Pyridyl carbazole-based tetradentate cyclometalated platinum (II) complex, electronic device and application of pyridyl carbazole-based tetradentate cyclometalated platinum (II) complex

Abstract

The invention belongs to the field of organic electroluminescence, and particularly relates to a pyridylcarbazole-based tetradentate cyclometalated platinum (II) complex, an electronic device and application of the pyridylcarbazole-based tetradentate cyclometalated platinum (II) complex. The charge distribution of the excited state of the compound is improved by introducing a substituent group at a proper position of the ligand, so that the excited state of the material has more metal-to-pyridine and carbene charge transfer states (3MLCT), the radiation rate is favorably improved, and the service life of the device is further prolonged. The provided material has very good chemical stability and thermal stability, and is easy to prepare an evaporation type OLED (Organic Light Emitting Diode) device. The current efficiency and the service life of the organic light-emitting device manufactured by using the compound as a light-emitting layer are obviously improved, and the lighting voltage is obviously reduced. After being combined with a fluorescent doping material (boron-containing compound), the compound can balance hole and electron transmission, so that energy transmission between a subject and an object is more efficient, and the photochromic purity of a device can be improved.

Description

Technical Field

[0001] The invention belongs to the field of organic electroluminescence, and in particular relates to a pyridylcarbazole-based tetradentate ring metal platinum (II) complex, an electronic device and applications thereof. Background Art

[0002] Organic light-emitting diodes (OLEDs) are a new generation of full-color display and lighting technology. Compared with liquid crystal displays, which have the disadvantages of slow response speed, small viewing angle, need for backlight, and high energy consumption, OLED, as an autonomous light-emitting device, does not require a backlight and is energy-saving; it also has low driving voltage, fast response speed, high resolution and contrast, wide viewing angle, and outstanding low-temperature performance; OLED devices can be made thinner and can be made into flexible structures. In addition, it also has the advantages of low production cost, simple production process, and large-scale production. Therefore, OLED has broad and huge application prospects in high-end electronic products and aerospace; with the gradual increase in investment, further in-depth research and development, and the upgrading and transformation of production equipment, OLEDs will have very broad application scenarios and development prospects in the future.

[0003] The core of OLED development is the design and development of luminescent materials. In the currently used OLED devices, the luminescent layer almost all uses the host-guest luminescent system mechanism, that is, the guest luminescent material is doped in the host material. The energy system of the host material is generally greater than that of the guest luminescent material. The energy is transferred from the host material to the guest material, so that the guest material is excited and emits light. Commonly used organic phosphorescent guest materials are generally heavy metal atoms such as iridium (III), platinum (II), Pd (II), etc. Commonly used phosphorescent organic materials mCBP (3,3′-bis (9-carbazolyl) -biphenyl) and 2,6-mCPy (2,6-bis (9-carbazolyl) -pyridine) have high efficiency and high triplet energy levels. When used as organic materials, the triplet energy can be effectively transferred from the luminescent organic material to the guest phosphorescent luminescent material. However, due to the characteristics of mCBP that holes are easy to transport and electrons are difficult to flow, and 2,6-mCPy has poor hole transport, the charge of the luminescent layer is unbalanced, resulting in a reduction in the current efficiency of the device. In addition, the number of heavy metal phosphorescent organic complex molecules and cyclometallated iridium (III) complex molecules currently used is limited. The content of metallic platinum in the earth's crust and the annual production worldwide are both about ten times that of metallic iridium. IrCl3 used to prepare iridium (III) complex phosphorescent materials .The price of H2O is also much higher than that of PtCl2 used to prepare phosphorescent materials of platinum (II) complexes. In addition, the preparation of phosphorescent materials of iridium (III) complexes involves four steps: iridium (III) dimer, iridium (III) intermediate ligand exchange, synthesis of mer-iridium (III) complexes, and conversion of mer- to fac-iridium (III) complex isomers, which greatly reduces the total yield and the cost of raw material IrCl3 . The utilization rate of H2O increases the preparation cost of iridium (III) complex phosphorescent materials. In contrast, the preparation of platinum (II) complex phosphorescent materials only involves the metallization of the ligand in the last step, which is the reaction of designing platinum salts. The utilization rate of platinum elements is high, which can further reduce the preparation cost of platinum (II) complex phosphorescent materials. In summary, the preparation cost of platinum (II) complex phosphorescent materials is much lower than that of iridium (III) complex phosphorescent materials. However, there are still some technical difficulties in the development of platinum complex materials and devices. How to improve the efficiency and life of the device is a relatively important research issue. Therefore, it is urgent to develop new phosphorescent metal platinum (II) complexes. Summary of the invention

[0004] In view of this, the purpose of the present invention is to provide a tetradentate metal platinum (II) complex based on pyridylcarbazole, an electronic device and its application. The tetradentate metal platinum (II) complex based on pyridylcarbazole of the present invention can be used as a guest phosphorescent material of the light-emitting layer to make the device have excellent performance. It can improve the current efficiency of organic electroluminescent devices, improve the device life, and also reduce the operating voltage of components.

[0005] To achieve the above technical objectives, the technical solution of the present invention is as follows:

[0006] The present invention provides a tetradentate metal platinum (II) complex based on pyridylcarbazole, wherein the complex has a structure as shown in formula (I):

[0007]

[0008] In formula (I), R 1 -R 6 Each independently represents a single substitution to the maximum amount of substitution, or no substitution; R 1 -R 6 Each is independently selected from the group consisting of hydrogen, deuterium, halogen, C1-C30 alkyl, C1-C30 haloalkyl, substituted or unsubstituted C6-C60 aryl, and combinations thereof;

[0009] R a , R bEach is independently selected from the group consisting of: hydrogen, deuterium, C1-C30 alkyl, substituted or unsubstituted C6-C60 aryl and combinations thereof; the substitution is deuterium, C1-C30 alkyl, C6-C60 aryl.

[0010] Furthermore, R a is selected from hydrogen, deuterium, CD3, C1-C10 alkyl, C6-C30 aryl and combinations thereof; R b The group consisting of hydrogen, deuterium, C1-C20 alkyl and combinations thereof.

[0011] Furthermore, R 1 -R 6 Each is independently selected from hydrogen, deuterium, CD3, F, CF3, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, phenyl and combinations thereof.

[0012] Preferably, the tetradentate metal platinum (II) complex based on pyridylcarbazole is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023] Furthermore, the present invention also provides the use of the tetradentate ring metal platinum (II) complex having the structure shown in formula (I) in electronic devices.

[0024] Furthermore, the electronic devices include organic electroluminescent devices (OLEDs), organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light emitting electrochemical cells (LECs), and organic laser diodes (O-lasers).

[0025] In another aspect, the present invention further provides an organic electroluminescent device, which comprises the tetradentate metal platinum (II) complex having a structure shown in formula (I) as described above.

[0026] Furthermore, the organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises the tetradentate metal platinum (II) complex having the structure shown in formula (I) as described above.

[0027] Preferably, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the tetradentate metal platinum (II) complex having the structure represented by formula (I) as described above.

[0028] Furthermore, the light-emitting layer also contains a fluorescent doping material; the fluorescent doping material is a boron-containing organic molecular light-emitting compound.

[0029] In another aspect, the present invention further provides an organic photoelectric device, which comprises: a substrate layer; a first electrode, the first electrode being on the substrate; an organic light-emitting functional layer, the organic light-emitting functional layer being on the first electrode; a second electrode, the second electrode being on the organic light-emitting functional layer; wherein the organic light-emitting functional layer comprises a tetradentate metal platinum (II) complex having a structure as shown in formula (I) above. For example, the platinum (II) complex can be included in the organic light-emitting functional layer as a light-emitting material.

[0030] Furthermore, the organic light-emitting functional layer also contains any one or more fluorescent doping materials.

[0031] The present invention also provides a composition, which comprises the tetradentate metal platinum (II) complex having the structure shown in formula (I) as above. Preferably, the composition further comprises a fluorescent doping material, and the fluorescent doping material is preferably a phosphorescent sensitized boron-containing compound.

[0032] The present invention also provides a preparation, which comprises the tetradentate metal platinum (II) complex having a structure shown in formula (I) as above or the composition as above and at least one solvent.

[0033] The solvent is not particularly limited and may be used, for example, unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, butyl chloride, butyl bromide, pentyl chloride, pentyl bromide, hexyl chloride, hexyl bromide, cyclohexyl chloride, cyclohexyl bromide, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, ether solvents such as tetrahydrofuran, tetrahydropyran, and ester solvents such as alkyl benzoate.

[0034] The present invention also provides a display or lighting device, which comprises one or more of the organic photoelectric devices described above.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] The present invention improves the charge distribution of the excited state of the compound by introducing a substituent group at an appropriate position of the ligand, so that the excited state of the material has more metal to pyridocarbene charge transfer states ( 3 MLCT), which is beneficial to improve its radiation rate and thus improve the life of the device. The provided materials have good chemical stability and thermal stability, and are easy to prepare vapor-deposited OLED devices. The organic electroluminescent device made by using the compound of the present invention as the light-emitting layer has obvious improvements in current efficiency and life, and significantly reduces the lighting voltage. After being combined with a fluorescent doping material (boron-containing compound), it can balance the transmission of holes and electrons, make the energy transfer between the host and the guest more efficient, and improve the light color purity of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 It is the room temperature emission spectrum of Pt-1~Pt-4 in dichloromethane solution. DETAILED DESCRIPTION

[0038] The contents of the present invention will be described in detail below. The description of the constituent elements described below may be based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.

[0039] The term "substituted" used in the present invention is intended to include all allowed substituents of organic compounds. In a wide aspect, allowed substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and non-aromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. For suitable organic compounds, allowed substituents can be one or more, the same or different. For the purpose of the present invention, the present invention is not intended to be any restriction in any way with the allowed substituents of organic compounds. Similarly, the term "substituted" or "substituted with" contains implicit conditions that this substitution conforms to the allowed valence of the substituted atom and the substituent, and the substitution leads to a stable compound (for example, a compound that will not spontaneously undergo transformation (for example, by rearrangement, cyclization, elimination, etc.)). It is also expected that, in some aspects, unless explicitly indicated to the contrary, a single substituent can be further optionally substituted (that is, further substituted or unsubstituted).

[0040] In defining various terms, “R 1 ”-“R 6 " are used as general symbols in the present invention to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed in the present invention, and when they are limited to certain substituents in one case, they can be limited to some other substituents in other cases. The "R" used in the present invention can be any substituent, not limited to those disclosed in the present invention, and when they are limited to certain substituents in one case, they can be limited to some other substituents in other cases. 1 ”, “R 2 ”…“R n " ”(wherein n is an integer) may independently have one or more of the groups listed above. For example, if R 1 If it is a straight chain alkyl, then one of the hydrogen atoms of the alkyl may be optionally substituted with a hydroxyl, alkoxy, alkyl, halogen, etc. Depending on the groups selected, the first group may be incorporated within the second group, or alternatively, the first group may be pendant, ie attached to the second group.

[0041] The term "alkyl" used in the present invention is a saturated hydrocarbon group of 1 to 60 carbon atoms that is branched or unbranched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups, including but not limited to the optionally substituted alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxyl, nitro, silyl, sulphur-oxo or sulfhydryl groups of the present invention.

[0042] The term "aryl" used in the present invention is a group containing any carbon-based aromatic group of 5 to 60 carbon atoms, and the carbon-based aromatic group includes but is not limited to phenyl, naphthyl, phenyl, biphenyl, phenoxyphenyl, anthracenyl, phenanthrenyl, etc. The term "aryl" also includes "heteroaryl", which is defined as a group containing an aromatic group, and the aromatic group has at least one heteroatom introduced into the ring of the aromatic group. Examples of heteroatoms include but are not limited to nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term "non-heteroaryl" (which is also included in the term "aryl") defines a group containing an aromatic group, and the aromatic group does not contain heteroatoms. Aryl can be substituted or unsubstituted. The aryl group may be substituted with one or more groups, including but not limited to the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, sulfo-oxo or thiol groups described herein.

[0043] Compounds of the present invention may contain "optionally substituted" parts. Typically, the term "substituted" (whether or not the term "optionally" is present in the front) means that one or more hydrogens of the indicated part are replaced by suitable substituents. Unless otherwise specified, "optionally substituted" groups may have suitable substituents at each substitutable position of the group, and when more than one position may be substituted with more than one substituent selected from a specified group in any given structure, the substituents at each position may be the same or different. The substituent combinations envisioned by the present invention are preferably those that form stable or chemically feasible compounds. In some respects, unless clearly indicated to the contrary, it is also contemplated that each substituent may be further optionally substituted (that is, further substituted or unsubstituted).

[0044] The compounds disclosed herein can exhibit desirable properties and have emission and / or absorption spectra that can be tuned by selecting appropriate ligands. In another aspect, the invention can exclude any one or more compounds, structures or portions thereof specifically recited herein.

[0045] The compounds of the present invention may be prepared using a variety of methods, including but not limited to those described in the examples provided herein.

[0046] It should be noted that the above general description and the following detailed description are only exemplary and explanatory, and are not limiting. The present application can be more easily understood by referring to the following specific implementation manner and the examples contained therein.

[0047] Before disclosing and describing the compounds, devices and / or methods of the present invention, it should be understood that they are not limited to specific synthetic methods (otherwise otherwise indicated), or specific reagents (otherwise otherwise indicated), as this can of course vary. It should also be understood that the terms used in the present invention are only used for the purpose of describing specific aspects and are not intended to be limiting. Although any methods and materials similar or equivalent to those described in the present invention can be used in the practice or test, exemplary methods and materials are described below. Synthesis Examples All raw materials and solvents are commercially available unless otherwise specified, and solvents are used directly without further treatment.

[0048] The substrate of the present invention can be any substrate used in typical organic optoelectronic devices. It can be a glass or transparent plastic substrate, or a substrate of an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance. Depending on the properties of the substrate, the use direction is different. As the material for the hole injection layer, the hole transport layer, and the electron injection layer, any material can be selected from the known related materials for OLED devices, and the present invention does not make specific restrictions thereon.

[0049] Synthesis Example

[0050] The following examples of compound synthesis, composition, device or method are only to provide a general method for the industry, and are not intended to limit the scope of protection of the patent. The data (quantity, temperature, etc.) mentioned in the patent are as accurate as possible, but there may be some errors. Unless otherwise specified, weighing is separate weighing, temperature is ℃, or room temperature, and pressure is close to normal pressure.

[0051] The following examples provide methods for preparing new compounds, but the preparation of such compounds is not limited to this method. In this professional and technical field, since the protected compounds in the present invention are easy to modify and prepare, their preparation can adopt the following methods or other methods. The following examples are only examples and are not intended to limit the scope of protection of this patent. Temperature, catalyst, concentration, reactants and reaction process can all be changed to select different conditions for preparing the compounds for different reactants.

[0052] 1 H NMR (500 MHz) spectra were measured on an ANANCE III (500M) NMR spectrometer. Unless otherwise specified, DMSO-d6 or CDCl3 containing 0.1% TMS was used as the solvent for NMR. 1When CDCl3 is used as the solvent, TMS (δ=0.00 ppm) is used as the internal standard for H NMR spectra. When DMSO-d6 is used as the solvent, TMS (δ=0.00 ppm) or the residual DMSO peak (δ=2.50 ppm) or the residual water peak (δ=3.33 ppm) is used as the internal standard. 13 In the C NMR spectrum, CDCl3 (δ=77.00 ppm) or DMSO-d6 (δ=39.52 ppm) was used as the internal standard. HPLC-MS was measured on an Agilent 6210TOF LC / MS mass spectrometer; HRMS spectrum was measured on an Agilent 6210TOF LC / MS liquid chromatography-time of flight mass spectrometer. 1 In H NMR spectrum data: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad.

[0053] Synthesis of intermediate A-1-OH

[0054] The synthetic route of intermediate A-1-OH is as follows:

[0055]

[0056] (1) Add 1a (1 g, 4.27 mmol, 1.2 equivalents), 1b (666 mg, 3.56 mmol, 1.0 equivalents), tetrakistriphenylphosphine palladium (82 mg, 0.07 mmol, 2 mol%) and potassium carbonate (984 mg, 7.12 mmol, 2.0 equivalents) to a three-necked reaction bottle with a magnetic rod. Then, replace the nitrogen three times, and add ethylene glycol dimethyl ether (6 mL) and water (6 mL) under a nitrogen atmosphere. Heat to 100 ° C and react for 36 hours, then cool to room temperature, remove the solvent by vacuum distillation, and separate the crude product by column chromatography on silica gel, eluent: dichloromethane / ethyl acetate = 10:1, to obtain 994 mg of a yellow solid, recorded as A-1-NH2, with a yield of 88%.

[0057] (2) Add A-1-NH2 (994 mg, 3.35 mmol, 1.0 equivalent) and triethylbenzylammonium chloride (4.38 g, 19.22 mmol, 4.5 equivalent) to a three-necked reaction bottle with a magnetic rod. Then, replace the nitrogen three times, and add tert-butyl nitrite (2.2 g, 21.35 mmol, 5.0 equivalent) and dichloromethane (10 mL) under a nitrogen atmosphere. Stir the reaction at room temperature in the dark for 36 hours, then remove the solvent by vacuum distillation. The crude product is separated by column chromatography using silica gel, eluent: dichloromethane / ethyl acetate = 10:1, to obtain 670 mg of a yellow oil, recorded as A-1-Cl, with a yield of 55%.

[0058] (3) Add A-1-Cl (7 g, 22.16 mmol, 1.0 equivalent), 1c (6.56 g, 33.24 mmol, 1.5 equivalent), tris(dibenzylideneacetone)dipalladium (201 mg, 0.22 mmol, 1 mol%), 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl (183 mg, 0.44 mmol, 2 mol%) and sodium tert-butoxide (4.3 g, 44.32 mmol, 2.0 equivalent) to a three-necked reaction bottle with a magnetic rod. Then, replace nitrogen three times and add toluene (200 mL) under nitrogen atmosphere. Heat to 110 °C and react for 24 hours, then cool to room temperature, remove the solvent by vacuum distillation, and separate the crude product by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 20:1, to obtain 10.12 g of gray solid, recorded as A-1-MOe, with a yield of 96%.

[0059] (4) A-1-MOe (10.12 g, 21.23 mmol, 1.0 equivalent) and 48% hydrobromic acid (50 mL, 212.3 mmol, 10 equivalent) were added to a single-mouth reaction bottle with a magnetic bar, heated to 120°C for reaction for 24 hours, and then cooled to room temperature. The pH was adjusted to 7-8 with saturated sodium bicarbonate solution, and the organic phase was extracted three times with dichloromethane. The organic phases were combined and distilled under reduced pressure to remove the solvent. The crude product was slurried with ethyl acetate / petroleum ether to obtain 9.5 g of a white solid, recorded as A-1-OH, with a yield of 97%.

[0060] Synthesis of intermediate B-1-OH

[0061] The synthetic route of intermediate B-1-OH is as follows:

[0062]

[0063] (1) Add 1d (4 g, 28.56 mmol, 1.2 equivalents), 1b (4.45 g, 23.8 mmol, 1.0 equivalents), tetrakistriphenylphosphine palladium (496 mg, 0.44 mmol, 2 mol%) and potassium carbonate (6.58 g, 47.6 mmol, 2.0 equivalents) to a three-necked reaction bottle with a magnetic rod. Then, the nitrogen was replaced three times, and ethylene glycol dimethyl ether (16 mL) and water (16 mL) were added under a nitrogen atmosphere. After heating to 100 ° C for 36 hours, it was cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated by column chromatography using silica gel, and the eluent was dichloromethane / ethyl acetate = 10:1 to obtain 4.71 g of a yellow solid, which was recorded as B-1-NH2, with a yield of 98%.

[0064] (2) Add B-1-NH2 (4.82 g, 23.82 mmol, 1.0 equivalent) and triethylbenzylammonium chloride (24.43 g, 107.11 mmol, 4.5 equivalent) to a three-necked reaction bottle with a magnetic rod. Then replace the nitrogen three times, and add tert-butyl nitrite (12.27 g, 199 mmol, 5.0 equivalent) and dichloromethane (80 mL) under a nitrogen atmosphere. Stir the reaction at room temperature in the dark for 36 hours, then remove the solvent by vacuum distillation. The crude product is separated by column chromatography using silica gel, eluent: dichloromethane / ethyl acetate = 10:1, to obtain 4.74 g of a red oil, recorded as B-1-Cl, with a yield of 90%.

[0065] (3) Add B-1-Cl (3 g, 14 mmol, 1.0 equivalent), 1c (4.14 g, 21 mmol, 1.5 equivalent), tris(dibenzylideneacetone)dipalladium (128 mg, 0.14 mmol, 1 mol%), 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl (166 mg, 0.28 mmol, 2 mol%) and sodium tert-butoxide (2.69 g, 28 mmol, 2.0 equivalent) to a three-necked reaction bottle with a magnetic rod. Then, replace the nitrogen three times and add toluene (60 mL) under a nitrogen atmosphere. Heat to 110 °C for 24 hours and then cool to room temperature. After removing the solvent by vacuum distillation, the crude product is separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 20:1, to obtain 3.3 g of gray solid, with a yield of 62%.

[0066] Synthesis of intermediate A-2-Cl

[0067] The synthetic route of intermediate A-2-Cl is as follows:

[0068]

[0069] (1) Add potassium phosphate (9.2 g, 4.32 mmol, 2.0 equivalent) to a three-necked reaction bottle with a magnetic rod, remove moisture with a hot air gun under vacuum, and then add A-1-OH (1 g, 2.16 mmol, 1.0 equivalent), 2-pyridinecarboxylic acid (53 mg, 0.43 mmol, 20 mol%), and cuprous iodide (82 mg, 0.43 mmol, 20 mol%). Then replace nitrogen three times, and add 1d (830 mg, 4.32 mmol, 2.0 equivalent) and dimethyl sulfoxide (20 mL) under nitrogen atmosphere. Heat to 90 ° C for 36 hours and then cool to room temperature. Add deionized water to quench, extract the organic phase with ethyl acetate three times, combine the organic phases and then remove the solvent by vacuum distillation. The crude product is separated by column chromatography on silica gel, and the eluent: ethyl acetate / petroleum ether = 40:1 to obtain 450 mg of yellow oil, with a yield of 36%.

[0070] Synthesis of intermediate A-3-Cl

[0071] The synthetic route of intermediate A-3-Cl is as follows:

[0072]

[0073] (1) Potassium phosphate (8.8 g, 20.72 mmol, 2.0 equivalents) was added to a three-necked reaction bottle with a magnetic rod, and the water was removed with a hot air gun under vacuum atmosphere, and then A-1-OH (9.59 g, 20.72 mmol, 1.0 equivalents), 2-pyridinecarboxylic acid (510 mg, 4.14 mmol, 20 mol%), and cuprous iodide (788 mg, 4.14 mmol, 20 mol%) were added. Then, nitrogen was replaced three times, and 1f (11.38 g, 41.44 mmol, 2.0 equivalents) and dimethyl sulfoxide (100 mL) were added under nitrogen atmosphere. The reaction mixture was heated to 90°C for 12 hours and then cooled to room temperature. Deionized water was added to quench the reaction. The organic phase was extracted three times with ethyl acetate. The organic phases were combined and then the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography using silica gel. The eluent was ethyl acetate / petroleum ether = 50:1 to obtain 9.89 g of a yellow oil, recorded as A-3-Cl, with a yield of 76%. 1 H NMR(500MHz,Chloroform-d)δ8.54(s,1H),8.09(dd,J=10,5Hz,2H),7.84(d,J=10Hz,1H),7.58(d,J=5Hz,1H),7.52–7.48(m,2H),7.47–7.42(m,1 H),7.35–7.30(m,1H),7.25(d,J=10Hz,2H),7.06(t,J=5Hz,1H),7.04–6 .99(m,2H),6.78(t,J=5Hz,1H),2.42(s,3H),1.39(s,18H),1.28(s,9H).

[0074] Synthesis of intermediate A-4-Cl

[0075] The synthetic route of intermediate A-4-Cl is as follows:

[0076]

[0077] (1) Add potassium phosphate (1.27 g, 6 mmol, 2.0 equivalents) to a three-necked reaction bottle with a magnetic rod, remove moisture with a hot air gun under vacuum, and then add B-1-OH (1 g, 3 mmol, 1.0 equivalents), 2-pyridinecarboxylic acid (37 mg, 0.3 mmol, 20 mol%), and cuprous iodide (57 mg, 0.3 mmol, 10 mol%). Then replace nitrogen three times, and add 1f (1.49 g, 6 mmol, 2.0 equivalents) and dimethyl sulfoxide (20 mL) under nitrogen atmosphere. Heat to 90 ° C for 12 hours and then cool to room temperature. Add deionized water to quench, extract the organic phase with ethyl acetate three times, combine the organic phases and then remove the solvent by vacuum distillation. The crude product is separated by column chromatography on silica gel, and the eluent: ethyl acetate / petroleum ether = 20:1, to obtain 1.13 g of yellow solid, with a yield of 70%.

[0078] Synthesis of intermediate C-2-NH2

[0079] The synthetic route of intermediate C-2-NH2 is as follows:

[0080]

[0081] (1) Add 2a (20 g, 134.01 mmol, 1.0 equivalent) and dichloromethane (200 mL) to a single-mouth reaction bottle with a magnetic rod, stir until dissolved, cool to 0°C, slowly add N-bromosuccinimide (50.09 g, 281.42 mmol, 2.1 equivalent), and then return to room temperature for stirring and reacting for 24 hours. Then add sodium thiosulfate (3.32 g, 13.4 mmol, 0.1 equivalent) to quench, extract the organic phase with dichloromethane three times, combine the organic phases, remove the solvent by vacuum distillation, and separate the crude product by column chromatography on silica gel, eluent: petroleum ether / ethyl acetate = 80:1, to obtain 40.98 g of red liquid, with a yield of 99%.

[0082] (2) Add C-1-NH2 (30 g, 97.71 mmol, 1.0 equivalent) and N,N-dimethylformamide (100 mL) to a single-mouth reaction bottle with a magnetic rod, stir until dissolved, cool to 0°C, slowly add 60% sodium hydride (4.3 g, 107.48 mmol, 1.1 equivalent), stir for 30 minutes, add 2b (13.79 g, 97.71 mmol, 1.0 equivalent), and then return to room temperature for stirring and reaction for 24 hours. Then add deionized water to quench, extract the organic phase with dichloromethane three times, combine the organic phases, remove the solvent by vacuum distillation, and separate the crude product by column chromatography with silica gel, eluent: petroleum ether / dichloromethane = 6:1, to obtain 33.48 g of red oil, with a yield of 80%.

[0083] (3) Add C-1-NO2 (5 g, 11.68 mmol, 1.0 equivalent), 2c (4.27 g, 35.04 mmol, 3.0 equivalent), tetrakistriphenylphosphine palladium (270 mg, 0.26 mmol, 2 mol%) and potassium carbonate (3.23 g, 23.36 mmol, 2.0 equivalent) to a three-necked reaction bottle with a magnetic rod. Then replace the nitrogen three times, and add toluene (30 mL) / ethanol (10 mL) / water (10 mL) under a nitrogen atmosphere. Heat to 90 ° C for 24 hours and then cool to room temperature. After removing the solvent by vacuum distillation, the crude product is separated by column chromatography on silica gel, eluent: petroleum ether / ethyl acetate = 40:1, to obtain 4.52 g of yellow solid, with a yield of 91%.

[0084] (4) Add C-2-NO2 (4.52 g, 10.7 mmol, 1.0 equivalent) and stannous chloride dihydrate (9.66 g, 42.8 mmol, 4.0 equivalent) to a three-necked reaction bottle with a magnetic rod. Then replace the nitrogen three times, and add ethyl acetate (30 mL) / ethanol (30 mL) under a nitrogen atmosphere. Heat to 80 ° C for 24 hours and then cool to room temperature. Add saturated sodium bicarbonate solution to quench, extract the organic phase with ethyl acetate three times, combine the organic phases and remove the solvent by vacuum distillation. The crude product is separated by column chromatography on silica gel, eluent: petroleum ether / ethyl acetate = 5:1, and 3.06 g of yellow solid is obtained, with a yield of 73%.

[0085] Synthesis of intermediate D-2-NH2

[0086] The synthetic route of intermediate D-2-NH2 is as follows:

[0087]

[0088] (1) Add 3a (24.52 g, 97.71 mmol, 1.0 equivalent) and N,N-dimethylformamide (100 mL) to a single-mouth reaction bottle with a magnetic rod, stir until dissolved, cool to 0°C, slowly add 60% sodium hydride (4.3 g, 107.48 mmol, 1.1 equivalent), stir for 30 minutes, add 2b (13.79 g, 97.71 mmol, 1.0 equivalent), and then return to room temperature for stirring and reacting for 24 hours. Then add deionized water to quench, extract the organic phase with dichloromethane three times, combine the organic phases, remove the solvent by vacuum distillation, and separate the crude product by column chromatography with silica gel, eluent: petroleum ether / dichloromethane = 6:1, to obtain 30.17 g of red oil, with a yield of 83%.

[0089] (2) Add D-1-NO2 (4.35 g, 11.68 mmol, 1.0 equivalent), 2-b (4.27 g, 35.04 mmol, 3.0 equivalent), tetrakistriphenylphosphine palladium (270 mg, 0.26 mmol, 2 mol%) and potassium carbonate (3.23 g, 23.36 mmol, 2.0 equivalent) to a three-necked reaction bottle with a magnetic rod. Then replace the nitrogen three times, and add toluene (30 mL) / ethanol (10 mL) / water (10 mL) under a nitrogen atmosphere. Heat to 90 ° C for 24 hours and then cool to room temperature. After removing the solvent by vacuum distillation, the crude product is separated by column chromatography on silica gel, eluent: petroleum ether / ethyl acetate = 40:1, to obtain 3.77 g of yellow solid, with a yield of 88%.

[0090] (3) Add D-2-NO2 (3.92 g, 10.7 mmol, 1.0 equivalent) and stannous chloride dihydrate (9.66 g, 42.8 mmol, 4.0 equivalent) to a three-necked reaction bottle with a magnetic rod. Then replace the nitrogen three times, and add ethyl acetate (30 mL) / ethanol (30 mL) under a nitrogen atmosphere. Heat to 80 ° C for 24 hours and then cool to room temperature. Add saturated sodium bicarbonate solution to quench, extract the organic phase with ethyl acetate three times, combine the organic phases and remove the solvent by vacuum distillation. The crude product is separated by column chromatography on silica gel, eluent: petroleum ether / ethyl acetate = 5:1, and 2.52 g of yellow solid is obtained, with a yield of 70%.

[0091] Synthesis of intermediate E-1-NH2

[0092] The synthetic route of intermediate E-1-NH2 is as follows:

[0093]

[0094] (1) Add 4a (2 g, 14.48 mmol, 1.0 equivalent) and N,N-dimethylformamide (20 mL) to a single-mouth reaction bottle with a magnetic rod, stir until dissolved, cool to 0°C, slowly add 60% sodium hydride (636 mg, 14.94 mmol, 1.1 equivalent), stir for 30 minutes, add 4b (2.17 g, 14.48 mmol, 1.0 equivalent), and then return to room temperature for stirring and reacting for 24 hours. Then add deionized water to quench, extract the organic phase with dichloromethane three times, combine the organic phases, remove the solvent by vacuum distillation, and separate the crude product by column chromatography with silica gel, eluent: petroleum ether / dichloromethane = 6:1, to obtain 1.42 g of red oil, with a yield of 63%.

[0095] (2) Add E-2-NO2 (1.42 g, 9.15 mmol, 1.0 equivalent) and stannous chloride dihydrate (8.26 g, 36.6 mmol, 4.0 equivalent) to a three-necked reaction bottle with a magnetic rod. Then replace the nitrogen three times, and add ethyl acetate (10 mL) / ethanol (10 mL) under a nitrogen atmosphere. Heat to 80 ° C for 24 hours and then cool to room temperature. Add saturated sodium bicarbonate solution to quench, extract the organic phase with ethyl acetate three times, combine the organic phases and remove the solvent by vacuum distillation. The crude product is separated by column chromatography on silica gel, eluent: petroleum ether / ethyl acetate = 5:1, and 859 mg of black oil is obtained, with a yield of 75%.

[0096] It should be noted that the above is only a feasible preparation scheme for one of the intermediates of the present invention. The synthesis process of intermediate A-1-OH, intermediate A-2-Cl, and E-1-NH2 can be referred to to prepare the intermediates required for each embodiment. The preparation of such intermediate compounds is not limited to this method. The preparation can be carried out by the methods listed above or by other methods known in the art. It is not intended to limit the scope of protection of the present invention.

[0097] Example 1: Synthesis of Pt-1

[0098] The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material Pt-1 is as follows:

[0099]

[0100] Synthesis of intermediate (F-1-2NH): A-2-Cl (200 mg, 0.35 mmol, 1.0 equivalent), C-2-NH2 (137 mg, 0.35 mmol, 1.0 equivalent), tris(dibenzylideneacetone)dipalladium (10 mg, 0.01 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (8 mg, 0.02 mmol, 6 mol%) and sodium tert-butoxide (67 mg, 0.7 mmol, 2.0 equivalent) were added to a three-necked reaction bottle with a magnetic pole. Then, nitrogen was replaced three times, and toluene (10 mL) was added under a nitrogen atmosphere. After heating to 120°C for 4 hours, the mixture was cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel column chromatography, and the eluent was petroleum ether / ethyl acetate = 20:1 to obtain 277 mg of a yellow solid with a yield of 85%.

[0101] Synthesis of ligand LYQ-1-PF6: Add F-1-2NH (277 mg, 0.3 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (98 mg, 0.6 mmol, 2.0 equivalent) to a three-necked reaction bottle with a magnetic pole. Then replace the nitrogen three times, and add triethyl orthoformate (5 mL) under a nitrogen atmosphere. Heat to 80 ° C for 25 minutes and then cool to room temperature. After removing the solvent by vacuum distillation, the crude product is separated by silica gel column chromatography, eluent: dichloromethane / ethyl acetate = 40:1, and 173 mg of yellow solid is obtained, with a yield of 53%.

[0102] Synthesis of Pt-1: Add LYQ-1-PF6 (177 mg, 0.16 mmol, 1.0 equivalent), (1,5-cyclooctadiene) platinum (II) dichloride (64 mg, 0.17 mmol, 1.05 equivalent) and sodium acetate (39 mg, 0.48 mmol, 3.0 equivalent) to a sealed tube with a magnetic pole. Then replace the nitrogen three times, and add diethylene glycol dimethyl ether (5 mL) under a nitrogen atmosphere. Heat to 120 ° C and stir the reaction for three days, then cool to room temperature, remove the solvent by vacuum distillation, and separate the crude product by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 2:1, to obtain 42 mg of cyan solid, with a yield of 23%. 1 H NMR(500MHz,DMSO-d6)δ9.00(s,1H),8.22(d,J=5Hz,1H),8.17(d,J=10Hz,1H),8.11(d,J=10Hz,1H),7.9 9(s,1H),7.85(d,J=5Hz,1H),7.63(t,J=15Hz,1H),7.58(d,J=10Hz,1H),7.49–7.45(m,2H),7.37(d,J=5 Hz,1H),7.25(d,J=15Hz,1H),7.18–7.11(m,5H),7.03(d,J=15Hz,1H),6.96(s,3H),6.89(d,J=10Hz,1H) ,6.77(d,J=5Hz,3H),6.47(t,J=15Hz,3H),6.03(t,J=15Hz,2H),2.05(s,3H),1.50(s,9H),1.14(s,18H).

[0103] Example 2: Synthesis of Pt-2

[0104] The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material Pt-2 is as follows:

[0105]

[0106] Synthesis of intermediate (F-2-2NH): A-2-Cl (250 mg, 0.44 mmol, 1.0 equivalent), D-2-NH2 (148 mg, 0.44 mmol, 1.0 equivalent), tris(dibenzylideneacetone)dipalladium (10 mg, 0.01 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (8 mg, 0.02 mmol, 6 mol%) and sodium tert-butoxide (85 mg, 0.88 mmol, 2.0 equivalent) were added to a three-necked reaction bottle with a magnetic pole. Then, nitrogen was replaced three times, and toluene (10 mL) was added under nitrogen atmosphere. After heating to 120°C for 4 hours, the mixture was cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel column chromatography, and the eluent was petroleum ether / ethyl acetate = 20:1 to obtain 158 mg of yellow solid with a yield of 41%.

[0107] Synthesis of ligand LYQ-2-PF6: Add F-2-2NH (158 mg, 0.18 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (59 mg, 0.36 mmol, 2.0 equivalent) to a three-necked reaction bottle with a magnet. Then replace the nitrogen three times, and add triethyl orthoformate (5 mL) under a nitrogen atmosphere. Heat to 80 ° C for 25 minutes and then cool to room temperature. After removing the solvent by vacuum distillation, the crude product is separated by silica gel column chromatography, eluent: dichloromethane / ethyl acetate = 40:1, to obtain 144 mg of yellow solid, with a yield of 78%.

[0108] Synthesis of Pt-2: Add LYQ-2-PF6 (144 mg, 0.14 mmol, 1.0 equivalent), (1,5-cyclooctadiene) platinum (II) dichloride (56 mg, 0.15 mmol, 1.05 equivalent) and sodium acetate (34 mg, 0.42 mmol, 3.0 equivalent) to a sealed tube with a magnetic pole. Then replace the nitrogen three times, and add diethylene glycol dimethyl ether (5 mL) under a nitrogen atmosphere. Heat to 120 ° C and stir the reaction for three days, then cool to room temperature, remove the solvent by vacuum distillation, and separate the crude product by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 2:1, to obtain 31 mg of cyan solid, yield 19%. 1H NMR(500MHz,DMSO-d6)δ8.77(s,1H),8.30(d,J=10Hz,1H),8.16(dd,J=10,5Hz,2H),8.00(s, 1H),7.80(d,J=10Hz,1H),7.63(s,2H),7.57(t,J=5Hz,1H),7.46(t,J=10Hz,1H),7.41(d,J=5 Hz,1H),7.26–7.19(m,4H),7.16(dd,J=10,5Hz,3H),7.08–7.01(m,4H),6.97(dd,J=15,10Hz, 4H),6.77(d,J=10Hz,1H),6.68(d,J=5Hz,2H),6.65–6.59(m,2H),2.28(s,3H),1.15(s,18H).

[0109] Example 3: Synthesis of Pt-3

[0110] The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material Pt-3 is as follows:

[0111]

[0112] Synthesis of intermediate (F-3-2NH): A-3-Cl (300 mg, 0.65 mmol, 1.0 equivalent), C-2-NH2 (255 mg, 0.65 mmol, 1.0 equivalent), tris(dibenzylideneacetone)dipalladium (18 mg, 0.02 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (16 mg, 0.04 mmol, 6 mol%) and sodium tert-butoxide (125 mg, 1.3 mmol, 2.0 equivalent) were added to a three-necked reaction bottle with a magnetic pole. Then, nitrogen was replaced three times, and toluene (10 mL) was added under nitrogen atmosphere. After heating to 120°C for 4 hours, the mixture was cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel column chromatography, and the eluent was petroleum ether / ethyl acetate = 20:1 to obtain 441 mg of yellow solid with a yield of 94%.

[0113] Synthesis of ligand LYQ-3-PF6: Add F-3-2NH (441 mg, 0.45 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (147 mg, 0.9 mmol, 2.0 equivalent) to a three-necked reaction bottle with a magnet. Then replace the nitrogen three times, and add triethyl orthoformate (5 mL) under a nitrogen atmosphere. Heat to 80 ° C for 25 minutes and then cool to room temperature. After removing the solvent by vacuum distillation, the crude product is separated by silica gel column chromatography, eluent: dichloromethane / ethyl acetate = 40:1, to obtain 426 mg of yellow solid, with a yield of 83%.

[0114] Synthesis of LYQ-3-Pt: Add LYQ-3-PF6 (250 mg, 0.22 mmol, 1.0 equivalent), (1,5-cyclooctadiene) platinum (II) dichloride (85 mg, 0.23 mmol, 1.05 equivalent) and sodium acetate (53 mg, 0.66 mmol, 3.0 equivalent) to a sealed tube with a magnetic pole. Then replace the nitrogen three times, and add diethylene glycol dimethyl ether (10 mL) under a nitrogen atmosphere. Heat to 120 ° C and stir the reaction for three days, then cool to room temperature, remove the solvent by vacuum distillation, and separate the crude product by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 2:1, to obtain 158 mg of cyan solid, with a yield of 61%. 1 H NMR(500MHz,DMSO-d6)δ8.98(s,1H),8.22(d,J=5Hz,1H),8.10(t,J=10Hz,2H),7.98(s,1H),7.84( d,J=5Hz,1H),7.63(t,J=10Hz,1H),7.50–7.44(m,3H),7.37(d,J=5Hz,1H),7.29(t,J=10Hz,1H),7. 17–7.13(m,4H),7.05(t,J=10Hz,1H),6.98–6.95(m,3H),6.90(d,J=5Hz,1H),6.79(d,J=10Hz,3H) ,6.54–6.44(m,3H),6.05(t,J=10Hz,2H),2.05(s,3H),1.50(s,10H),1.41(s,10H),1.13(s,20H).

[0115] Example 4: Synthesis of Pt-24

[0116] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt-24 is as follows:

[0117]

[0118] Synthesis of intermediate (F-4-2NH): A-2-Cl (250 mg, 0.44 mmol, 1.0 equivalent), D-2-NH2 (148 mg, 0.44 mmol, 1.0 equivalent), tris(dibenzylideneacetone)dipalladium (10 mg, 0.01 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (8 mg, 0.02 mmol, 6 mol%) and sodium tert-butoxide (85 mg, 0.88 mmol, 2.0 equivalent) were added to a three-necked reaction bottle with a magnetic pole. Then, nitrogen was replaced three times, and toluene (10 mL) was added under nitrogen atmosphere. After heating to 120°C for 4 hours, the mixture was cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel column chromatography, and the eluent was petroleum ether / ethyl acetate = 20:1 to obtain 158 mg of yellow solid with a yield of 41%.

[0119] Synthesis of ligand LYQ-4-PF6: Add F-2-2NH (158 mg, 0.18 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (59 mg, 0.36 mmol, 2.0 equivalent) to a three-necked reaction bottle with a magnetic pole. Then replace the nitrogen three times, and add triethyl orthoformate (5 mL) under a nitrogen atmosphere. Heat to 80 ° C for 25 minutes and then cool to room temperature. After removing the solvent by vacuum distillation, the crude product is separated by silica gel column chromatography, eluent: dichloromethane / ethyl acetate = 40:1, to obtain 144 mg of yellow solid, with a yield of 78%.

[0120] Synthesis of Pt-24: LYQ-4-PF6 (200 mg, 0.26 mmol, 1.0 equivalent), (1,5-cyclooctadiene) platinum (II) dichloride (101 mg, 0.27 mmol, 1.05 equivalent) and sodium acetate (64 mg, 0.78 mmol, 3.0 equivalent) were added to a sealed tube with a magnetic pole. Then the nitrogen was replaced three times, and diethylene glycol dimethyl ether (10 mL) was added under a nitrogen atmosphere. After heating to 120 ° C and stirring for three days, the reaction was cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 2:1, and 116 mg of cyan solid was obtained, with a yield of 54%. 1 H NMR(500MHz,DMSO-d6)δ9.30(s,1H),8.23(d,J=10Hz,1H),8.19–8.14(m,3H),7.90(d,J=15Hz,1H),7.71(d,J=5Hz,1H ),7.57(s,1H),7.55–7.49(m,4H),7.42(dt,J=20,5Hz,2H),7.34–7.26(m,3H),6.98(s,1H),2.30(s,3H),1.44(s,9H).

[0121] Example 5: Synthesis of Pt-8

[0122] Pt-8 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-1. The target product was obtained as a yellow solid of 562 mg with a yield of 70%. Molecular weight [M+H] + :866.33.

[0123] Example 6: Synthesis of Pt-31

[0124] Pt-31 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-1. The target product was obtained as a yellow solid (624 mg) with a yield of 56%. Molecular weight [M+H] + :1018.40.

[0125] Example 7: Synthesis of Pt-37

[0126] Pt-37 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-1. The target product was obtained as a yellow solid (661 mg) with a yield of 82%. Molecular weight [M+H] + :1074.46.

[0127] Example 8: Synthesis of Pt-65

[0128] Pt-65 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-1. The target product was obtained as a yellow solid (484 mg) with a yield of 67%. Molecular weight [M+H] + :1186.58.

[0129] Example 9: Synthesis of Pt-81

[0130] Pt-81 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-1. The target product was obtained as a yellow solid (455 mg) with a yield of 60%. Molecular weight [M+H] + :1037.44.

[0131] Example 10: Synthesis of Pt-174

[0132] Pt-174 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-1. The target product was obtained as a yellow solid (410 mg) with a yield of 66%. Molecular weight [M+H] + :1279.57.

[0133] Example 11: Synthesis of Pt-183

[0134] Pt-183 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-1. The target product was obtained as a yellow solid (492 mg) with a yield of 82%. Molecular weight [M+H] + :1203.53.

[0135] Example 12: Synthesis of Pt-241

[0136] Pt-241 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-1. The target product was obtained as a yellow solid (467 mg) with a yield of 72%. Molecular weight [M+H] + :1065.48.

[0137] Example 13: Synthesis of Pt-256

[0138] Pt-256 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-1. The target product was obtained as a yellow solid of 528 mg with a yield of 68%. Molecular weight [M+H] + :924.41.

[0139] Example 14: Synthesis of Pt-273

[0140] Pt-273 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-1. The target product was obtained as a yellow solid (436 mg) with a yield of 49%. Molecular weight [M+H] + :1166.52.

[0141] Photophysical properties:

[0142] Table 1. Photophysical properties of some metal complexes in dichloromethane solution

[0143] Complex Maximum emission wavelength Half peak width Pt-1 455.8nm 19.4nm Pt-2 456.2nm 21.2nm Pt-24 460.6nm 39.6nm Pt-37 457.4nm 33.8nm

[0144] Figure 1 It is the room temperature emission spectrum of Pt-1~Pt-4 in dichloromethane solution. Figure 1 As can be seen from Table 1, the metal complexes provided by the present invention are all in the blue and deep blue light emission regions, have high color purity, and have a narrow half-peak width, and are very good blue light phosphorescent materials.

[0145] Fabrication of OLED devices:

[0146] As a reference preparation method for a device embodiment, the present invention deposits a p-doped material on the surface of an ITO glass or an anode with a light-emitting area of ​​2mm×2mm, or co-evaporates the p-doped material with a hole injection material at a concentration of 1% to 50% to form a 5-100nm hole injection layer (HIL), a 5-200nm hole transport layer (HTL), and then forms a 10-100nm light-emitting layer (EML) (which may contain the compound described in the present invention) on the hole transport layer, forms an electron transport layer (ETL) of 20-200nm and a cathode of 50-200nm; if necessary, an electron blocking layer (EBL) is added between the HTL and EML layers, and an electron injection layer (EIL) is added between the ETL and the cathode to manufacture an OLED device. The OLED is tested by a standard method. The device materials involved in the present invention can be obtained by known synthesis methods unless otherwise specified.

[0147] In a preferred specific embodiment, the structure of device example 1 provided by the present invention is: ITO / P-4 (10nm) / NPD (60nm) / HTH-85 (5nm) / platinum (II) complex: HTH-85:ETH-45 (25nm) (Pt-1:HTH-85:ETH-45 mass ratio is 10:60:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0148] Device Examples 2 to 14 and Comparative Example 1 were prepared using structures similar to that of Device Example 1, except that Pt-2, Pt-3, Pt-8, Pt-24, Pt-31, Pt-37, Pt-65, Pt-81, Pt-174, Pt-183, Pt-241, Pt-256, Pt-273, and R1 were used to replace Pt-1 in Device Example 1. The luminescence properties of the comparative examples and device examples prepared above were tested by standard methods, and the data are shown in Table 2. The device structures involved are as follows: wherein P-4 is HATCN, and ET-14 is BPyTP.

[0149]

[0150]

[0151] Table 2 Device luminescence characteristics data table

[0152]

[0153] As can be seen from Table 2, compared with Comparative Example 1, Device Examples 1 to 14 prepared in the present application all show good device performance in terms of driving voltage, current efficiency and device life. The improvement in the performance of each device example is based on the specific compound material of the present invention having better electron transmission ability. It can be seen that when it is used as a light-emitting layer material to prepare an electronic device, it has higher current efficiency and device life while reducing the driving voltage. In addition, the devices prepared by the present invention are all deep blue light devices, and the CIEy values ​​are all less than 0.19. It shows that the compounds provided by the present invention have certain commercial application value.

[0154] In a preferred specific embodiment, the structure of device example 15 provided by the present invention is: ITO / P-4 (10nm) / NPD (60nm) / HTH-85 (5nm) / platinum (II) complex: boron-containing compound: HTH-85:ETH-45 (25nm) (Pt-1: BN1: HTH-85: ETH-45 mass ratio is 10:1:59:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0155] Device Examples 16 to 18 and Comparative Example 2 were prepared using structures similar to that of Device Example 11, except that the platinum (II) complex and the boron-containing compound in Device Example 15 were replaced by the compounds listed in Table 3. The device structures and luminescence characteristics are shown in Table 3.

[0156] Table 3. Device structure and luminescence characteristics data table

[0157]

[0158]

[0159] As shown in Table 3, the compounds of the present invention are used as sensitizing materials and are applied to devices together with boron-containing compounds as luminescent materials, and the performance of each device is also significantly improved. This further shows that the compounds provided by the present invention have certain commercial application value. In addition, after adding the boron-containing compound to the sensitized device structure, the CIEy value can be further reduced, thereby further improving the purity of the device luminescent color.

[0160] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A tetradentate metal platinum (II) complex based on phenylpyridine, characterized in that: The complex has a structure as shown in formula (I): In formula (I), R 1 -R 6 Each independently represents a single substitution to the maximum amount of substitution, or no substitution; R 1 -R 6 Each is independently selected from the group consisting of hydrogen, deuterium, halogen, C1-C30 alkyl, C1-C30 haloalkyl, substituted or unsubstituted C6-C60 aryl, and combinations thereof; R a , R b Each is independently selected from the group consisting of: hydrogen, deuterium, C1-C30 alkyl, substituted or unsubstituted C6-C60 aryl and combinations thereof; the substitution is deuterium, C1-C30 alkyl, C6-C60 aryl.

2. The tetradentate ring metal platinum (II) complex according to claim 1, characterized in that The R a is selected from hydrogen, deuterium, CD3, C1-C10 alkyl, C6-C30 aryl and combinations thereof; R b The group consisting of hydrogen, deuterium, C1-C20 alkyl and combinations thereof.

3. The tetradentate ring metal platinum (II) complex according to claim 1, characterized in that R 1 -R 6 Each is independently selected from hydrogen, deuterium, CD3, F, CF3, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, phenyl and combinations thereof.

4. The tetradentate ring metal platinum (II) complex according to claim 1, characterized in that The tetradentate metal platinum (II) complex is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:

5. Use of the tetradentate metal platinum (II) complex according to any one of claims 1 to 4 in electronic devices, wherein the electronic devices include one or more of an organic electroluminescent device, an organic integrated circuit, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field quenching device, a light emitting electrochemical cell or an organic laser diode.

6. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises the tetradentate metal platinum (II) complex according to any one of claims 1 to 4.

7. An organic electroluminescent device, characterized in that: The organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the tetradentate metal platinum (II) complex according to any one of claims 1 to 4.

8. The organic electroluminescent device according to claim 7, characterized in that: The light-emitting layer also contains fluorescent doping materials.

9. An organic optoelectronic device, characterized in that: The organic photoelectric device comprises: a substrate layer; a first electrode, which is on the substrate; an organic light-emitting functional layer, which is on the first electrode; and a second electrode, which is on the organic light-emitting functional layer; wherein the organic light-emitting functional layer contains the tetradentate metal platinum (II) complex according to any one of claims 1 to 4.

10. The organic optoelectronic device according to claim 9, characterized in that: The organic light-emitting functional layer also contains fluorescent doping materials.

11. A composition, characterized in that The composition comprises the tetradentate platinum (II) complex according to any one of claims 1 to 4.

12. A preparation, characterized in that The preparation comprises the tetradentate platinum (II) complex according to any one of claims 1 to 4.

13. A display or lighting device, characterized in that: The device comprises one or more of the organic electroluminescent devices according to any one of claims 6 to 8.

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