Divalent metal complexes, their preparation method and use, and organic optoelectronic devices

Abstract

The present invention relates to the technical field of optoelectronic materials, in particular to a divalent metal complex such as a divalent platinum complex, its preparation method and use, and an organic optoelectronic device comprising said complex. The divalent metal complex has a structure as shown in formula (I). The divalent metal complex has a green light peak wavelength of 515 to 535 nm, and the CIE spectrum covers the green light region well. Furthermore, the divalent metal complex has relatively high current efficiency and energy efficiency. [Formula 1] JPEG2025526440000061.jpg48169

Description

Detailed Description of the Invention

[0001] [Technical Field] The present invention relates to the technical field of optoelectronic materials, in particular to divalent metal complexes such as divalent platinum complexes, their preparation and use, and organic optoelectronic devices containing said complexes.

[0002] 〔background〕 The development of optoelectronic materials is becoming increasingly important in modern society, and much research has been done in this field, especially on materials for optical or electroluminescent devices. Organometallic complex materials can emit light of various colors when an electric current is passed through them, and they are considered promising for applications in flat panel displays and solid-state lighting. Products related to molecular-level semiconductor technology, such as organic light-emitting diode (OLED) technology, have many advantages in terms of applicability, low power consumption, etc.

[0003] In terms of light emission, green is one of the three primary colors (RGB). Currently, optoelectronic materials applicable to light-emitting and lighting devices are primarily red and green phosphorescent organometallic materials and blue fluorescent organometallic materials. While these materials have achieved great success in lighting and advanced display applications, they suffer from short emission lifetimes, high heat generation, and low practical efficiency in large-scale display applications. In addition to the basic RGB primary color elements, there is also an urgent need for the application of white light elements. White light is a combination of visible light, and by using the combination of blue light, green phosphorescent light, and red phosphorescent light, a white phosphorescent light source with high efficiency and high stability can be formed.

[0004] Therefore, highly efficient green phosphorescent light-emitting materials and devices have practical application value in organic optoelectronic devices, especially in display equipment and / or lighting equipment.

[0005] DISCLOSURE OF THE INVENTION The present invention aims to overcome the problem that green-emitting complex materials in current OLED technology are not sufficiently superior in terms of emission color, efficiency, and stability. It provides a divalent metal complex, preferably a divalent platinum complex, its preparation and use, and an organic optoelectronic device containing the divalent metal complex, preferably the divalent platinum complex. Light-emitting devices fabricated using green phosphorescent divalent metal complexes, such as the divalent platinum complexes provided by the present invention, have a green light wavelength peak in the range of 530 to 540 nm, a green light range well covered by the CIE. In addition, the devices also have higher current and power efficiencies, better meeting the requirements of flat panel displays.

[0006] To achieve one or more of the above objects, a first aspect of the present invention provides a divalent metal complex comprising: having a structure represented by formula (I):

[0007] [ka]

[0008] In formula (I), M is Pt or Pd, preferably Pt; A is O or S, preferably O; R1 is trimethylsilyl, optionally substituted C1-C 30 Alkyl, optionally substituted C3-C 12 Cycloalkyl, optionally substituted C5-C 30 Aryl, optionally substituted C2-C 30 Heteroaryl, optionally substituted C1-C 30 Alkoxy, optionally substituted C3-C 12 Cycloalkyloxy, optionally substituted C5-C 30 Aryloxy, optionally substituted C5-C 30 Arylamino, optionally substituted C5-C 30 Heteroaryloxy or optionally substituted C5-C 30 heteroarylamino, and, R2~R 17 are the same or different and each independently represents a hydrogen atom, an isotope of hydrogen, a halogen atom, cyano, isocyano, thiocyano, isothiocyanato, trimethylsilyl, or an optionally substituted C1-C 30 Alkyl, optionally substituted C3-C 12 Cycloalkyl, optionally substituted C5-C 30 Aryl, optionally substituted C2-C 30 Heteroaryl, optionally substituted C1-C 30 Alkoxy, optionally substituted C3-C 12 Cycloalkyloxy, optionally substituted C5-C 30 Aryloxy, optionally substituted C5-C 30 Arylamino, optionally substituted C5-C 30 Heteroaryloxy and optionally substituted C5-C 30 heteroarylamino; Here, "optionally substituted" means that the group is C1 to C 30 Alkyl, C3-C 12 Cycloalkyl, C1-C 30 Alkoxy, C5-C 30 Aryl, C2-C 30 Heteroaryl, C5-C 30 It means that it may be further substituted with one or more groups selected from aryloxy and halogen, or it may not be substituted. A divalent metal complex is provided.

[0009] In some embodiments, the divalent metal complex is a divalent platinum complex having a structure represented by formula (I'):

[0010] [ka]

[0011] In formula (I'), R1 is trimethylsilyl, optionally substituted C1-C30 Alkyl, optionally substituted C3-C 12 Cycloalkyl, optionally substituted C5-C 30 Aryl, optionally substituted C2-C 30 Heteroaryl, optionally substituted C1-C 30 Alkoxy, optionally substituted C3-C 12 Cycloalkyloxy, optionally substituted C5-C 30 Aryloxy, optionally substituted C5-C 30 Arylamino, optionally substituted C5-C 30 Heteroaryloxy or optionally substituted C5-C 30 heteroarylamino, and, R2~R 17 are the same or different and each independently represents a hydrogen atom, an isotope of hydrogen, a halogen atom, cyano, isocyano, thiocyano, isothiocyanato, trimethylsilyl, or an optionally substituted C1-C 30 Alkyl, optionally substituted C3-C 12 Cycloalkyl, optionally substituted C5-C 30 Aryl, optionally substituted C2-C 30 Heteroaryl, optionally substituted C1-C 30 Alkoxy, optionally substituted C3-C 12 Cycloalkyloxy, optionally substituted C5-C 30 Aryloxy, optionally substituted C5-C 30 Arylamino, optionally substituted C5-C 30 Heteroaryloxy and optionally substituted C5-C 30 heteroarylamino; Here, "optionally substituted" means that the group is C1 to C 30 Alkyl, C3-C 12 Cycloalkyl, C1-C 30 Alkoxy, C5-C 30 Aryl, C2-C 30 Heteroaryl, C5-C 30This means that it may be further substituted with one or more groups selected from aryloxy and halogen, or it may not be substituted.

[0012] A second aspect of the present invention is a method for preparing a divalent metal complex as described above, comprising the steps of: (1) performing a first coupling reaction between a compound a represented by formula (a) and a phenol compound b represented by formula (b) to obtain a compound c represented by formula (c);

[0013] [ka]

[0014] (2) performing a functional group transformation reaction on the compound c represented by formula (c) to obtain a compound represented by formula (d);

[0015] [ka]

[0016] (3) performing a second coupling reaction between a compound d represented by formula (d) and a compound h represented by formula (h) to obtain a compound represented by formula (e); and performing a third coupling reaction between the compound e represented by formula (e) and an amine compound i represented by formula (i) to obtain a compound f represented by formula (f); or, (4) performing a third coupling reaction between the compound d represented by formula (d) and an o-aniline compound j represented by formula (j) to obtain a compound f represented by formula (f);

[0017] [ka]

[0018] (5) subjecting the compound f represented by formula (f) to a ring-closing reaction to obtain a compound g represented by formula (g); Preferably, the compound f represented by formula (f) is subjected to a ring-closure reaction with ammonium hexafluorophosphate and triethyl orthoformate to obtain a compound g represented by formula (g);

[0019] [ka]

[0020] (6) subjecting the compound g represented by formula (g) to a cyclometallation reaction in the presence of a divalent platinum or palladium compound to obtain the divalent metal complex represented by formula (I); Including, Here, the groups R1 to R2 in formula (I), formula (a), formula (b), formula (c), formula (d), formula (e), formula (f), formula (g), formula (h), formula (i), and formula (j) 17 The definitions of A and B are the same as those in the first aspect above, X in formula (a), formula (c), formula (e), formula (h), and formula (j) are the same or different and each is F, Br, I, Cl, or OTf; A method is provided.

[0021] Preferably, the process of the present invention is a process for preparing a divalent platinum complex of formula (I'), comprising: (1) carrying out a first coupling reaction between a furan compound a represented by formula (a) and a phenol compound b represented by formula (b) together with a substituent under the protection of a protective gas to obtain a compound c represented by formula (c); (2) carrying out a functional group conversion reaction of the compound c represented by formula (c) under the protection of a protective gas to convert the X group into amino, thereby obtaining a compound represented by formula (d); (3) under the protection of protective gas, carrying out a second coupling reaction between the compound d represented by formula (d) and the compound h represented by formula (h) together with a substituent to obtain a compound represented by formula (e), and carrying out a third coupling reaction between the compound e represented by formula (e) and an amine compound i represented by formula R1-NH2 to obtain a compound f represented by formula (f); or, (4) carrying out a third coupling reaction between the compound d represented by formula (d) and an o-aniline compound j represented by formula (j) under the protection of a protective gas to obtain a compound f represented by formula (f); (5) subjecting the compound f represented by formula (f) to a ring-closure reaction with ammonium hexafluorophosphate and triethyl orthoformate under the protection of a protective gas to obtain a compound represented by formula (g); (6) a step of subjecting the compound g represented by formula (g) to a cyclometallation reaction in the presence of cyclooctadiene platinum(II) dichloride or platinum dichloride to obtain a divalent platinum complex represented by formula (I'); Including,

[0022] [ka]

[0023] wherein the definitions of the groups in formula (I'), formula (a), formula (b), formula (c), formula (d), formula (e), formula (f), formula (g), formula (h), and formula (j) are the same as those in the first aspect above; X in formula (a), formula (c), formula (e), formula (h), and formula (j) are the same or different and each is F, Br, I, Cl, or OTf; It is a method.

[0024] A third aspect of the present invention provides the use of a divalent metal complex as described above, such as a divalent platinum complex, in an organic optoelectronic device, such as an organic electroluminescent device.

[0025] A fourth aspect of the present invention provides the use of a divalent metal complex as described above, such as a divalent platinum complex, in a green phosphorescent organic optoelectronic device.

[0026] A fifth aspect of the present invention is an organic optoelectronic device, comprising: Preferably, the organic electroluminescent device is an anode layer, a light-emitting layer, and a cathode layer; the light-emitting layer comprises the aforementioned divalent metal complex, preferably a divalent platinum complex; In some embodiments, 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; At least one of the light-emitting layer, the electron-transporting layer, and the hole-transporting layer comprises a divalent metal complex as described above, such as a divalent platinum complex.

[0027] Divalent metal complexes, such as divalent platinum complexes, provided by the present invention can be used as electroluminescent or photoluminescent materials. For example, the divalent metal complexes, such as divalent platinum complexes, can be used as green light-emitting materials or phosphorescent light-emitting materials. Furthermore, divalent metal complexes, such as divalent platinum complexes, provided by the present invention can be used to fabricate light-emitting devices. The green wavelength peak of the light-emitting device is in the range of 530 to 540 nm, and the majority of the spectrum of the light-emitting device is located in the green light range. Calculated chromaticity coordinates indicate that the light-emitting device belongs to a green light-emitting device, and the calculated chromaticity coordinates well cover the green light range. The light-emitting device can have a maximum current efficiency (CE) of 63.70 cd / A and a maximum power efficiency (PE) of 81.30 lm / W. Additionally, the full width at half maximum (FWHM) of the green light spectrum obtained from divalent metal complexes provided by the present invention, such as the divalent platinum complexes, can be less than 30 nm, and the photoluminescence quantum yield can be up to greater than 95%.

[0028] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph of the emission spectra of the complex 2 prepared in Example 1 of the present invention in solution and thin film; FIG. 2 is a graph of the emission spectra of complex 4 prepared in Example 2 of the present invention in solution and thin film; FIG. 3 is a graph of the emission spectra of the complex 16 prepared in Example 3 of the present invention in solution and thin film; FIG. 4 is a graph of the ultraviolet-visible absorption spectrum of complex 2 prepared in Example 1 of the present invention; FIG. 5 shows the structure of Complex 2 prepared in Example 1 of the present invention. 1 H-NMR nuclear magnetic spectrum; FIG. 6 shows the structure of Complex 4 prepared in Example 2 of the present invention. 1 H-NMR nuclear magnetic spectrum; FIG. 7 shows the structure of complex 16 prepared in Example 3 of the present invention. 1 H-NMR nuclear magnetic spectrum; Figure 8 is a purity characterization graph of complex 25 prepared in Example 4 of the present invention; FIG. 9 is a graph of the mass spectrum of complex 25 prepared in Example 4 of the present invention; FIG. 10 is a graph of the mass spectrum of complex 16 prepared in Example 3 of the present invention; Figure 11 shows the structure diagram of an OLED light-emitting element; Figure 12 shows the emission spectrum of the device using complex 4; FIG. 13 is a graph of the EQE-current density curve for an OLED device made with complex 4; Figure 14 shows a graph of the electroluminescence decay over time of a device made with complex 4; FIG. 15 is a schematic diagram of a synthesis scheme for a green phosphorescent divalent platinum complex.

[0029] Detailed Description The range endpoints and any values disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the range endpoints, range endpoints and individual point values, and individual point values can be combined to obtain one or more new numerical ranges and should be considered specifically disclosed herein.

[0030] The wavelength of green light that is generally perceptible to the human eye is generally considered to be between 500 and 560 nm. However, higher chromaticity standards exist for the green color required for displays. Currently, there are two generally accepted standards: one is the U.S. National Television Systems Committee's definition of green light's CIE chromaticity coordinates (0.21, 0.71), and the other is the BT2020 standard proposed by the International Telecommunication Union in 2016, which requires CIE coordinates of (0.170, 0.797). The latter standard imposes higher chromaticity requirements than the former, and therefore also imposes higher requirements on the monochromaticity of the light source. Monochromatic light with an emission wavelength between 520 and 535 nm can better meet the chromaticity requirements of the BT2020 standard. That is, the synthesized complex has an emission peak of 520 to 535 nm and a narrow spectrum, which can better meet the chromaticity requirements of the BT2020 standard and is required to have better monochromaticity of the material so that it can be better used in displays.

[0031] The present invention provides a light-emitting material that can satisfy the above requirements.

[0032] As described above, the present invention provides a divalent metal complex, The divalent metal complex has a structure represented by formula (I):

[0033] [ka]

[0034] In formula (I), M is Pt or Pd, preferably Pt; A is O or S, preferably O; R1 is trimethylsilyl, optionally substituted C1-C 30 Alkyl, optionally substituted C3-C 12 Cycloalkyl, optionally substituted C5-C 30 Aryl, optionally substituted C2-C 30 Heteroaryl, optionally substituted C1-C 30 Alkoxy, optionally substituted C3-C 12 Cycloalkyloxy, optionally substituted C5-C 30 Aryloxy, optionally substituted C5-C 30 Arylamino, optionally substituted C5-C 30 Heteroaryloxy or optionally substituted C5-C 30 heteroarylamino, and, R2~R 17 are the same or different and each independently represents a hydrogen atom, an isotope of hydrogen, a halogen atom, cyano, isocyano, thiocyano, isothiocyanato, trimethylsilyl, or an optionally substituted C1-C 30 Alkyl, optionally substituted C3-C 12 Cycloalkyl, optionally substituted C5-C 30 Aryl, optionally substituted C2-C 30 Heteroaryl, optionally substituted C1-C 30 Alkoxy, optionally substituted C3-C 12 Cycloalkyloxy, optionally substituted C5-C 30 Aryloxy, optionally substituted C5-C 30 Arylamino, optionally substituted C5-C 30 Heteroaryloxy and optionally substituted C5-C 30 heteroarylamino; Here, "optionally substituted" means that the group is C1 to C 30 Alkyl, C3-C12 Cycloalkyl, C1-C 30 Alkoxy, C5-C 30 Aryl, C2-C 30 Heteroaryl, C5-C 30 It means that it may be further substituted with one or more groups selected from aryloxy and halogen, or it may not be substituted. The present invention provides a divalent metal complex characterized by the above-mentioned.

[0035] In a preferred embodiment, in formula (I), M is Pt and A is O. Under such circumstances, the present invention provides a divalent platinum complex comprising: The divalent platinum complex has a structure represented by formula (I'):

[0036] [ka]

[0037] In formula (I'), R1~R 17 provides divalent platinum complexes, each as defined in formula (I) above.

[0038] The present inventors have surprisingly found that the divalent platinum or palladium complex molecules disclosed herein, coordinated by neutral tetradentate ligands containing dibenzofuran or dibenzothiophene structures, are capable of emitting green light as phosphorescent light-emitting materials, and possess the properties of good stability, high efficiency, and narrow emission range, making them particularly suitable for use as organic green emitters in OLED-related products.

[0039] In addition, the divalent metal complexes provided by the present invention are easy to prepare and purify by sublimation, can be dissolved in common organic solvents, and are suitable for evaporation and solution device processing. The luminescent properties of the complexes of the present invention are characterized by good color purity, which overcomes the lack of stable and highly efficient narrowband green phosphorescent materials in the field of flat panel displays, and simultaneously achieves the functions of green light emission and improving device performance.

[0040] The stable complex luminescent materials provided by the present invention are more suitable for the requirements of flat panel displays, as shown by the CIE coordinates and luminous efficiency.

[0041] In some embodiments, in the above formula (I) or formula (I'), R1 is an optionally substituted C1-C 12 Alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C5-C 30 Aryl, optionally substituted C2-C 30 Heteroaryl, optionally substituted C1-C 12 Alkoxy, optionally substituted C5-C 30 Aryloxy or optionally substituted C5-C 30 is arylamino, and, R2~R 17 are the same or different and each independently represents a hydrogen atom, an isotope of hydrogen, a halogen atom, cyano, isocyano, thiocyano, isothiocyanato, or an optionally substituted C1-C 12 Alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C5-C 30 Aryl, optionally substituted C2-C 30 Heteroaryl, optionally substituted C1-C 12 Alkoxy, optionally substituted C5-C 30 Aryloxy and optionally substituted C5-C 30 arylamino; Here, "optionally substituted" means that the group is C1 to C 12 Alkyl, C3-C8 cycloalkyl, C1-C 12 Alkoxy, C5-C 30 Aryl, C2-C 30 Heteroaryl, C5-C 30 This means that it may be further substituted with one or more groups selected from aryloxy and halogen, or it may not be substituted.

[0042] In some embodiments, in the above formula (I) or formula (I'), R1 is an optionally substituted C1-C 10 Alkyl, optionally substituted C3-C7 cycloalkyl, optionally substituted C5-C 24 Aryl or optionally substituted C2-C 24 is heteroaryl, R2~R 17 are the same or different and each independently represents a hydrogen atom, an isotope of hydrogen, a halogen atom, cyano, or an optionally substituted C1-C 10 Alkyl, optionally substituted C3-C7 cycloalkyl, optionally substituted C5-C 24 Aryl and optionally substituted C-C 24 heteroaryl; Here, "optionally substituted" means that the group is C1 to C 10 Alkyl, C3-C7 cycloalkyl, C1-C 10 Alkoxy, C5-C 24 Aryl, C2-C 24 Heteroaryl, C5-C 24 This means that it may be further substituted with one or more groups selected from aryloxy and halogen, or it may not be substituted.

[0043] In some embodiments, in the above formula (I) or formula (I'), R1 is an optionally substituted C1-C6 alkyl, an optionally substituted C3-C6 cycloalkyl, an optionally substituted C5-C14 Aryl or optionally substituted C2-C 14 is heteroaryl, R2~R 17 are the same or different, and each independently represents a hydrogen atom, an isotope of hydrogen, a halogen atom, cyano, an optionally substituted C1-C6 alkyl, an optionally substituted C3-C6 cycloalkyl, an optionally substituted C5-C 14 Aryl and optionally substituted C-C 14 heteroaryl; Here, "optionally substituted" means that the group is selected from the group consisting of C1 to C6 alkyl, C3 to C6 cycloalkyl, C5 to C 14 Aryl, C2-C 14 It means that it may be unsubstituted or further substituted with one or more groups selected from heteroaryl and halogen. The C1-C6 alkyl may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl (including all isomers), and hexyl (including all isomers), or may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl (including all isomers), and hexyl (including all isomers). The C3-C6 cycloalkyl may be selected from cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, or may include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The C5-C6 alkyl may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl (including all isomers), and hexyl (including all isomers). 14 The aryl may be selected from phenyl, naphthyl, fluorenyl, anthracenyl, and biphenyl, or may include phenyl, naphthyl, fluorenyl, anthracenyl, and biphenyl. 14Heteroaryl may be selected from or include furyl, imidazolyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxadiazolyl, oxazolyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, thiadiazolyl, thiazolyl, thienyl, triazinyl, and triazolyl.

[0044] In some embodiments, in the above formula (I) or formula (I'), R1 is an optionally substituted C1-C4 alkyl, an optionally substituted C5-C6 cycloalkyl, an optionally substituted C6-C 14 Aryl or optionally substituted C3-C 14 is heteroaryl, R2~R 17 are the same or different, and each independently represents a hydrogen atom, an isotope of hydrogen, a halogen atom, cyano, an optionally substituted C1-C4 alkyl, an optionally substituted C5-C6 cycloalkyl, an optionally substituted C6-C 14 Aryl and optionally substituted C3-C 14 heteroaryl; Here, "optionally substituted" means that the group is selected from the group consisting of C1-C4 alkyl, C5-C6 cycloalkyl, C6-C 14 Aryl, C3-C 14It means that it may be unsubstituted or may be further substituted with one or more groups selected from heteroaryl and halogen. The C1-C4 alkyl may be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl. The C5-C6 cycloalkyl may be selected from cyclopentyl and cyclohexyl, or may include cyclopentyl and cyclohexyl. The C6-C 14 The aryl may be selected from phenyl, naphthyl, fluorenyl, anthracenyl, and biphenyl, or may include phenyl, naphthyl, fluorenyl, anthracenyl, and biphenyl. 14 Heteroaryl may be selected from or include furyl, imidazolyl, isothiazolyl, isoxazolyl, oxazolyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, thiazolyl, thienyl, and triazinyl.

[0045] In some embodiments, in the above formula (I) or formula (I'), R1 is a polyatomic substituent, R2~R 17 are each independently selected from the group consisting of a hydrogen atom, a hydrogen isotope, a halogen atom, cyano, isocyano, thiocyano, isothiocyanato, and a polyatomic substituent. 12 Alkyl, C5-C 30 Aromatic group, C1~C 12The alkyl group includes unsubstituted straight-chain alkyl, substituted straight-chain alkyl, unsubstituted cycloalkyl, or substituted cycloalkyl. The aromatic group includes unsubstituted aryl, substituted aryl, aryloxy, arylamino, or heteroaryl. Preferably, according to the present invention, the polyatomic substituent is C1-C 10 Alkyl, or C5-C 24 It includes an aromatic group. According to the present invention, preferably, the alkyl includes an aryl-substituted alkyl, trimethylsilyl, unsubstituted cycloalkyl, or substituted cycloalkyl. According to the present invention, preferably, the aromatic group may include an alkyl-substituted aryl, or an aryl-substituted aryl.

[0046] In some embodiments, in the above formula (I) or formula (I'), R1 is methyl, methyl with three deuterated hydrogen atoms (trideuterated methyl), benzyl, diphenylmethyl, triphenylmethyl, ethyl, 2-phenylethyl, 2,2-diphenylethyl, 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, phenyl with five deuterated hydrogen atoms (pentadeuterated 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-diethyl Phenyl, 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, 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,selected from 6-tricyclobutylphenyl, 2,4,6-tricyclopentylphenyl, biphenyl-2-yl, and 4'-tert-butylbiphenyl-2-yl; and, R2~R 17are the same or different and each independently represents a hydrogen atom, deuterium, a halogen atom, methyl, methyl having three deuterated hydrogen atoms, benzyl, diphenylmethyl, triphenylmethyl, ethyl, 2-phenylethyl, 2,2-diphenylethyl, 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, cyclohex ... xyl, cycloheptyl, phenyl, phenyl with five deuterated hydrogen atoms, 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 phenyl, 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 phenyl, 3,5-diethylphenyl, 3,5-diisopropylphenyl, 3,5-diisobutylphenyl, 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,Selected from the group consisting of 6-tricyclobutylphenyl, 2,4,6-tricyclopentylphenyl, cyano, biphenyl-2-yl, and 4'-tert-butylbiphenyl-2-yl.

[0047] In some embodiments of the present invention, for the complex of formula (I) above: M is Pt; A is O, R1 is selected from the group consisting of isopropyl, phenyl having five deuterated hydrogen atoms, 2,6-diisopropylphenyl, and biphenyl-2-yl; and, R2~R 17 are the same or different and each is independently selected from the group consisting of hydrogen, deuterium, isopropyl, tert-butyl, and cyano.

[0048] In the present invention, "isotope atoms of hydrogen" may be selected from deuterium and tritium, with deuterium being preferred. In the present invention, "halogen" refers to fluorine, chlorine, bromine, and / or iodine.

[0049] In some embodiments of the present invention, one or more hydrogen atoms in the divalent metal complexes represented by formula (I) or formula (I') of the present invention may be replaced by deuterium atoms.

[0050] According to the present invention, in some embodiments, in the divalent metal complex, such as a divalent platinum complex, R to R 17 each independently represents a deuterated substituent -CDH2, -CD2H, -CD3, -CDR a R b , or -CD2R a R may be selected from a and R b are each independently H, C1 to C 12 Alkyl, C5-C 30 Aromatic group, C1~C 12The alkyl group may be selected from the group consisting of unsubstituted straight chain alkyl, substituted straight chain alkyl, unsubstituted cycloalkyl, and substituted cycloalkyl. The aromatic group may be unsubstituted aryl, substituted aryl, aryloxy, arylamino, or heteroaryl. Preferably, R a and R b are each independently hydrogen, C1 to C 10 Alkyl, or C5-C 24 Preferably, the alkyl group is selected from an aromatic group. Preferably, the alkyl group comprises an aryl-substituted alkyl group, trimethylsilyl, or haloalkyl group. The halogen in the haloalkyl group is selected from fluorine, chlorine, bromine, and iodine. Preferably, the aromatic group may comprise an alkyl-substituted aryl group or an aryl-substituted aryl group.

[0051] It should be noted that in the present invention, for example in the group "-CDH2", "C" refers to carbon, "D" refers to deuterium (D), an isotope of hydrogen, also called heavy hydrogen, and so on.

[0052] According to the present invention, in some embodiments, in the divalent metal complex, such as a divalent platinum complex, R to R 17 may each independently be selected from deuterated aryl or substituted deuterated aryl-Ar-dn, where Ar is selected from unsubstituted aryl, aryl-substituted aryl, or alkyl-substituted aryl. n is selected from the group consisting of one deuterium substitution, multiple deuterium substitutions, or all hydrogens replaced by deuterium.

[0053] According to the present invention, the divalent platinum complexes of the present invention may be complexes 1-30.

[0054] [ka] TIFF2025526440000012.tif182170TIFF2025526440000013.tif94170

[0055] A second aspect of the present invention is a method for preparing the divalent metal complexes described above, comprising the steps of: (1) performing a first coupling reaction between a compound a represented by formula (a) and a phenol compound b represented by formula (b) to obtain a compound c represented by formula (c);

[0056] [ka]

[0057] (2) performing a functional group conversion reaction on the compound c represented by formula (c) to obtain a compound represented by formula (d);

[0058] [ka]

[0059] (3) performing a second coupling reaction between a compound d represented by formula (d) and a compound h represented by formula (h) to obtain a compound represented by formula (e); and performing a third coupling reaction between the compound e represented by formula (e) and an amine compound i represented by formula (i) to obtain a compound f represented by formula (f); or, (4) performing a third coupling reaction between the compound d represented by formula (d) and an o-aniline compound j represented by formula (j) to obtain a compound f represented by formula (f);

[0060] [ka]

[0061] (5) subjecting the compound f represented by formula (f) to a ring-closing reaction to obtain a compound g represented by formula (g); Preferably, the compound f represented by formula (f) is subjected to a ring-closure reaction with ammonium hexafluorophosphate and triethyl orthoformate to obtain a compound g represented by formula (g);

[0062] [ka]

[0063] (6) subjecting the compound g represented by formula (g) to a cyclometallation reaction in the presence of a divalent platinum or palladium compound to obtain the divalent metal complex represented by formula (I); Including, Here, the groups R1 to R2 in formula (I), formula (a), formula (b), formula (c), formula (d), formula (e), formula (f), formula (g), formula (h), formula (i), and formula (j) 17 The definitions of A and B are the same as those in the first aspect above, X in formula (a), formula (c), formula (e), formula (h), and formula (j) are the same or different and each is F, Br, I, Cl, or OTf; A method is provided.

[0064] Preferably, the process of the present invention is a process for preparing a divalent platinum complex of formula (I'), comprising: (1) carrying out a first coupling reaction between a furan compound a represented by formula (a) and a phenol compound b represented by formula (b) together with a substituent under the protection of a protective gas to obtain a compound c represented by formula (c); (2) carrying out a functional group conversion reaction of the compound c represented by formula (c) under the protection of a protective gas to convert the X group into amino, thereby obtaining a compound represented by formula (d); (3) under the protection of protective gas, carrying out a second coupling reaction between the compound d represented by formula (d) and the compound h represented by formula (h) together with a substituent to obtain a compound represented by formula (e), and carrying out a third coupling reaction between the compound e represented by formula (e) and an amine compound i represented by formula R1-NH2 to obtain a compound f represented by formula (f); or, (4) carrying out a third coupling reaction between the compound d represented by formula (d) and an o-aniline compound j represented by formula (j) under the protection of a protective gas to obtain a compound f represented by formula (f); (5) subjecting the compound f represented by formula (f) to a ring-closure reaction with ammonium hexafluorophosphate and triethyl orthoformate under the protection of a protective gas to obtain a compound g represented by formula (g); (6) a step of subjecting the compound g represented by formula (g) to a cyclometallation reaction in the presence of cyclooctadiene platinum(II) dichloride or platinum dichloride to obtain a divalent platinum complex represented by formula (I'); Including,

[0065] [ka]

[0066] wherein the definitions of the groups in formula (I'), formula (a), formula (b), formula (c), formula (d), formula (e), formula (f), formula (g), formula (h), and formula (j) are the same as those in the first aspect above; X in formula (a), formula (c), formula (e), formula (h), and formula (j) are the same or different and each is F, Br, I, Cl, or OTf; It is a method.

[0067] In the present invention, the protective gas may be selected from nitrogen, helium, neon, argon, and the like.

[0068] In the method of the present invention, the step (1) may include a step of charging the compound a represented by the formula (a) and the compound b represented by the formula (b), which are raw materials, into a reaction vessel such as a sealed tube. The first coupling reaction may include a step of carrying out the reaction in the presence of a first catalyst, a first ligand, a first base, and a first solvent. The first catalyst may be a copper catalyst. The copper catalyst may be one or more selected from cuprous iodide, cuprous bromide, cuprous chloride, and cuprous oxide. The first ligand may be N 1 ,N 2 -Dimethylethane-1,2-diamine, 2,2,6,6-tetramethylheptadione, N 1 ,N 2 The first base may be one or more selected from 5-bis(5-methyl-[1,1'-biphenyl]-2-yl)oxamide, trans-cyclohexanediamine, and 1-methylimidazole. The first base may be an inorganic base, and the inorganic base may be one or more selected from cesium carbonate, potassium carbonate, potassium phosphate, cesium fluoride, and potassium hydroxide. The first solvent may be one or more selected from dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, ethylene glycol dimethyl ether, deionized water, and toluene.

[0069] According to the present invention, in the step (1), the molar ratio of the compound a represented by the formula (a), the compound b represented by the formula (b), the first catalyst, the first ligand, and the first base to be supplied may be (0.5 to 3):1:(0.01 to 0.3):(0.01 to 0.5):(1 to 5), preferably (1 to 1.5):1:(0.01 to 0.1):(0.01 to 0.4):(1.2 to 3), and more preferably (1 to 1.2):1:(0.02 to 0.04):(0.02 to 0.04):(1.2 to 1.5).

[0070] According to the present invention, in step (1), the conditions for the first coupling reaction may include a temperature of 90 to 130°C and a time of 5 to 36 hours, preferably a temperature of 100 to 110°C and a time of 7 to 9 hours.

[0071] In the method of the present invention, step (2) may include a step of charging the compound c represented by formula (c) and an ammonia source (a substance that converts an X group, such as a halogen, to an amino group) into a reaction vessel, such as a sealed tube. The reaction in step (2) may be carried out in the presence of a second catalyst, a second ligand, a second base, and a second solvent. In the present invention, the ammonia source may be one or more selected from aqueous ammonia, liquid ammonia, benzylamine, and trifluoroacetamide. The reaction that converts the X group, such as a halogen, to an amino group generally uses the second catalyst, which may be a copper catalyst or a palladium catalyst. Preferably, the copper catalyst may be one or more selected from cuprous iodide, cuprous bromide, and cuprous chloride, and the palladium catalyst may be one or more selected from tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium, and palladium acetate. The second ligand is a phosphine ligand, N 1 ,N 2The second base may be one or more selected from the group consisting of 2-(di-t-butylphosphine)biphenyl, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, and 1,1'-binaphthyl-2,2'-bis(diphenylphosphine). The second base may be an inorganic base or an organic base. The inorganic base may be one or more selected from the group consisting of cesium carbonate, potassium carbonate, potassium phosphate, cesium fluoride, and potassium hydroxide. The organic base may be one or more selected from the group consisting of sodium tert-butoxide, potassium tert-butoxide, and lithium tert-butoxide. The second solvent may be one or more selected from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, ethylene glycol dimethyl ether, deionized water, and toluene.

[0072] According to the present invention, in the step (2), the supply molar ratio of the compound c represented by the formula (c), the ammonia source, the second catalyst, the second ligand, and the second base may be 1:(1 to 5):(0.01 to 1):(0.01 to 1.5):(1 to 6), preferably 1:(2.0 to 3.0):(0.01 to 0.5):(0.01 to 1.0):(1 to 4), and more preferably 1:(2.0 to 2.5):(0.02 to 0.04):(0.04 to 0.06):(1.5 to 2.5).

[0073] According to the present invention, in step (2), the reaction conditions may include a temperature of 90 to 130°C and a time of 8 to 25 hours, preferably a temperature of 100 to 120°C and a time of 12 to 15 hours.

[0074] In the present invention, when the X group, such as a halogen, is converted to an amino group, the X group may be converted to an amine having a protecting group, and as a result, the protecting group must be removed. To remove the protecting group, reduction with palladium / carbon or reduction using iron powder as a reducing agent may be carried out under H protective gas, and the solvent may be a protic solvent such as methanol, ethanol, or tetrahydrofuran. The molar ratio of the amine having a protecting group to the reducing agent may be 1:(0.01-0.5), preferably 1:(0.05-0.1), more preferably 1:(0.1-0.3), the desired temperature may be room temperature, and the reaction time may be 8-25 hours, preferably 12-15 hours.

[0075] In the method of the present invention, step (3) may include a step of charging the compound d represented by formula (d) and the compound h represented by formula (h) into a reaction vessel such as a sealed tube and carrying out a second coupling reaction to obtain a compound represented by formula (e). The second coupling reaction may be carried out in the presence of a third catalyst, a third ligand, a third base, and a third solvent. The third catalyst in the reaction may be selected from a copper catalyst and a palladium catalyst. The copper catalyst may be one or more selected from cuprous iodide, cuprous bromide, and cuprous chloride, and the palladium catalyst may be one or more selected from tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium, and palladium acetate. The third ligand may be a phosphine ligand, N 1 ,N 2 -Dimethylethane-1,2-diamine, 2,2,6,6-tetramethylheptadione, N 1 ,N 2The third base may be one or more selected from 5-bis(5-methyl-[1,1'-biphenyl]-2-yl)oxamide, trans-cyclohexanediamine, 1-methylimidazole, and L-proline, and the phosphine ligand may be one or more selected from 2-(di-t-butylphosphine)biphenyl, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, and 1,1'-binaphthyl-2,2'-bis(diphenylphosphine). The third base may be an inorganic base or an organic base. The inorganic base may be one or more selected from cesium carbonate, potassium carbonate, potassium phosphate, cesium fluoride, and potassium hydroxide, and the organic base may be one or more selected from sodium tert-butoxide, potassium tert-butoxide, and lithium tert-butoxide. The third solvent may be one or more selected from dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, ethylene glycol dimethyl ether, deionized water, and toluene.

[0076] According to the present invention, in the step (3), the molar ratio of the compound d represented by formula (d), the compound h represented by formula (h), the third catalyst, the third ligand, and the third base to be supplied may be 1:(1 to 3):(0.01 to 0.5):(0.01 to 1):(0.5 to 5), preferably 1:(1 to 1.5):(0.05 to 0.1):(0.1 to 0.2):(1 to 3), and more preferably 1:(1.1 to 1.2):(0.05 to 0.08):(0.1 to 0.2):(1.5 to 2).

[0077] According to the present invention, in step (3), the conditions for the second coupling reaction may include a temperature of 90 to 150°C and a time of 11 to 25 hours, preferably a temperature of 130 to 140°C and a time of 20 to 23 hours.

[0078] According to the present invention, the step (3) may further include a step of charging the compound e represented by formula (e) and an amine having a substituent (e.g., the amine compound i represented by formula (i) or R1-NH2) into a reaction vessel such as a sealed tube and conducting a third coupling reaction to obtain the compound f represented by formula (f). Alternatively, the step (4) may include a step of charging the compound d represented by formula (d) and the o-aniline compound j represented by formula (j) into a reaction vessel such as a sealed tube and conducting a third coupling reaction to obtain the compound f represented by formula (f). The third coupling reaction may be carried out in the presence of a fourth catalyst, a fourth ligand, a fourth base, and a fourth solvent. The fourth catalyst in the reaction may be selected from a copper catalyst and a palladium catalyst. The copper catalyst may be one or more selected from cuprous iodide, cuprous bromide, and cuprous chloride, and the palladium catalyst may be one or more selected from tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium, and palladium acetate. The fourth ligand may be a phosphine ligand, N 1 ,N 2 -Dimethylethane-1,2-diamine, 2,2,6,6-tetramethylheptadione, N 1 ,N 2The fourth base may be one or more selected from 5-bis(5-methyl-[1,1'-biphenyl]-2-yl)oxamide, trans-cyclohexanediamine, 1-methylimidazole, and L-proline, and the phosphine ligand may be one or more selected from 2-(di-t-butylphosphine)biphenyl, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, and 1,1'-binaphthyl-2,2'-bis(diphenylphosphine). The fourth base may be an inorganic base or an organic base, and the inorganic base may be one or more selected from cesium carbonate, potassium carbonate, potassium phosphate, cesium fluoride, and potassium hydroxide, and the organic base may be one or more selected from sodium tert-butoxide, potassium tert-butoxide, and lithium tert-butoxide. The fourth solvent may be one or more selected from dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, ethylene glycol dimethyl ether, deionized water, and toluene.

[0079] According to the present invention, in the step (3), the molar ratio of the compound e represented by formula (e), the amine compound i having a substituent, the fourth catalyst, the fourth ligand, and the fourth base to be supplied may be 1:(1 to 5):(0.05 to 1):(0.01 to 1):(1 to 6), preferably 1:(1 to 2.5):(0.05 to 0.6):(0.01 to 1):(1 to 4), and more preferably 1:(1.1 to 1.5):(0.05 to 0.2):(0.05 to 0.08):(1.5 to 3).

[0080] According to the present invention, in the step (4), the molar ratio of the compound d represented by the formula (d), the o-aniline compound j represented by the formula (j), the fourth catalyst, the fourth ligand, and the fourth base to be supplied may be 1:(1 to 5):(0.05 to 1):(0.01 to 1):(1 to 6), preferably 1:(1 to 2.5):(0.05 to 0.6):(0.01 to 1):(1 to 4), and more preferably 1:(1.1 to 1.5):(0.05 to 0.2):(0.05 to 0.08):(1.5 to 3).

[0081] According to the present invention, in steps (3) and (4), the conditions for the third coupling reaction may include a temperature of 100 to 150°C and a time of 8 to 25 hours, preferably a temperature of 120 to 130°C and a time of 20 to 23 hours.

[0082] In the method of the present invention, the step (5) may include a step of charging the compound f represented by the formula (f) into a reaction vessel such as a sealed tube and carrying out the ring-closing reaction to obtain the compound g represented by the formula (g). Preferably, the step (5) includes a step of charging the compound f represented by the formula (f), ammonium hexafluorophosphate, and triethyl orthoformate into a reaction vessel such as a sealed tube and carrying out the ring-closing reaction to obtain the compound g represented by the formula (g). Triethyl orthoformate can also function as a solvent in the ring-closing reaction.

[0083] According to the present invention, in step (5), the supply molar ratio of the compound f represented by formula (f) to ammonium hexafluorophosphate may be 1:(1 to 3), preferably 1:(1 to 1.5), and more preferably 1:(1.1 to 1.3).

[0084] According to the present invention, in step (5), the conditions for the ring-closure reaction may include a temperature of 110 to 130°C and a time of 23 to 25 hours, preferably a temperature of 120 to 125°C and a time of 24 to 25 hours.

[0085] According to the present invention, step (6) may comprise a step of subjecting compound g represented by formula (g) to a cyclometallation reaction in the presence of a divalent platinum or palladium compound to obtain the divalent metal complex represented by formula (I). Preferably, step (6) may comprise a step of subjecting compound g represented by formula (g) to a cyclometallation reaction in the presence of cyclooctadieneplatinum(II) dichloride or platinum dichloride to obtain the divalent platinum complex represented by formula (I'). The cyclometallation reaction may comprise a step of uniformly mixing and reacting compound g represented by formula (g), a divalent platinum or palladium compound such as cyclooctadieneplatinum(II) dichloride or platinum dichloride, sodium acetate, and a solvent such as tetrahydrofuran or N,N-dimethylformamide.

[0086] According to the present invention, in step (6), the molar ratio of the compound g represented by formula (g) to the divalent platinum or palladium compound, such as cyclooctadiene platinum(II) dichloride or platinum dichloride, is 1:(0.5-3), preferably 1:(0.5-1.1), more preferably 1:(0.9-1).

[0087] According to the present invention, in step (6), the conditions for the cyclometallation reaction may include heating to 100 to 140°C in the presence of a protective gas, for example, under a nitrogen atmosphere, and reacting for 71 to 75 hours with stirring, preferably heating to 120 to 130°C and reacting for 72 to 74 hours with stirring.

[0088] According to the present invention, in some embodiments, the method for synthesizing the divalent platinum complex of the present invention may include a scheme as shown in Figure 15. Preferably, in the present invention, the divalent platinum complex of the present invention is synthesized according to the scheme shown in Figure 15.

[0089] In the present invention, the first coupling reaction may be an Ullmann coupling reaction, and / or the second coupling reaction may be an Ullmann coupling reaction or a Buchwald-Hartwig coupling reaction; and / or The third coupling reaction may be an Ullmann coupling reaction or a Buchwald-Hartwig coupling reaction. The Ullmann coupling reaction and the Buchwald-Hartwig coupling reaction are known in the art, and those skilled in the art may select appropriate reaction conditions and parameters accordingly.

[0090] A third aspect of the present invention provides the use of a divalent metal complex of the present invention, such as a divalent platinum complex, in an organic optoelectronic device, which may be a green phosphorescent organic optoelectronic device or a green phosphorescent organic electroluminescent device.

[0091] According to the present invention, in some embodiments, the organic optoelectronic device comprises a display device and / or a lighting device.

[0092] A fourth aspect of the present invention is an organic optoelectronic device, comprising: Preferably an organic electroluminescent device such as an OLED, an anode layer, a light-emitting layer, and a cathode layer; the light-emitting layer comprises a divalent metal complex according to the present invention, preferably a divalent platinum complex; In some embodiments, the organic optoelectronic device may include a substrate, an anode layer, a hole transport layer, an emissive 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 comprises a divalent metal complex of the present invention, preferably a divalent platinum complex. In some embodiments, the light-emitting layer preferably comprises the divalent metal complex, preferably a divalent platinum complex.

[0093] According to the present invention, in some embodiments, the light-emitting layer comprises a green phosphorescent divalent platinum complex of the present invention.

[0094] According to the present invention, the divalent metal complex of the present invention, preferably the divalent platinum complex, is a light-emitting material, a host material, or a guest material in the light-emitting layer.

[0095] In some embodiments, the organic electroluminescent device of the present invention is an OLED. OLED structures are known in the art. The present invention may employ various OLED structures known in the art.

[0096] 11 shows a structural diagram of an exemplary OLED light-emitting element. As shown in FIG. 11, the OLED element includes an anode (typically a conductive transparent material such as indium tin oxide (ITO)), a hole injection layer (P-HIL or HIL), a hole transport layer (HTL), an emissive layer (EML), an electron transport layer (ETL), an electron injection layer (EIL), and a metal cathode layer (cathode). As known to those skilled in the art, one or more layers may be omitted. For example, one or more of the hole injection layer (P-HIL or HIL), the hole transport layer (HTL), the electron transport layer (ETL), and the electron injection layer (EIL) may be omitted.

[0097] As known in the art, the EML may include one or more emissive materials and one or more hosts. In the present invention, the EML may include the divalent metal complex of the present invention.

[0098] As known in the art, EIL refers to an electron injection layer and may be a part of ETL. HIL may be a part of HTL. EIL, ETL, HTL, and HIL may be a single layer or a multilayer. Furthermore, the device may further include a cathode capping layer (CPL), whose function is to adjust the light path so as to improve light extraction efficiency.

[0099] In some embodiments, ITO is used as the anode of the OLED device, and Al is used as the cathode of the OLED device. The device may have a structure of ITO / HIL (10 nm) / HTL-1 (30 nm) / HTL-2 (10 nm) / EML (20 nm, doped with 5 wt.% green-light complex) / ETL (60 nm) / EIL (2 nm) / Al. The HIL is a hole-injection layer and may include, but is not limited to, materials such as HATCN and MoO. The HTL is a hole-transport layer and may include, but is not limited to, materials such as TAPC, NPD, TCTA, BPBPA, and 2,6-tBu-mCPy. The EML layer is an emissive layer and is a blend layer of 5% complex:host material:95%. The host material may include, but is not limited to, CBP, mCBP, 2,6mCPy, mCP, DMIC-CZ, BQDBC, and the like. The EIL layer is an electron injection layer and may include, but is not limited to, materials such as LiQ, LiF, etc. The ETL layer is an electron transport layer and may include, but is not limited to, materials such as TmPyPb, TPBi, DPPS, Bphen, BmPyPb, etc. As known by those skilled in the art, the device may also use materials other than those mentioned above but known in the art.

[0100] The abbreviations and full names of the above materials are as follows: HATCN (2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene material, 2,3,6,7,10,11-Hexaazatriphenylenehexacabonitrile); MoO3 (Molybdenum trioxide, Molybdenum(VI) oxide); TAPC (4,4'-cyclohexylbis[N,N-bis(4-methylphenyl)aniline], 4,4'-cyclohexylidenebis[N,N-bis(p-tolyl)aniline]); NPD (N,N'-diphenyl-N,N'-di(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, N,N'-Bis-(1-naphthalenyl)-N,N'-bis-phenyl-(1,1'-biphenyl)-4,4'-diamine); TCTA (4,4',4''-Tris(carbazol-9-yl)triphenylamine); BPBPA (4,4'-Bis[N,N-di(biphenyl-4-yl)amino]-1,1'-biphenyl); 2,6-tBu-mCPy (2,6-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)pyridine); CBP (4,4'-Bis(9-carbazolyl)-1,1'-biphenyl); mCBP (3,3'-Bis(9H-carbazol-9-yl)-1,1'-biphenyl, 3,3'-Di(9H-carbazol-9-yl)-1,1'-biphenyl); 2,6mCPy (2,6-Bis(9H-carbazol-9-yl)pyridine, 2,6-Di(9H-carbazol-9-yl)pyridine); mCP (1,3-Di-9-carbazolylbenzene); DMIC-CZ (7,7-dimethyl-5-phenyl-2-(9-phenyl-9H-carbazol-3-yl)-5,7-dihydroindeno[2,1-b]carbazole); BQDBC(7-(4-([1,1'-biphenyl]-4-yl)quinazolin-2-yl)-7H-dibenzo[c,g]carbazole, CAS:1831055-87-80); LiQ (8-Hydroxyquinolinolato-lithium); LiF (lithium fluoride); TmPyPb (1,3,5-tris[(3-pyridyl)-phen-3-yl]benzene); TPBi (1,3,5-Tris(1-phenyl-1H-benzimidazol-2-yl)benzene); DPPS (Diphenylbis(4-(pyridin-3-yl)phenyl)silane); Bphen (4,7-diphenyl-1,10-phenanthroline); BmPyPb (1,3-bis(3,5-bipyridin-3-ylphenyl)benzene, 1,3-bis[3,5-di(pyridin-3-yl)phenyl]benzene).

[0101] [Example] The present invention will be explained in more detail below by means of examples.

[0102] Measurement of the luminous properties of electroluminescent materials: CIE chromaticity coordinate parameters according to the standards of the International Commission on Illumination.

[0103] Nuclear magnetic resonance hydrogen spectra were measured using a JEOL (JEOL) JNM-ECZ400S / L1 instrument. The complexes were dissolved in deuterated chloroform or deuterated dimethyl sulfoxide containing tetramethylsilane (TMS) to measure the nuclear magnetic hydrogen spectra ( 1 H-NMR) was tested, and the frequency was 300 MHz or 400 MHz.

[0104] Mass spectra were measured using a WATERS Corporation ACQUITY UPLC H-Class instrument, and intermediate compounds were subjected to electrospray ionization mass spectrometry (ESI-MS) and final products were subjected to matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS).

[0105] The emission peak, emission lifetime, and emission efficiency of the complex solutions or films were measured using a Horiba Fluorolog-3 instrument. The spectra of the platinum complexes in dichloromethane solutions at room temperature and in 5 wt % doped polymethyl methacrylate films were measured. The dichloromethane solution spectra were measured in a glove box after sufficient nitrogen bubbling through the solvent. The doped polymer films were prepared by spin-coating in a glove box using chloroform as the solvent and a quartz plate as the film carrier. Film samples were tested in a glove box or vacuum chamber to reduce the oxygen quenching effect on the complex emission. The photoluminescence quantum yield of the platinum complex solutions was measured using an integrating sphere. Time-resolved spectroscopy and lifetime tests were performed on the dichloromethane solutions of the platinum complexes at room temperature, and lifetime tests were performed on the doped PMMA films both in nitrogen and under vacuum.

[0106] The energy levels of the complex were tested by using a CHI600D electrochemical workstation device from Shanghai Chenhua Instrument Co., Ltd. In the test, a three-electrode system was selected, a platinum column was used as the working electrode, a platinum wire was used as the counter electrode, and silver / silver chloride was used as the reference electrode. The sample was tested under a nitrogen atmosphere using 0.1 M tetrabutylammonium hexafluorophosphate-containing ultra-dry dimethylformamide as the solvent, ferrocene as the internal standard, and a scan rate of 100 mV / s.

[0107] <Example 1> This example illustrates the preparation of complex 2.

[0108] <<Synthesis of c1>>

[0109]

Chemical formula

[0110] Into a 200 mL sealed tube equipped with a magnetic rotor, 3-(pyridin-2-yl)phenol (2.56 g, 15 mmol), 2-bromo-4-chlorodibenzothiophene (4.18 g, 15 mmol), copper(I) iodide (0.3 mmol, 0.02 equivalent), BPPO (N 1 ,N 2 -bis(5-methyl-[1,1'-biphenyl]-2-yl)oxamide) (0.3 mmol, 0.02 equivalent), K3PO4 (18 mmol, 1.2 equivalents), and N,N-dimethylformamide (60 mL) were added in sequence. The resulting mixture was bubbled with nitrogen for 10 minutes, then heated to 100 °C and stirred for 8 hours. The mixture was cooled to room temperature, water was added to quench the reaction, and it was extracted with ethyl acetate. The organic phases were combined, washed with an appropriate amount of saturated aqueous sodium chloride 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 using petroleum ether:ethyl acetate = 15:1 as the eluent to obtain the product c1 in a yield of 65%.

[0111] <<Synthesis of d1>>

[0112]

Chem.

[0113] Into a 150 mL Schlenk tube, c1 (3.71 g, 10 mmol), benzylamine (2.14 g, 20 mmol), tris(dibenzylideneacetone)dipalladium (0.2 mmol, 0.02 eq), 2-(di-t-butylphosphine)biphenyl (0.4 mmol, 0.04 eq), sodium t-butoxide (15 mmol, 1.5 eq), and toluene (50 mL) were added. The resulting mixture was bubbled with nitrogen for 10 minutes and stirred at 100 °C for 12 hours. After cooling, water and ethyl acetate (EA) were added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and the organic phase was dried over anhydrous Na2SO4. The resulting solution was purified by silica gel chromatography using PE:EA = 10:1 as the eluent to obtain an intermediate (brown viscous liquid, yield 80%).

[0114] Into a 100 mL round-bottom flask, the intermediate (442 mg, 1 mmol), Pd / C (0.1 eq), and ethanol (10 mL) were added. The resulting mixture was stirred at room temperature for 12 hours under a hydrogen atmosphere. After the reaction was complete, the mixture was filtered and dried via rotary evaporation to obtain the product d1 (pale yellow viscous liquid, yield 90%).

[0115] <<Synthesis of f1>>

[0116]

Chem.

[0117] Into a sealed tube, intermediate d1 (352 mg, 1 mmol), 2-bromo-N-isopropylaniline (234 mg, 1.1 mmol), tris(dibenzylideneacetone)dipalladium (45.5 mg, 0.05 mmol), 1,1'-binaphthyl-2,2'-bis-diphenylphosphine (31.1 mg, 0.05 mmol), sodium t-butoxide (144 mg, 1.5 mmol), and toluene (4 mL) were added. After bubbling with nitrogen for 15 minutes, the mixture was heated at 130 °C for 20 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and dried over anhydrous Na2SO4. The resulting solution was purified by silica gel chromatography using PE:EA = 6:1 as the eluent, and the eluent was dried via rotary evaporation to obtain product f1 (yellow viscous liquid, yield 85%).

[0118] <<Synthesis of g1>>

[0119]

Chemical formula

[0120] Into a sealed tube, intermediate f1 (485 mg, 1 mmol), ammonium hexafluorophosphate (180 mg, 1.1 mmol), and triethyl orthoformate (2 mL) were added. The mixture was heated at 120 °C overnight. After cooling to room temperature, ethyl acetate was added to precipitate a yellow solid, and the yellow solid was filtered to obtain product g1 (brown solid, yield 50%).

[0121] <<Synthesis of Complex 2>>

[0122]

Chemical formula

[0123] Into a sealed tube, hexafluorophosphonium carbene g1 (641 mg, 1 mmol), dichloro(1,5-cyclooctadiene)platinum(II) (Pt(COD)Cl2, 336 mg, 0.9 mmol), sodium acetate (86 mg, 1.05 mmol), and THF (2 mL) were added. The mixture was heated at 120 °C for 3 days. After cooling to room temperature, the mixture was dried via rotary evaporation, and the resulting solution was purified by silica gel chromatography using DCM:PE = 4:1 as the eluent to obtain the target product, complex 2 (bright yellow powder, yield 40%).

[0124] 1H NMR spectrum results of complex 2: 1 1H-NMR (400 MHz, CDCl3) δ 9.24 (d, J = 8.4 Hz, 1H), 9.00 (d, J = 4.8 Hz, 1H), 7.98 (d, J = 7.6 Hz, 1H), 7.89 - 7.81 (m, 2H), 7.71 (s, 1H), 7.65 (d, J = 8.4 Hz, 1H), 7.59 (d, J = 8.4 Hz, 1H), 7.51 - 7.48 (m, 2H), 7.45 - 7.41 (m, 1H), 7.38 - 7.34 (m, 2H), 7.31 - 7.27 (m, 2H), 7.14 - 7.10 (m, 1H), 5.63 - 5.56 (m, 1H), 1.77 (d, J = 7.2 Hz, 6H); MS (ESI): 689.3 [M + H]+; The emission peak in dichloromethane (DCM) solution is 533 nm, full width at half maximum (FWHM) = 55 nm, and the emission peak in polymethyl methacrylate (PMMA) is 532 nm, FWHM = 71 nm.

[0125] <Example 2> This example illustrates the preparation of complex 4.

[0126] <<Synthesis of e2>>

[0127] [Chemical formula]

[0128] Into a sealed tube in a glove box, d1 (3.52 g, 10 mmol), 1,2-dibromobenzene (2.57 g, 11 mmol), tris(dibenzylideneacetone)dipalladium (455 mg, 0.5 mmol), 2-(di-tert-butylphosphine)biphenyl (298 mg, 1 mmol), sodium tert-butoxide (1.44 g, 15 mmol), and toluene (40 mL) were added. After bubbling the mixture with nitrogen for 15 minutes, the mixture was heated at 130 °C for 20 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and dried over anhydrous Na2SO4. The resulting solution was purified by silica gel chromatography using PE:EA = 6:1 as the eluent, and the eluent was dried via rotary evaporation to obtain the product e2 (yellow viscous liquid, yield 85%).

[0129] <<Synthesis of f2>>

[0130] [Chemical formula]

[0131] Into a sealed tube in a glove box, e2 (506 mg, 1 mmol), 2,6-diisopropylaniline (195 mg, 1.1 mmol), tris(dibenzylideneacetone)dipalladium (45.5 mg, 0.05 mmol), 1,1'-binaphthyl-2,2'-bis-diphenylphosphine (31.1 mg, 0.05 mmol), sodium t-butoxide (144 mg, 1.5 mmol), and toluene (4 mL) were added. After bubbling nitrogen through the mixture for 15 minutes, the mixture was heated at 130 °C for 20 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and dried over anhydrous Na2SO4. The resulting solution was purified by silica gel chromatography using PE:EA = 6:1 as the eluent, and the eluent was dried via rotary evaporation to obtain the product f2 (yellow viscous liquid, yield 85%).

[0132] <<Synthesis of g2>>

[0133] [Chemical formula]

[0134] Into a sealed tube, f2 (603 mg, 1 mmol), ammonium hexafluorophosphate (180 mg, 1.1 mmol), and triethyl orthoformate (2 mL) were added. The mixture was heated at 120 °C for 24 hours. After cooling to room temperature, ethyl acetate was added to precipitate a yellow solid, and the yellow solid was filtered to obtain the product g2 (brown solid, 50% yield).

[0135] <<Synthesis of Complex 4>>

[0136] [Chemical formula]

[0137] Into a sealed tube, g2 (760 mg, 1 mmol), dichloro(1,5-cyclooctadiene)platinum(II) (Pt(COD)Cl2, 336 mg, 0.9 mmol), sodium acetate (86 mg, 1.05 mmol), and THF (2 mL) were added. The mixture was heated at 120 °C for 3 days. After cooling to room temperature, the mixture was dried via rotary evaporation, and the resulting solution was purified by silica gel chromatography using DCM:PE = 4:1 as the eluent to obtain the target product, Complex 4 (bright yellow powder, 30% yield).

[0138] 1H NMR spectrum results of Complex 4: 1H-NMR(400MHz,CDCl3)δ9.28(d,J=8.4Hz,1H),8.05-8.03(m,1H),7.83(s,1H),7.79-7.70(m,3H),7.65-7.61(m,1H),7.56-7.53(m,2H),7.51-7.47(m,3H),7.42-7.37(m,2H),7.35-7.29(m,2H),6.99-6.96(m,1H),6.90(d,J=8.0Hz,1H),6.45-6.41(m,1H),2.82-2.75(m,2H),1.07(d,J=6.8Hz,6H),1.04(d,J=6.8Hz,6H); MS(ESI):828.6[M+Na] + ; The emission peak in dichloromethane (DCM) solution is 523 nm, full width at half maximum (FWHM) = 26 nm, and the emission peak in polymethyl methacrylate (PMMA) is 522 nm, FWHM = 24 nm.

[0139] <Example 3> This example illustrates the preparation of complex 16.

[0140] <<Synthesis of c3>>

[0141]

Chemical Structure

[0142] In a 200 mL sealed tube with a magnetic rotor, 3-(4-(tert-butyl)pyridin-2-yl)phenol (3.41 g, 15 mmol), 2-bromo-4-chlorodibenzofuran (4.18 g, 15 mmol), cuprous iodide (0.3 mmol, 0.02 equivalent), BPPO (0.3 mmol, 0.02 equivalent), K3PO4 (18 mmol, 1.2 equivalents), and N,N-dimethylformamide (60 mL) were added in sequence. The resulting mixture was bubbled with nitrogen for 10 minutes, then heated to 100 °C and stirred for 8 hours. The mixture was cooled to room temperature, water was added to quench the reaction, and it was extracted with ethyl acetate. The organic phases were combined, washed with an appropriate amount of saturated aqueous sodium chloride 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 using petroleum ether:ethyl acetate = 15:1 as the eluent to obtain product c3 in a yield of 65%.

[0143] <<Synthesis of d3>>

[0144] [Chemical formula]

[0145] In a 150 mL Schlenk tube, intermediate c3 (4.27 g, 10 mmol), benzylamine (2.14 g, 20 mmol), tris(dibenzylideneacetone)dipalladium (183 mg, 0.2 mmol), 2-(di-tert-butylphosphine)biphenyl (119 mg, 0.4 mmol), sodium tert-butoxide (1.44 g, 15 mmol), and toluene (40 ml) were added. The resulting mixture was bubbled with nitrogen for 10 minutes and stirred at 100 °C for 12 hours. After cooling, water and ethyl acetate (EA) were added, and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and the organic phase was dried over anhydrous Na2SO4. The resulting solution was purified by silica gel column chromatography using PE:EA = 10:1 as the eluent to obtain an intermediate product (brown viscous liquid, yield 80%).

[0146] To a 100 mL round-bottom flask, the intermediate product (498 mg, 1 mmol), Pd / C (0.1 equivalent), and ethanol (10 mL) were added, and the resulting mixture was stirred at room temperature for 12 hours under a hydrogen atmosphere. After the reaction was complete, the mixture was filtered and dried via rotary evaporation to obtain d3 (light yellow viscous liquid, yield 90%).

[0147] <<Synthesis of e3>>

[0148]

Chemical formula

[0149] Into a sealed tube in a glove box, d3 (4.08 g, 10 mmol), 1,2-dibromobenzene (2.57 g, 11 mmol), tris(dibenzylideneacetone)dipalladium (455 mg, 0.5 mmol), 2-(di-tert-butylphosphine)biphenyl (298 mg, 1 mmol), sodium tert-butoxide (1.44 g, 15 mmol), and toluene (40 mL) were added. After bubbling the mixture with nitrogen for 15 minutes, the mixture was heated at 130 °C for 20 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and dried over anhydrous Na2SO4. The resulting solution was purified by silica gel chromatography using PE:EA = 6:1 as the eluent, and the eluent was dried via rotary evaporation to obtain the product e3 (yellow viscous liquid, yield 85%).

[0150] <<Synthesis of f3>>

[0151]

Chemical formula

[0152] Into a sealed tube, e3 (562 mg, 1 mmol), 2,6 - diisopropyl aniline (195 mg, 1.1 mmol), tris(dibenzylideneacetone)dipalladium (45.5 mg, 0.05 mmol), 1,1’ - binaphthyl - 2,2’ - bis - diphenylphosphine (31.1 mg, 0.05 mmol), sodium tert - butoxide (144 mg, 1.5 mmol), and toluene (4 mL) were added. After bubbling the mixture with nitrogen for 15 minutes, the mixture was heated at 130 °C for 20 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and dried over anhydrous Na2SO4. The resulting solution was purified by silica gel chromatography using PE:EA = 6:1 as the eluent, and the eluent was dried via rotary evaporation to obtain the product f3 (yellow viscous liquid, yield 85%).

[0153] <<Synthesis of g3>>

[0154] [Chemical formula]

[0155] Into a sealed tube, f3 (659 mg, 1 mmol), ammonium hexafluorophosphate (180 mg, 1.1 mmol), and triethyl orthoformate (2 mL) were added. The mixture was heated at 120 °C for 24 hours. After cooling to room temperature, ethyl acetate was added to precipitate a yellow solid, and the yellow solid was filtered to obtain the product g3 (brown solid, yield 50%).

[0156] <<Synthesis of Complex 16>>

[0157] [Chemical formula]

[0158] To a sealed tube were added g3 (816 mg, 1 mmol), dichloro(1,5-cyclooctadiene)platinum(II) (Pt(COD)Cl2, 336 mg, 0.9 mmol), sodium acetate (86 mg, 1.05 mmol), and THF (2 mL). The mixture was heated at 120 °C for 3 days. After cooling to room temperature, the mixture was dried via rotary evaporation, and the resulting solution was purified by silica gel chromatography using DCM:PE = 4:1 as the eluent to obtain the target product, complex 16 (bright yellow powder, yield 40%).

[0159] 1H NMR spectral results of complex 16: 1 1H-NMR (400 MHz, CDCl3) δ 9.27 (d, J = 8.4 Hz, 1H), 8.04 (d, J = 7.6 Hz, 1H), 7.82 (s, 1H), 7.78 - 7.74 (m, 2H), 7.71 (d, J = 8.0 Hz, 1H), 7.55 - 7.49 (m, 5H), 7.41 - 7.28 (m, 5H), 6.89 (d, J = 8.0 Hz, 1H), 6.82 (d, J = 6.0 Hz, 1H), 6.37 (dd, J = 6.0, 2.4 Hz, 1H), 2.83 - 2.76 (m, 2H), 1.33 (s, 9H), 1.05 (d, J = 6.8 Hz, 6H), 1.03 (d, J = 6.8 Hz, 6H); MS (ESI): 885.0 [M+Na] + ; The emission peak in dichloromethane (DCM) solution is 519 nm, full width at half maximum (FWHM) = 24 nm, and the emission peak in polymethyl methacrylate (PMMA) is 521 nm, FWHM = 23 nm.

[0160] <Example 4> This example illustrates the preparation of complex 25.

[0161] <<Synthesis of f4>>

[0162]

Chemical formula

[0163] Into a sealed tube, e2 (562 mg, 1 mmol), [1,1'-biphenyl]-2-amine (186 mg, 1.1 mmol), tris(dibenzylideneacetone)dipalladium (45.5 mg, 0.05 mmol), 1,1'-binaphthyl-2,2'-bis-diphenylphosphine (31.1 mg, 0.05 mmol), sodium tert-butoxide (144 mg, 1.5 mmol), and toluene (4 mL) were added. After bubbling the mixture with nitrogen for 15 minutes, the mixture was heated at 130 °C for 20 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and dried over anhydrous Na2SO4. The resulting solution was purified by silica gel chromatography using PE:EA = 6:1 as the eluent, and the eluent was dried via rotary evaporation to obtain the product f4 (yellow viscous liquid, yield 85%).

[0164] <<Synthesis of g4>>

[0165]

Chem.

[0166] Into a sealed tube, f4 (595 mg, 1 mmol), ammonium hexafluorophosphate (180 mg, 1.1 mmol), and triethyl orthoformate (2 mL) were added. The mixture was heated at 120 °C for 24 hours. After cooling to room temperature, ethyl acetate was added to precipitate a yellow solid, and the yellow solid was filtered to obtain the product g4 (brown solid, yield 50%).

[0167] <<Synthesis of Complex 25>>

[0168]

Chem.

[0169] To a sealed tube, g4 (752 mg, 1 mmol), dichloro(1,5-cyclooctadiene)platinum(II) (Pt(COD)Cl2, 336 mg, 0.9 mmol), sodium acetate (86 mg, 1.05 mmol), and THF (2 mL) were added. The mixture was heated at 120 °C for 3 days. After cooling to room temperature, the mixture was dried via rotary evaporation, and the resulting solution was purified by silica gel chromatography using DCM:PE = 4:1 as the eluent to obtain the target product, complex 25 (bright yellow powder, yield 40%).

[0170] 1H NMR spectrum results of complex 25: 1 1H-NMR (400 MHz, CDCl3) δ 9.16 (d, J = 8.4 Hz, 1H), 8.02 (d, J = 7.6, 1H), 7.87 - 7.81 (m, 3H), 7.77 - 7.72 (m, 2H), 7.65 - 7.61 (m, 2H), 7.56 - 7.48 (m, 5H), 7.47 - 7.38 (m, 3H), 7.36 - 7.30 (m, 2H), 7.23 - 7.13 (m, 3H), 7.11 - 7.07 (m, 1H), 6.80 (d, J = 8.0 Hz, 1H), 6.46 - 6.43 (m, 1H); MS (ESI): 828.3 [M+CH3OH] + ; The emission peak in dichloromethane (DCM) solution is 527 nm, full width at half maximum (FWHM) = 28 nm, and the emission peak in polymethyl methacrylate (PMMA) is 527 nm, FWHM = 28 nm.

[0171] <Example 5> This example is presented to illustrate the preparation of complex 19.

[0172] <<Synthesis of e5>>

[0173]

Chemical formula

[0174] Into a sealed tube in a glove box, d3 (4.08 g, 10 mmol), 1,2-dibromo-4-cumene (3.34 g, 12 mmol), tris(dibenzylideneacetone)dipalladium (733 mg, 0.8 mmol), 2-(di-tert-butylphosphine)biphenyl (596 mg, 2 mmol), sodium tert-butoxide (1.92 g, 20 mmol), and toluene (40 mL) were added. After the mixture was bubbled with nitrogen for 15 minutes, the mixture was heated at 130 °C for 20 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and dried over anhydrous Na2SO4. The resulting solution was purified by silica gel chromatography using PE:EA = 6:1 as the eluent, and the eluent was dried via rotary evaporation to obtain the product e5 (yellow viscous liquid, yield 68%).

[0175] <<Synthesis of f5>>

[0176]

Chemical formula

[0177] Into a sealed tube in a glove box, e5 (605 mg, 1 mmol), benzene-d5-amine (148 mg, 1.5 mmol), tris(dibenzylideneacetone)dipalladium (183 mg, 0.2 mmol), 2-(di-tert-butylphosphine)biphenyl (31.1 mg, 0.08 mmol), sodium tert-butoxide (144 mg, 1.5 mmol), and toluene (4 mL) were added. After the mixture was bubbled with nitrogen for 15 minutes, the mixture was heated at 130 °C for 20 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and dried over anhydrous Na2SO4. The resulting solution was purified by silica gel chromatography using PE:EA = 6:1 as the eluent, and the eluent was dried via rotary evaporation to obtain the product f5 (yellow viscous liquid, yield 60%).

[0178] <<Synthesis of g5>>

[0179] [ka]

[0180] To a sealed tube was added f5 (623 mg, 1 mmol), ammonium hexafluorophosphate (212 mg, 1.3 mmol), and triethyl orthoformate (2 mL). The mixture was heated at 120° C. for 25 h. After cooling to room temperature, ethyl acetate was added to precipitate a yellow precipitate, which was filtered to give product g5 (brown solid, 55% yield).

[0181] <<Synthesis of Complex 19>>

[0182] [ka]

[0183] To a sealed tube was added g5 (780 mg, 1 mmol), dichloro(1,5-cyclooctadiene)platinum(II) (Pt(COD)Cl, 370 mg, 1 mmol), sodium acetate (86 mg, 1.05 mmol), and THF (2 mL). The mixture was heated at 120 °C for 3 days. After cooling to room temperature, the mixture was dried via rotary evaporation, and the resulting solution was purified by silica gel chromatography using DCM:PE=4:1 as the eluent to give the desired product, complex 19 (light yellow powder, 40% yield).

[0184] MS(ESI):856.3[M+CH3OH] + ; The emission peak in dichloromethane (DCM) solution is 530 nm with a full width at half maximum (FWHM) of 48 nm, and the emission peak in polymethyl methacrylate (PMMA) is 532 nm with a FWHM of 45 nm.

[0185] Example 6 This example illustrates the preparation of complex 20.

[0186] <<Synthesis of e6>>

[0187]

Chem.

[0188] Into a sealed tube in a glove box, d3 (4.08 g, 10 mmol), 3,4-dibromobenzonitrile (3.13 g, 12 mmol), tris(dibenzylideneacetone)dipalladium (733 mg, 0.8 mmol), 2-(di-tert-butylphosphine)biphenyl (596 mg, 2 mmol), sodium tert-butoxide (1.92 g, 20 mmol), and toluene (40 mL) were added. After bubbling the mixture with nitrogen for 15 minutes, the mixture was heated at 130 °C for 20 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and dried over anhydrous Na2SO4. The resulting solution was purified by silica gel chromatography using PE:EA = 6:1 as the eluent, and the eluent was dried via rotary evaporation to obtain the product e6 (yellow viscous liquid, yield 62%).

[0189] <<Synthesis of f6>>

[0190]

Chem.

[0191] Into a sealed tube, e6 (588 mg, 1 mmol), 2,6 - diisopropylaniline (265 mg, 1.5 mmol), tris(dibenzylideneacetone)dipalladium (183 mg, 0.2 mmol), 2-(di - tert - butylphosphine)biphenyl (31.1 mg, 0.08 mmol), sodium tert - butoxide (144 mg, 1.5 mmol), and toluene (4 mL) were added. After bubbling the mixture for 15 minutes, the mixture was heated at 130 °C for 20 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and dried over anhydrous Na2SO4. The resulting solution was purified by silica gel chromatography using PE:EA = 6:1 as the eluent, and the eluent was dried via rotary evaporation to obtain the product f6 (yellow viscous liquid, yield 50%).

[0192] <<Synthesis of g6>>

[0193]

Chemical Structure

[0194] Into a sealed tube, f6 (685 mg, 1 mmol), ammonium hexafluorophosphate (212 mg, 1.3 mmol), and triethyl orthoformate (2 mL) were added. The mixture was heated at 120 °C for 25 hours. After cooling to room temperature, ethyl acetate was added to precipitate a yellow solid, and the yellow solid was filtered to obtain the product g6 (brown solid, yield 55%).

[0195] <<Synthesis of Complex 20>>

[0196]

Chemical Structure

[0197] To a sealed tube, g6 (842 mg, 1 mmol), dichloro(1,5-cyclooctadiene)platinum(II) (Pt(COD)Cl2, 370 mg, 1 mmol), sodium acetate (86 mg, 1.05 mmol), and THF (2 mL) were added. The mixture was heated at 120 °C for 3 days. After cooling to room temperature, the mixture was dried via rotary evaporation, and the resulting solution was purified by silica gel chromatography using DCM:PE = 4:1 as the eluent to obtain the target product, complex 20 (bright yellow powder, yield 40%).

[0198] MS(ESI): 888.7[M+H] + ; The emission peak in dichloromethane (DCM) solution is 526 nm, full width at half maximum (FWHM) = 34 nm, and the emission peak in polymethyl methacrylate (PMMA) is 530 nm, FWHM = 30 nm.

[0199] <Example 7> This example illustrates the preparation of complex 28.

[0200] <<Synthesis of f7>>

[0201]

Chemical formula

[0202] Into a sealed tube, e6 (588 mg, 1 mmol), [1,1'-biphenyl]-2-amine (254 mg, 1.5 mmol), tris(dibenzylideneacetone)dipalladium (183 mg, 0.2 mmol), 2-(di-tert-butylphosphino)biphenyl (31.1 mg, 0.08 mmol), sodium tert-butoxide (144 mg, 1.5 mmol), and toluene (4 mL) were added. After bubbling the mixture with nitrogen for 15 minutes, the mixture was heated at 130 °C for 20 hours. After cooling, ethyl acetate was added and the mixture was filtered. The aqueous phase was extracted with ethyl acetate, the organic phases were combined, washed with brine, and dried over anhydrous Na2SO4. The resulting solution was purified by silica gel chromatography using PE:EA = 6:1 as the eluent, and the eluent was dried via rotary evaporation to obtain the product f7 (yellow viscous liquid, yield 55%).

[0203] <<Synthesis of g7>>

[0204] [Chemical formula]

[0205] Into a sealed tube, f7 (677 mg, 1 mmol), ammonium hexafluorophosphate (212 mg, 1.3 mmol), and triethyl orthoformate (2 mL) were added. The mixture was heated at 120 °C for 25 hours. After cooling to room temperature, ethyl acetate was added to precipitate a yellow solid, and the yellow solid was filtered to obtain the product g7 (brown solid, yield 53%).

[0206] <<Synthesis of Complex 28>>

[0207] [Chemical formula]

[0208] To a sealed tube was added g7 (834 mg, 1 mmol), dichloro(1,5-cyclooctadiene)platinum(II) (Pt(COD)Cl, 370 mg, 1 mmol), sodium acetate (86 mg, 1.05 mmol), and THF (2 mL). The mixture was heated at 120 °C for 3 days. After cooling to room temperature, the mixture was dried via rotary evaporation, and the resulting solution was purified by silica gel chromatography using DCM:PE=4:1 as the eluent to give the desired product, complex 28 (light yellow powder, 34% yield).

[0209] MS(ESI):880.8[M+H] + ; The emission peak in dichloromethane (DCM) solution is 533 nm with a full width at half maximum (FWHM) of 42 nm, and the emission peak in polymethyl methacrylate (PMMA) is 535 nm with a FWHM of 34 nm.

[0210] <Comparative Example 1> The complex of Comparative Example 1 was prepared in the same manner as Example 1, except that the main structure of the complex of Example 1 contains a dibenzofuran structural unit, while the complex of Comparative Example 1 is phenyl (see CN112125932A). Both Example 1 and Comparative Example 1 have the same substituent, isopropyl, and the complex of Comparative Example 1 has the following structure:

[0211] [ka]

[0212] <Comparative Example 2> The complex of Comparative Example 2 was prepared in the same manner as Example 2, except that the main structure of the complex of Example 2 contains a dibenzofuran structural unit, while the complex of Comparative Example 2 is phenyl (see CN112125932A). Both Example 2 and Comparative Example 2 have the same substituent, 2,6-diisopropylphenyl, and the complex of Comparative Example 2 has the following structure:

[0213] [ka]

[0214] <Test Example 1> Photophysical characterization of platinum complexes 2, 4, 16, 19, 20, 25, and 28.

[0215] Representative data on the color purity of the emitters were obtained from the emission spectra of PMMA (polymethyl methacrylate) films and dichloromethane solutions prepared with 5% complexes: the complexes were each dissolved in dichloromethane (DCM) at 5 wt % to form solutions, doped into polymethyl methacrylate (PMMA) to obtain films, and the resulting solutions or films were tested.

[0216] Similar tests were carried out and comparisons were made for Comparative Examples 1 and 2. Table 1 shows the emission spectrum data of the complexes.

[0217] The peak wavelengths of complexes 2, 4, 16, 19, 20, 25, and 28 prepared in Examples 1 to 7 of the present invention were between 515 nm and 535 nm. The full widths at half maximum of complexes 4, 16, and 25 prepared in Examples 2 to 4 were between 20 and 30 nm, and all complexes belonged to narrow-band green emitting materials. The full width at half maximum of complex 2 prepared in Example 1 was 55 nm / 71 nm, but the luminescence lifetime of the film of complex 2 was slightly lower and the photoluminescence quantum yield Φ was higher.

[0218] In Table 1, λ is the peak wavelength of the divalent platinum complex dissolved in dichloromethane and doped into a polymethyl methacrylate (PMMA) film, and FWHM is its full width at half maximum. The emission lifetime τ and photoluminescence quantum yield Φ in the solution and film are also listed in Table 1.

[0219] [Table 1] a / b Data measured in dichloromethane solution / PMMA film.

[0220] From the above data, it can be seen that the green wavelength peak of the divalent platinum complex provided by the present invention is in the range of 515 to 535 nm, the green wavelength is red-shifted by about 10 nm, and the luminous efficiency is significantly improved compared to Comparative Examples 1 and 2 having the same substituents, resulting in green light with higher saturation. Therefore, the divalent platinum complex can be used as a green phosphorescent electroluminescent material or photoluminescent material, which meets the requirement of high color purity emission for high-definition displays.

[0221] Figures 1-3 show graphs of the emission spectra of divalent platinum complexes 2, 4, and 16, respectively, in solution and in film. Under excitation with 380 nm ultraviolet light, the emission wavelengths of the three complexes in dichloromethane solution were between 519 nm and 533 nm, and in polymethyl methacrylate (PMMA) were between 521 nm and 532 nm. The peak wavelengths of all the complexes were in the green light region, and the full widths at half maximum of the spectra were narrow, indicating that the complexes are excellent green phosphorescent materials.

[0222] Figure 1 shows the emission spectra of complex 2 prepared in Example 1 of the present invention in solution and film. The spectra are photoluminescence spectra under 380 nm UV excitation. The peak wavelength of the emission spectrum in a 5% mass concentration dichloromethane solution was 533 nm, with a full width at half maximum of 55 nm. The peak wavelength of the emission spectrum in a 5% mass concentration polymethyl methacrylate film was 532 nm, with a full width at half maximum of 71 nm. Both spectra show narrowband green light, demonstrating that complex 2 is suitable for green phosphorescence applications. Under 380 nm UV excitation, the emission wavelength in a dichloromethane solution was 533 nm, with the emission region of the complex mainly encompassing the green and yellow regions. Due to the large intermolecular spacing in solution, there was no obvious aggregation state emission, and clear single-molecule emission was observed. In the polymethylmethacrylate film, the emission peak did not change obviously, but the full width at half maximum increased obviously, and the emission region broadened to the red light region compared to the solution, indicating that the molecules had a clear aggregation-state emission effect. The spectral width can be controlled by adjusting the doping concentration, which is also very beneficial for the fabrication during the evaporation method at a later stage.

[0223] Figure 2 is a graph of the emission spectra of complex 4 prepared in Example 2 of the present invention in solution and in film. The peak wavelength of the emission spectrum of the dichloromethane solution was 523 nm, and the full width at half maximum was 26 nm. The peak wavelength of the emission spectrum of the polymethyl methacrylate (5%) film was 522 nm, and the full width at half maximum was 24 nm. As shown in Figure 2, under 380 nm ultraviolet light excitation, the solution and film exhibited similar emission spectra, with similar emission wavelengths and full width at half maximum. Compared with the spectrum of complex 2, the emission peak was significantly blue-shifted by 10 nm, and the full width at half maximum was significantly narrower. Figure 2 demonstrates that complex 4 has the advantages of a stable emission spectrum and high color purity.

[0224] Figure 3 shows the emission spectra of complex 16, prepared in Example 3 of the present invention, in solution and in film. The peak wavelength of the emission spectrum for the dichloromethane solution was 519 nm, with a full width at half maximum of 24 nm. The peak wavelength of the emission spectrum for the polymethyl methacrylate (5%) film was 521 nm, with a full width at half maximum of 23 nm. The emission spectrum of complex 16 was blue-shifted by 2-4 nm and narrowed by 1-2 nm compared to that of complex 4, indicating that the introduction of tert-butyl into complex 16 can slightly increase the emission energy level and structural rigidity during the emission process. Under 380 nm UV excitation, the solution and film exhibited similar emission spectra, with similar emission wavelengths and full widths at half maximum. This molecule is based on complex 4 to which a tert-butyl group has been added. Compared with the spectrum of complex 4, the emission peak was blue-shifted by 2–4 nm and the full width at half maximum was narrowed, indicating that this type of complex can tune and control the emission region by adjusting one or more substituents while retaining the properties of high efficiency, narrow spectrum, and stable emission.

[0225] Figure 4 is a graph of the UV-visible absorption spectrum of Complex 2 prepared in Example 1 of the present invention. According to the absorption spectrum, the absorption spectrum of the dichloromethane solution of the complex has a very high intensity in the region of 200-400 nm, which is caused by transitions at the ligand center. The absorption in the region of 300-400 nm is due to the π-π transition in the complex with a furan center. * The absorption peaks at 400 nm and above can be assigned to metal-to-ligand charge transfer (MLCT) between the central metal ion and the ligands of the complex, and to ligand-to-ligand charge transfer (LLCT) between different ligand moieties. This indicates that this type of molecule has complex exciton transition characteristics, has very efficient energy absorption, and can be used as a preferred molecular structure for doped material molecules. The absorption peaks between 400 nm and 480 nm are due to metal-to-ligand charge transfer ( 1The absorption bands related to the MLCT were very clear, indicating that this series of compounds exhibited stronger 1 It has been shown that the complex has the MLCT effect. It is believed that this effect can increase the phosphorescence efficiency of the molecule, and therefore this type of complex molecule can be used as a preferred molecule for doping material in phosphorescent devices. Therefore, this type of complex molecule has obvious charge transfer absorption characteristics from the ligand center and metal to the ligand, and the energy absorption of this type of complex molecule is very efficient, so the complex can be used as a preferred molecular structure for doping material molecules.

[0226] FIG. 5 shows the structure of complex 2 prepared in Example 1 of the present invention. 1 6 is a H-NMR nuclear magnetic spectrum of Complex 4 prepared in Example 2 of the present invention. 1 7 is a H-NMR nuclear magnetic spectrum of complex 16 prepared in Example 3 of the present invention. 1 5, 6, and 7 show that the complex was successfully prepared by the present invention and that the complex can exist independently and stably, and can be isolated, purified, and characterized by the H-NMR spectrum.

[0227] 8 is a purity characterization graph of complex 25 prepared in Example 4 of the present invention. The test was carried out by ultra-high performance liquid chromatography using an ACQUITY H-class chromatograph from Waters Corporation, USA, with 100% water or methanol / water (10% / 90%) as the mobile phase.

[0228] This figure shows that the purity was 99.29%, indicating that the method provided by the present invention can provide an ultra-pure product, and that the complex can be subjected to suitable scale-up of processing.

[0229] 9 is a graph of the mass spectrum of the complex 25 prepared in Example 4 of the present invention. The molecular signal of the mass spectrum shows that the peak value of M / Z (ratio of mass to charge of ion) is 828.3, which is consistent with the molecular ion peak of compound 25, indicating that the structure of the complex is the designed structure.

[0230] 10 is a graph of the mass spectrum of the complex 16 prepared in Example 3 of the present invention. The molecular signal of the mass spectrum shows that the peak value of M / Z is 885.0, which is consistent with the molecular ion peak of compound 16, indicating that the structure of the complex is the designed structure.

[0231] <Test Example 2> Characterization of the band gap and related optical properties of complexes 2, 4, 16, 19, 20, 25, 28, and comparative examples 1-2 is shown in Table 2 below.

[0232] Photoelectron energy level testing of electroluminescent materials: the band gap (E g The values of the lowest unoccupied molecular orbital (LUMO), lowest occupied molecular orbital (LUMO), and highest occupied molecular orbital (HOMO) were measured using cyclic voltammetry (CV). The entire test procedure was performed on a CHI600D electrochemical workstation (Shanghai Chenhua Instruments Co., Ltd.) in a glove box (Lab2000, Etelux). A Pt column was used as the working electrode, Ag / AgCl was used as the reference electrode, and a Pt wire was used as the auxiliary electrode to form a three-electrode system. The medium used in the test procedure was a 0.1 M solution of tetrabutylammonium hexafluorophosphate (Bu4NPF6) in dimethylformamide (DMF), and all measured potentials were based on the added internal standard ferrocene (Fc). In Table 2, the units are electron volts (eV).

[0233] [Table 2]

[0234] As can be seen from Table 2, complexes 2, 4, 16, 19, 20, 25, and 28 prepared in Examples 1 to 7 of the present invention have different structures from the complexes of Comparative Examples 1 and 2, resulting in different band gap values (E g Complex 2 has a LUMO value comparable to complexes 4, 16, 19, 20, 25, and 28, but not a HOMO value.

[0235] <Application example> The complexes 2, 4, 16, 19, 20, 25, and 28, and the complexes of Comparative Examples 1 and 2 were each doped into a host material as a light-emitting material to prepare an OLED device, and the doping amount was 5%.

[0236] Figure 12 shows the emission spectrum of a device fabricated using platinum complex 4. The structure used was ITO / HATCN (10 nm) / TAPC (10 nm) / TCTA (8 nm) / 2,6mCPy:5 wt% platinum complex (20 nm) / 2,6-tBumCPy (10 nm) / LiQ (2 nm) / Al (120 nm). As shown by the electroluminescence spectrum, the emission peak was located at 531 nm, which was 9 nm red-shifted relative to the photoluminescence peak in the PMMA medium, and the full width at half maximum was 29 nm, almost unchanged. The luminescent properties of the emissive complex itself were maintained. The calculated chromaticity coordinates were CIE (0.35, 0.63). The spectrum demonstrated that the device had a narrowband electroluminescent effect suitable for use as a green light-emitting element.

[0237] FIG. 13 is a graph of the EQE-current density curve for an OLED device made with complex 4.

[0238] The EQE graph shows that the external quantum efficiency of the device is greater than 15% at low current densities and the device exhibits a low roll-off with increasing current density, exceeding 1 mA / cm 2 The external quantum efficiency was 14.8% at a current density of 1.0, which indicates that the device made with complex 4 has good device emission stability.

[0239] Figure 14 shows a graph of the electroluminescence decay over time for the device made with complex 4. The photoluminescence decay of the OLED device made with complex 4 is slow, with a lifetime of LT at a luminance of 1760 nits. 95 can reach 160 hours.

[0240] The electroluminescent performance of the device was tested using an IVL test fixture, and the lifetime of the device was measured using a lifetime test fixture, the IVL test fixture being a Frosted FS-MP96-H16, and the lifetime test fixture being a Frosted FS-2000GA4-X16-H8.

[0241] <Application test example> Complexes 2, 16, 19, 20, 25, and 28, as well as the complexes prepared in Comparative Examples 1-2, were used in place of complex 4 described in the above Application Example to fabricate OLED light-emitting devices and test their properties.

[0242] The characteristic data of the light-emitting device fabricated using the divalent platinum complex is shown in Table 3. CIE(x,y) is a chromaticity coordinate parameter according to the standard of the International Commission on Illumination. The data for current efficiency CE and power efficiency PE are shown in Table 3. -2 The value was at the device luminance of .

[0243] [Table 3]

[0244] Table 3 shows a comparison of the luminescence performance data of light-emitting devices fabricated from various platinum complexes. The electroluminescence wavelength of the light-emitting device was primarily determined by the photoluminescence of the platinum complex itself, and the purity of the photoluminescence spectrum of the platinum complex itself was directly related to the spectral purity of the electroluminescence. Under the same conditions, the efficiency of the light-emitting device also matched the luminescence quantum efficiency trend of the platinum complex itself, and the color purity of the light emitted by the light-emitting device was directly related to the spectral color purity of the light emitted by the doped material itself under photoexcitation. A comparison of the electroluminescence spectrum of the platinum complex light-emitting device with the photoluminescence spectrum in the film shows that the electroluminescence spectrum of the light-emitting device was slightly red-shifted compared to the photoluminescence spectrum of the film, but the peak wavelength was still in the green light region (530 nm to 540 nm), and the majority of the spectrum was also in the green light region. The calculated chromaticity coordinates indicate that the light-emitting device belongs to the green light-emitting device and has excellent coverage of the green light region. The highest current efficiency (CE) of the light-emitting device was 63.70 cd / A, and the highest power efficiency (PE) was 81.30 lm / W.

[0245] Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the technical spirit of the present invention, many simple modifications may be made to the technical solutions of the present invention, including combining various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosure of the present invention, and all belong to the protection scope of the present invention. [Brief explanation of the drawings]

[0246] [Figure 1] 1 is a graph showing the emission spectra of the complex 2 prepared in Example 1 of the present invention in solution and thin film. [Figure 2] 1 is a graph showing the emission spectra of the complex 4 prepared in Example 2 of the present invention in solution and thin film. [Figure 3]1 is a graph showing the emission spectra of the complex 16 prepared in Example 3 of the present invention in solution and thin film. [Figure 4] 1 is a graph of the ultraviolet-visible absorption spectrum of Complex 2 prepared in Example 1 of the present invention. [Figure 5] 1 is a 1H-NMR nuclear magnetic spectrum of complex 2 prepared in Example 1 of the present invention. [Figure 6] 1 is a 1H-NMR nuclear magnetic spectrum of complex 4 prepared in Example 2 of the present invention. [Figure 7] 1 is a 1H-NMR nuclear magnetic spectrum of complex 16 prepared in Example 3 of the present invention. [Figure 8] 1 is a purity characterization graph of complex 25 prepared in Example 4 of the present invention. [Figure 9] 1 is a graph of the mass spectrum of complex 25 prepared in Example 4 of the present invention. [Figure 10] 1 is a graph of the mass spectrum of complex 16 prepared in Example 3 of the present invention. [Figure 11] The structure of an OLED light-emitting element is shown. [Figure 12] 1 shows the emission spectrum of a device using complex 4. [Figure 13] 1 is a graph of EQE-current density curves for an OLED device made with complex 4. [Figure 14] 1 shows a graph of the electroluminescence decay over time for a device made with complex 4. [Figure 15] FIG. 1 is a schematic diagram of a synthesis scheme for a green phosphorescent divalent platinum complex.

Claims

1. A divalent metal complex, The divalent metal complex has a structure of formula (I): 【Chemical 1】 In formula (I), M is Pt or Pd, preferably Pt; A is O or S, preferably O; R １ is trimethylsilyl, optionally substituted C １ ~C ３０ Alkyl, optionally substituted C ３ ~C １２ Cycloalkyl, optionally substituted C ５ ~C ３０ aryl, optionally substituted C ２ ~C ３０ Heteroaryl, optionally substituted C １ ~C ３０ Alkoxy, optionally substituted C ３ ~C １２ cycloalkyloxy, optionally substituted C ５ ~C ３０ Aryloxy, optionally substituted C ５ ~C ３０ arylamino, optionally substituted C ５ ~C ３０ heteroaryloxy, or optionally substituted C ５ ~C ３０ heteroarylamino, and, R ２ ~R １７ are the same or different, and each independently represents a hydrogen atom, an isotope of hydrogen, a halogen atom, cyano, isocyano, thiocyano, isothiocyanato, trimethylsilyl, or an optionally substituted C １ ~C ３０ Alkyl, optionally substituted C ３ ~C １２ Cycloalkyl, optionally substituted C ５ ~C ３０ Aryl, optionally substituted C ２ ~C ３０ Heteroaryl, optionally substituted C １ ~C ３０ Alkoxy, optionally substituted C ３ ~C １２ cycloalkyloxy, optionally substituted C ５ ~C ３０ Aryloxy, optionally substituted C ５ ~C ３０ arylamino, optionally substituted C ５ ~C ３０ heteroaryloxy, and optionally substituted C ５ ~C ３０ heteroarylamino; Here, "optionally substituted" means that the group is １ ~C ３０ Alkyl, C ３ ~C １２ Cycloalkyl, C １ ~C ３０ Alkoxy, C ５ ~C ３０ Aryl, C ２ ~C ３０ Heteroaryl, C ５ ~C ３０ It means that it may be further substituted with one or more groups selected from aryloxy and halogen, or it may not be substituted. A divalent metal complex comprising:

2. In formula (I), R １ is an optionally substituted C １ ~C １２ Alkyl, optionally substituted C ３ ~C ８ Cycloalkyl, optionally substituted C ５ ~C ３０ Aryl, optionally substituted C ２ ~C ３０ Heteroaryl, optionally substituted C １ ~C １２ Alkoxy, optionally substituted C ５ ~C ３０ aryloxy, or optionally substituted C ５ ~C ３０ is arylamino, Preferably, R １ is an optionally substituted C １ ~C １０ Alkyl, optionally substituted C ３ ~C ７ Cycloalkyl, optionally substituted C ５ ~C ２４ aryl, or optionally substituted C ２ ~C ２４ is heteroaryl, R ２ ~R １７ are the same or different, and each independently represents a hydrogen atom, an isotope of hydrogen, a halogen atom, cyano, isocyano, thiocyano, isothiocyanato, or an optionally substituted C １ ~C １２ Alkyl, optionally substituted C ３ ~C ８ Cycloalkyl, optionally substituted C ５ ~C ３０ Aryl, optionally substituted C ２ ~C ３０ Heteroaryl, optionally substituted C １ ~C １２ Alkoxy, optionally substituted C ５ ~C ３０ Aryloxy, and optionally substituted C ５ ~C ３０ arylamino; Preferably, R ２ ~R １７ are the same or different and each independently represents a hydrogen atom, an isotope of hydrogen, a halogen atom, cyano, an optionally substituted C １ ~C １０ Alkyl, optionally substituted C ３ ~C ７ Cycloalkyl, optionally substituted C ５ ~C ２４ aryl, and optionally substituted C ２ ~C ２４ heteroaryl; Here, "optionally substituted" means that the group is １ ~C １２ Alkyl, C ３ ~C ８ Cycloalkyl, C １ ~C １２ Alkoxy, C ５ ~C ３０ Aryl, C ２ ~C ３０ Heteroaryl, C ５ ~C ３０ means that it may be further substituted with one or more groups selected from aryloxy and halogen, or may not be substituted; Preferably, "optionally substituted" means that the group is １ ~C １０ Alkyl, C ３ ~C ７ Cycloalkyl, C １ ~C １０ Alkoxy, C ５ ~C ２４ Aryl, C ２ ~C ２４ Heteroaryl, C ５ ~C ２４ It means that it may be further substituted with one or more groups selected from aryloxy and halogen, or it may not be substituted. The divalent metal complex of claim 1.

3. In formula (I), R １ is an optionally substituted C １ ~C ６ Alkyl, optionally substituted C ３ ~C ６ Cycloalkyl, optionally substituted C ５ ~C １４ aryl, or optionally substituted C ２ ~C １４ is heteroaryl, Preferably, R １ is an optionally substituted C １ ~C ４ Alkyl, optionally substituted C ５ ~C ６ Cycloalkyl, optionally substituted C ６ ~C １４ aryl, or optionally substituted C ３ ~C １４ is heteroaryl, R ２ ~R １７ are the same or different and each independently represents a hydrogen atom, an isotope of hydrogen, a halogen atom, cyano, an optionally substituted C １ ~C ６ Alkyl, optionally substituted C ３ ~C ６ Cycloalkyl, optionally substituted C ５ ~C １４ aryl, and optionally substituted C ２ ~C １４ heteroaryl; Preferably, R ２ ~R １７ are the same or different and each independently represents a hydrogen atom, an isotope of hydrogen, a halogen atom, cyano, an optionally substituted C １ ~C ４ Alkyl, optionally substituted C ５ ~C ６ Cycloalkyl, optionally substituted C ６ ~C １４ aryl, and optionally substituted C ３ ~C １４ heteroaryl; Here, "optionally substituted" means that the group is １ ~C ６ Alkyl, C ３ ~C ６ Cycloalkyl, C ５ ~C １４ Aryl, C ２ ~C １４ means that it may be further substituted with one or more groups selected from heteroaryl and halogen, or may be unsubstituted; Preferably, "optionally substituted" means that the group is １ ~C ４ Alkyl, C ５ ~C ６ Cycloalkyl, C ６ ~C １４ Aryl, C ３ ~C １４ It means that it may be further substituted with one or more groups selected from heteroaryl, and halogen, or may be unsubstituted. The divalent metal complex according to claim 1 or 2.

4. R １ is methyl, methyl with three deuterated hydrogen atoms, benzyl, diphenylmethyl, triphenylmethyl, ethyl, 2-phenylethyl, 2,2-diphenylethyl, 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, and phenyl with five deuterated hydrogen atoms. , 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-diisopropyl Phenyl, 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-dii isopropylphenyl, 3,5-diisobutylphenyl, 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, 2,4,6-tricyclopentylphenyl, biphenyl-2-yl, and 4'-tert-butylbiphenyl-2-yl; R ２ ~R １７ are the same or different and each independently represents a hydrogen atom, deuterium, a halogen atom, methyl, methyl having three deuterated hydrogen atoms, benzyl, diphenylmethyl, triphenylmethyl, ethyl, 2-phenylethyl, 2,2-diphenylethyl, 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, cyclohex ... xyl, cycloheptyl, phenyl, phenyl in which five hydrogen atoms are deuterated, 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 phenyl, 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 phenyl, 3,5-diethylphenyl, 3,5-diisopropylphenyl, 3,5-diisobutylphenyl, 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,selected from the group consisting of 6-tricyclobutylphenyl, 2,4,6-tricyclopentylphenyl, cyano, biphenyl-2-yl, and 4'-tert-butylbiphenyl-2-yl, The divalent metal complex according to any one of claims 1 to 3.

5. M is Pt; A is O, R １ is selected from the group consisting of isopropyl, phenyl having five deuterated hydrogen atoms, 2,6-diisopropylphenyl, and biphenyl-2-yl; and, R ２ ~R １７ are the same or different and each is independently selected from the group consisting of hydrogen, deuterium, isopropyl, tert-butyl, and cyano; The divalent metal complex according to any one of claims 1 to 4.

6. One or more hydrogen atoms in the divalent metal complex represented by formula (I) are replaced with one or more deuterium atoms. The divalent metal complex according to any one of claims 1 to 5.

7. The divalent metal complex has a structure represented by Complex 1 to Complex 30. 【Chemistry 2】 【change】 The divalent metal complex according to any one of claims 1 to 6.

8. A method for preparing the divalent metal complex of any one of claims 1 to 7, comprising the steps of: (1) performing a first coupling reaction between a compound a represented by formula (a) and a phenol compound b represented by formula (b) to obtain a compound c represented by formula (c); 【Chemistry 3】 (2) performing a functional group conversion reaction on the compound c represented by formula (c) to obtain a compound represented by formula (d); 【Chemistry 4】 (3) performing a second coupling reaction between the compound d represented by formula (d) and a compound h represented by formula (h) to obtain a compound represented by formula (e); and performing a third coupling reaction between the compound e represented by formula (e) and an amine compound i represented by formula (i) to obtain a compound f represented by formula (f); or, (4) performing a third coupling reaction between the compound d represented by formula (d) and an o-aniline compound j represented by formula (j) to obtain a compound f represented by formula (f); 【Chemistry 5】 (5) subjecting the compound f represented by formula (f) to a ring-closure reaction to obtain a compound g represented by formula (g); Preferably, the compound f represented by formula (f) is subjected to a ring-closure reaction with ammonium hexafluorophosphate and triethyl orthoformate to obtain a compound g represented by formula (g); 【Chemistry 6】 (6) subjecting the compound g represented by formula (g) to a cyclometallation reaction in the presence of a divalent platinum or palladium compound to obtain the divalent metal complex represented by formula (I); Including, Here, the group R １ ~R １７ The definitions of A and B are the same as those in any one of claims 1 to 7, X in formula (a), formula (c), formula (e), formula (h), and formula (j) are the same or different and each is F, Br, I, Cl, or OTf; A method characterized by:

9. The divalent metal complex is a divalent platinum complex of formula (I'): (1) carrying out a first coupling reaction between a furan compound a represented by formula (a) and a phenol compound b represented by formula (b) together with a substituent under the protection of a protective gas to obtain a compound c represented by formula (c); (2) carrying out a functional group conversion reaction of the compound c represented by formula (c) under the protection of a protective gas to convert the X group into amino, thereby obtaining a compound represented by formula (d); (3) Under the protection of protective gas, the compound d represented by formula (d) and the compound h represented by formula (h) are subjected to a second coupling reaction together with a substituent to obtain a compound represented by formula (e), and the compound e represented by formula (e) and the compound represented by formula R １ -NH ２ and a third coupling reaction with an amine compound i represented by formula (f) to obtain a compound f represented by formula (f); or, (4) carrying out a third coupling reaction between the compound d represented by formula (d) and an o-aniline compound j represented by formula (j) under the protection of a protective gas to obtain a compound f represented by formula (f); (5) subjecting the compound f represented by formula (f) to a ring-closure reaction with ammonium hexafluorophosphate and triethyl orthoformate under the protection of a protective gas to obtain a compound g represented by formula (g); (6) a step of subjecting the compound g represented by formula (g) to a cyclometallation reaction in the presence of cyclooctadiene platinum(II) dichloride or platinum dichloride to obtain a divalent platinum complex represented by formula (I'); Including, 【Chemistry 7】 wherein the definitions of the groups in formula (I'), formula (a), formula (b), formula (c), formula (d), formula (e), formula (f), formula (g), formula (h), and formula (j) are the same as those defined in any one of claims 1 to 7; X in formula (a), formula (c), formula (e), formula (h), and formula (j) are the same or different and each is F, Br, I, Cl, or OTf; The method of claim 8.

10. the first coupling reaction is an Ullmann coupling reaction; and / or the second coupling reaction is an Ullmann coupling reaction or a Buchwald-Hartwig coupling reaction; and / or the third coupling reaction is an Ullmann coupling reaction or a Buchwald-Hartwig coupling reaction; 10. The method according to claim 8 or 9.

11. In step (1), the first coupling reaction comprises conducting the reaction in the presence of a first catalyst, a first ligand, a first base, and a first solvent; and / or the first catalyst is a copper catalyst; the copper catalyst is at least one selected from the group consisting of cuprous iodide, cuprous bromide, cuprous chloride, and cuprous oxide; and / or the first ligand is N １ , N ２ -dimethylethane-1,2-diamine, 2,2,6,6-tetramethylheptadione, N １ , N ２ -bis(5-methyl-[1,1'-biphenyl]-2-yl)oxamide, trans-cyclohexanediamine, and 1-methylimidazole; and / or the first base is an inorganic base; the inorganic base is at least one selected from cesium carbonate, potassium carbonate, potassium phosphate, cesium fluoride, and potassium hydroxide; and / or the first solvent is one or more selected from dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, ethylene glycol dimethyl ether, deionized water, and toluene; and / or the molar ratio of the compound a represented by formula (a), the compound b represented by formula (b), the first catalyst, the first ligand, and the first base to be supplied is (0.5 to 3):1:(0.01 to 0.3):(0.01 to 0.5):(1 to 5); and / or the conditions of the first coupling reaction include a temperature of 90 to 130°C and a time of 5 to 36 hours; The method according to any one of claims 8 to 10.

12. In step (2), the functional group transformation reaction comprises carrying out the reaction in the presence of an ammonia source, a second catalyst, a second ligand, a second base, and a second solvent; and / or the ammonia source is one or more selected from aqueous ammonia, liquid ammonia, benzylamine, and trifluoroacetamide; and / or the second catalyst is a copper catalyst or a palladium catalyst; and / or the copper catalyst is one or more selected from cuprous iodide, cuprous bromide, and cuprous chloride; and / or the palladium catalyst is at least one selected from the group consisting of tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium, and palladium acetate; and / or the second ligand is a phosphine ligand, N １ , N ２ -dimethylethane-1,2-diamine, trans-cyclohexanediamine, 1-methylimidazole, and L-proline; and / or the phosphine ligand is one or more selected from 2-(di-tert-butylphosphine)biphenyl, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, and 1,1'-binaphthyl-2,2'-bis(diphenylphosphine); and / or the second base is an inorganic base or an organic base; and / or the inorganic base is one or more selected from cesium carbonate, potassium carbonate, potassium phosphate, cesium fluoride, and potassium hydroxide; and / or the organic base is one or more selected from sodium tert-butoxide, potassium tert-butoxide, and lithium tert-butoxide; and / or the second solvent is one or more selected from dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, ethylene glycol dimethyl ether, deionized water, and toluene; and / or the molar ratio of the compound c represented by formula (c), the ammonia source, the second catalyst, the second ligand, and the second base to be supplied is 1:(1 to 5):(0.01 to 1):(0.01 to 1.5):(1 to 6); and / or the conditions of the functional group conversion reaction include a temperature of 90 to 130°C and a time of 8 to 25 hours; and / or the functional group conversion reaction further comprises a step of removing protection from the amino having a protecting group generated in the conversion of the halogen to the amino, and palladium / carbon or iron powder is used as a reducing agent for the reduction; and / or the molar ratio of the amine having the protecting group to the reducing agent is 1:(0.01-0.5); The method according to any one of claims 8 to 11.

13. In step (3), the second coupling reaction comprises conducting the reaction in the presence of a third catalyst, a third ligand, a third base, and a third solvent; and / or the third catalyst is a copper catalyst or a palladium catalyst; and / or the copper catalyst is one or more selected from cuprous iodide, cuprous bromide, and cuprous chloride; and / or the palladium catalyst is at least one selected from the group consisting of tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium, and palladium acetate; and / or the third ligand is a phosphine ligand, N １ , N ２ -dimethylethane-1,2-diamine, 2,2,6,6-tetramethylheptadione, N １ , N ２ -bis(5-methyl-[1,1'-biphenyl]-2-yl)oxamide, trans-cyclohexanediamine, 1-methylimidazole, and L-proline; and / or the phosphine ligand is one or more selected from 2-(di-tert-butylphosphine)biphenyl, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, and 1,1'-binaphthyl-2,2'-bis(diphenylphosphine); and / or the third base is an inorganic base or an organic base; and / or the inorganic base is one or more selected from cesium carbonate, potassium carbonate, potassium phosphate, cesium fluoride, and potassium hydroxide; and / or the organic base is one or more selected from sodium tert-butoxide, potassium tert-butoxide, and lithium tert-butoxide; and / or the third solvent is one or more selected from dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, ethylene glycol dimethyl ether, deionized water, and toluene; and / or the supply molar ratio of the compound d represented by formula (d), the compound h represented by formula (h), the third catalyst, the third ligand, and the third base is 1:(1 to 3):(0.01 to 0.5):(0.01 to 1):(0.5 to 5); and / or the conditions of the second coupling reaction include a temperature of 90 to 150°C and a time of 11 to 25 hours; The method according to any one of claims 8 to 12.

14. In steps (3) and (4), the third coupling reaction includes conducting the reaction in the presence of a fourth catalyst, a fourth ligand, a fourth base, and a fourth solvent; and / or the fourth catalyst is a copper catalyst or a palladium catalyst; and / or the copper catalyst is one or more selected from cuprous iodide, cuprous bromide, and cuprous chloride; and / or the palladium catalyst is at least one selected from the group consisting of tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium, and palladium acetate; and / or the fourth ligand is a phosphine ligand, N １ , N ２ -dimethylethane-1,2-diamine, 2,2,6,6-tetramethylheptadione, N １ , N ２ -bis(5-methyl-[1,1'-biphenyl]-2-yl)oxamide, trans-cyclohexanediamine, 1-methylimidazole, and L-proline; and / or the phosphine ligand is one or more selected from 2-(di-tert-butylphosphine)biphenyl, 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl, and 1,1'-binaphthyl-2,2'-bis(diphenylphosphine); and / or the fourth base is an inorganic base or an organic base; and / or the inorganic base is one or more selected from cesium carbonate, potassium carbonate, potassium phosphate, cesium fluoride, and potassium hydroxide; and / or the organic base is one or more selected from sodium tert-butoxide, potassium tert-butoxide, and lithium tert-butoxide; and / or the fourth solvent is one or more selected from dimethyl sulfoxide, N,N-dimethylformamide, 1,4-dioxane, ethylene glycol dimethyl ether, deionized water, and toluene; and / or the molar ratio of the compound e represented by formula (e), the amine compound i having the substituent, the fourth catalyst, the fourth ligand, and the fourth base to be supplied is 1:(1 to 5):(0.05 to 1):(0.01 to 1):(1 to 6); and / or the supply molar ratio of the compound d represented by formula (d), the o-aniline compound j represented by formula (j), the fourth catalyst, the fourth ligand, and the fourth base may be 1:(1 to 5):(0.05 to 1):(0.01 to 1):(1 to 6); and / or the conditions of the third coupling reaction include a temperature of 110 to 150°C and a time of 8 to 25 hours; The method according to any one of claims 8 to 13.

15. In step (5), the feed molar ratio of the compound f of formula (f) to ammonium hexafluorophosphate is 1:(1-3); and / or the ring-closure reaction conditions include a temperature of 110 to 130°C and a time of 23 to 25 hours; The method according to any one of claims 8 to 14.

16. In step (6), The cyclometallation reaction includes a step of uniformly mixing and reacting the compound g represented by formula (g), a divalent platinum or palladium compound, preferably cyclooctadiene platinum dichloride or platinum dichloride, sodium acetate, and a solvent such as tetrahydrofuran or N,N-dimethylformamide, and / or the molar ratio of the compound g represented by formula (g) to the divalent platinum or palladium compound, preferably cyclooctadiene platinum dichloride or platinum dichloride, is 1:(0.5-3); and / or the cyclometallation reaction conditions include heating to 100-140°C under a nitrogen atmosphere and reacting for 71-75 hours under stirring; The method according to any one of claims 8 to 15.

17. Use of a divalent metal complex according to any one of claims 1 to 7 in an organic optoelectronic device, preferably a green phosphorescent organic optoelectronic device, more preferably a green phosphorescent organic electroluminescent device.

18. An organic optoelectronic device, Preferably, the organic electroluminescent device is an anode layer, a light-emitting layer, and a cathode layer; The light-emitting layer comprises a divalent metal complex, preferably a divalent platinum complex, according to any one of claims 1 to 7. An organic optoelectronic device comprising:

19. a substrate, an anode layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode layer; At least one of the light-emitting layer, the electron transport layer, and the hole transport layer comprises a divalent metal complex, preferably a divalent platinum complex, according to any one of claims 1 to 7; Preferably, the light-emitting layer comprises a divalent metal complex, preferably a divalent platinum complex.

19. The organic optoelectronic device according to claim 18,

20. the divalent metal complex, preferably a divalent platinum complex, is an emissive material, a host material, or a guest material in the emissive layer; The organic optoelectronic device according to any one of claims 18 to 19.

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