphenyl, 3,5-dicyclobutylphenyl, 3,5-dicyclopentylphenyl, 2,3,5,6-tetramethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 2,4,6-triisopropylphenyl, 2,4,6-triisobutylphenyl, 2,4,6-tricyclohexylphenyl, 2,4,6-tricyclopropylphenyl, 2,4,6-tricyclobutylphenyl or 2,4,6-tricyclopentylphenyl.

2. A blue phosphorescent divalent platinum complex, characterized in that: The blue phosphorescent divalent platinum complex is selected from at least one of the following:

3. The blue phosphorescent divalent platinum complex according to claim 2, wherein The blue phosphorescent divalent platinum complex is selected from at least one of the following:

4. A method for preparing the blue phosphorescent divalent platinum complex according to claim 1, characterized in that: The method includes: (1) Under protective gas, a first coupling reaction is performed on the compound represented by formula (II) and a boronic acid having a substituent to obtain a compound represented by formula (III); (2) Under protective gas, the compound represented by formula (III) is subjected to a second coupling reaction with trifluoroacetamide to obtain the compound represented by formula (IV); (3) Under protective gas, the compound represented by formula (IV) is subjected to a third coupling reaction with substituted o-bromoaniline to obtain a compound represented by formula (V); (4) Under protective gas, the compound represented by formula (V) is subjected to a ring-closure reaction with ammonium hexafluorophosphonate to obtain a compound represented by formula (VI); (5) subjecting the compound represented by formula (VI) to a cyclometallation reaction to obtain a divalent platinum complex represented by formula (I); Wherein, the definitions of the groups in formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI) are the same as those described in claim 1.

5. The method according to claim 4, wherein In step (1), the first coupling reaction is further carried out in the presence of a catalyst, a ligand, a base and a solvent; And / or, the catalyst is a palladium catalytic system; and / or, the ligand is a phosphine ligand; and / or, the base is an inorganic base; and / or, the solvent is selected from 1,4-dioxane and / or ethylene glycol dimethyl ether; and / or, the molar ratio of the compound represented by formula (II), the catalyst, the ligand and the base is 1:(0.05-2):(0.1-5):(2.5-10); And / or, the reaction conditions of the first coupling reaction include: temperature of 90-110° C. and time of 11-13 h.

6. The method according to claim 5, wherein: The palladium catalyst is selected from one or more of tris(dibenzylideneacetone)dipalladium, tetrakistriphenylphosphine palladium and palladium acetate; And / or, the phosphine ligand is selected from one or more of 2-(di-tert-butylphosphino)biphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxy-biphenyl and 1,1'-binaphthyl-2,2'-bisdiphenylphosphine.

7. The method according to claim 4, wherein: The second coupling reaction further comprises being carried out in the presence of a catalyst, a ligand, a base and a solvent; and / or, the catalyst is a copper catalyst; And / or, the ligand is selected from N 1 ,N 2 -Dimethylethane-1,2-diamine, 2,2,6,6-tetramethylheptanedione N 1 ,N 2 - one or more of bis(5-methyl-[1,1'-biphenyl]-2-yl)oxamide, trans-cyclohexanediamine, 1-methylimidazole and L-proline; and / or, the base is selected from one or more of cesium carbonate, potassium carbonate, potassium phosphate, cesium fluoride and potassium hydroxide; and / or, the solvent is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, ethylene glycol dimethyl ether, deionized water and toluene; and / or, the molar ratio of the compound represented by formula (III), trifluoroacetamide, catalyst, ligand and base is 1:(2-10):(0.1-3):(0.5-5):(2-10); And / or, the conditions of the second coupling reaction include: temperature of 110-130° C. and time of 23-25 ​​h.

8. The method according to claim 7, wherein: The copper catalyst is selected from one or more of cuprous iodide, cuprous bromide and cuprous chloride.

9. The method according to claim 4, wherein: The third coupling reaction further comprises being carried out in the presence of a catalyst, a ligand, a base and a solvent; And / or, the catalyst is a copper catalyst or a palladium catalyst; And / or, the ligand is selected from phosphine ligand, N 1 ,N 2 -dimethylethane-1,2-diamine, 2,2,6,6-tetramethylheptanedione, N 1 ,N 2 - one or more of bis(5-methyl-[1,1'-biphenyl]-2-yl)oxamide, trans-cyclohexanediamine, 1-methylimidazole and L-proline; and / or, the base is an inorganic base or an organic base; and / or, the solvent is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, ethylene glycol dimethyl ether, deionized water and toluene; and / or, the molar ratio of the compound represented by formula (IV), o-bromoaniline, catalyst, ligand and base is 1:(2-10):(0.1-5):(0.5-5):(2-10); And / or, the conditions of the third coupling reaction include: temperature of 90-110° C. and time of 23-25 ​​h.

10. The method according to claim 4, wherein: The ring-closure reaction further comprises being carried out in the presence of a solvent, triethyl orthoformate; and / or, the molar ratio of the compound represented by formula (V), ammonium hexafluorophosphonate, and triethyl orthoformate is 1:(1.2-5):(0.25-3); And / or, the conditions of the ring-closure reaction include: temperature of 110-130° C. and time of 23-25 ​​h.

11. The method according to claim 4, wherein The cyclometallation reaction further comprises being carried out in the presence of platinum dichloride and N,N-dimethylformamide; and / or, the compound represented by formula (VI) and platinum dichloride are fed in a ratio of 1:(1.1-5); And / or, the cyclometallation reaction conditions include: under nitrogen, temperature of 120-140° C., and time of 71-73 h.

12. Use of the blue phosphorescent divalent platinum complex according to any one of claims 1 to 3 in an organic optoelectronic device.

13. An organic photoelectric device, characterized in that: The device comprises a substrate, an anode layer, a hole transport layer, a light-emitting layer, an electron transport layer and a metal cathode layer, wherein at least one of the light-emitting layer, the electron transport layer and the hole transport layer comprises the blue phosphorescent divalent platinum complex according to any one of claims 1 to 3.

14. The organic photoelectric device according to claim 13, wherein: The light-emitting layer contains a blue phosphorescent divalent platinum complex.

15. The organic photoelectric device according to claim 13 or 14, wherein: The blue phosphorescent divalent platinum complex is a luminescent material, a host material or a guest material in the luminescent layer.

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