Fused-ring carbazole tetradentate metal platinum (II) complex, electronic device and application of fused-ring carbazole tetradentate metal platinum (II) complex

Abstract

The invention belongs to the field of organic electroluminescence, and particularly relates to a fused-ring carbazole tetradentate metal platinum (II) complex, an electronic device and application of the fused-ring carbazole tetradentate metal platinum (II) complex. According to the invention, interaction among molecules is reduced through introduction of diphenyl, and a ring-fused carbazole system is introduced to different positions of carbazole, so that the component proportion of a localized state (LE) in an excited triplet state of the cyclotetradentate platinum (II) complex is increased, the cyclotetradentate platinum (II) complex has low acromion, and the molecular luminescence color purity of the material is improved. The material provided by the invention has good chemical stability and thermal stability, and is easy to prepare an evaporation type OLED device. After being combined with a fluorescent doping material, the material can balance hole and electron transmission, so that energy transmission between a subject and an object is more efficient. The current efficiency and the service life of the organic electroluminescent device manufactured by using the compound as a luminescent layer are obviously improved, and the lighting voltage is obviously reduced. Especially, the photochromic purity of the device can be improved by jointly applying the compound and a phosphorescent sensitized boron-containing compound.

Description

Technical Field

[0001] The invention belongs to the field of organic electroluminescence, and specifically relates to a cyclic carbazole tetradentate 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. Moreover, 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 its annual production worldwide are both about ten times that of metallic iridium. The price of IrCl3·H2O used to prepare iridium (III) complex phosphorescent materials is also much higher than that of PtCl2 used to prepare platinum (II) complex phosphorescent materials. In addition, the preparation of iridium (III) complex phosphorescent materials involves four steps of reactions, including iridium (III) dimer, iridium (III) intermediate ligand exchange, synthesis of mer-iridium (III) complex, and conversion of mer- to fac-iridium (III) complex isomers, which greatly reduces the total yield, greatly reduces the utilization rate of the raw material IrCl3.H2O, and increases the preparation cost of iridium (III) complex phosphorescent materials. In contrast, the preparation of platinum (II) complex phosphorescent materials only involves the last step of ligand metallization reaction of designed platinum salt, with high utilization of platinum, which can further reduce the preparation cost of platinum (II) complex phosphorescent materials.

[0004] In summary, the preparation cost of platinum (II) complex phosphorescent materials is much lower than that of iridium (III) complex phosphorescent materials. In addition, how to reduce the height of the shoulder peak in the emission spectrum to improve the color purity of the luminescence of the material molecules? This problem is especially important for blue and deep blue light emitting materials because they have a great impact on the efficiency and energy utilization of commercial top-emitting devices. 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

[0005] In view of this, the purpose of the present invention is to provide a tetradentate metal platinum (II) complex of a cyclic carbazole. The tetradentate metal platinum (II) complex of the present invention is used as a light-emitting layer to prepare an organic electroluminescent device, which can make the device have excellent performance. It can improve the current efficiency of the organic electroluminescent device, improve the device life, and also reduce the operating voltage of the component.

[0006] To achieve the above technical objectives, the technical solution of the present invention is as follows:

[0007] The present invention provides a tetradentate metal platinum (II) complex of a cyclic carbazole having a general structure as shown in formula (I) to formula (V):

[0008]

[0009]

[0010] In formula (I) to formula (V), X is selected from C, O or S; R 1 -R 9 Each independently represents a single substitution to the maximum amount of substitution, or no substitution; R 1 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, halogen, CN, C1-C30 alkyl, C1-C30 deuterated alkyl, C1-C30 haloalkyl, C1-C30 cycloalkyl, C1-C30 heterocycloalkyl, C6-C60 aryl or condensed aromatic hydrocarbon group, C6-C60 heteroaryl or condensed heteroaromatic hydrocarbon group, C6-C60 aromatic amine group and combinations thereof; when containing heteroatoms, the heteroatoms are selected from N and O.

[0011] Furthermore, R 1 , R 6 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, phenyl and combinations thereof.

[0012] Preferably, R 1 , R 6 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, and combinations thereof.

[0013] Furthermore, R 2 -R 5Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, CF3, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, naphthyl, pyridyl, quinolyl, cyclopentane, cyclohexane, a five-membered heterocycle, diphenylamine, and combinations thereof.

[0014] Preferably, the tetradentate metal platinum (II) complex of cyclic carbazole is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031] Furthermore, the present invention also provides the use of the above cyclic carbazole tetradentate metal platinum (II) complex having the structures shown in formula (I) to formula (V) in electronic devices.

[0032] 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).

[0033] In another aspect, the present invention further provides an organic electroluminescent device, which comprises the above-mentioned cyclic carbazole tetradentate metal platinum (II) complex having the structure shown in formula (I) to formula (V).

[0034] Furthermore, the organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises the above-mentioned cyclic carbazole tetradentate metal platinum (II) complex having structures shown in formula (I) to formula (V).

[0035] Preferably, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the above-mentioned cyclic carbazole tetradentate metal platinum (II) complex having the structure represented by formula (I) to formula (V).

[0036] Furthermore, the light-emitting layer further comprises a fluorescent doping material; the fluorescent doping material is preferably a boron-containing organic molecular light-emitting material.

[0037] In another aspect, the present invention also provides an organic photoelectric device, which comprises: a substrate layer; a first electrode, which is on the substrate; an organic light-emitting functional layer, which is on the first electrode; a second electrode, which is on the organic light-emitting functional layer; wherein the organic light-emitting functional layer comprises a tetradentate metal platinum (II) complex of a cyclic carbazole having a structure shown in formula (I) as above. For example, the platinum (II) complex can be included in the organic light-emitting functional layer as a light-emitting material.

[0038] Furthermore, the organic light-emitting functional layer further comprises any one or more fluorescent doping materials, and the fluorescent doping material is preferably a boron-containing organic molecular light-emitting material, and is preferably a phosphorescence-sensitized boron-containing compound.

[0039] In the present invention, the organic photoelectric device can be prepared by evaporating metal or conductive oxides and their alloys on a substrate to form an anode by using a method such as sputtering coating, electron beam evaporation, vacuum evaporation, etc.; a hole injection layer, a hole transport layer, a light-emitting layer, an air blocking layer and an electron transport layer are sequentially evaporated on the surface of the prepared anode, and then a cathode is evaporated. In addition to the above method, an organic electroluminescent device is prepared by evaporating a cathode, an organic layer and an anode on a substrate in sequence. The organic layer can also include a multilayer structure such as a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer and an electron transport layer. In the present invention, the organic layer is prepared by using a polymer material according to solvent engineering (spin-coating, tape-casting, doctor-blading, screen-printing, inkjet printing or thermal-imaging, etc.) instead of the evaporation method, which can reduce the number of device layers.

[0040] The present invention also provides a composition, which comprises a tetradentate metal platinum (II) complex of a cyclic carbazole having a structure shown in formula (I) to formula (V) as above. Preferably, the composition further comprises a fluorescent doping material, and the fluorescent doping material is preferably a boron-containing organic molecular luminescent material, preferably a phosphorescently sensitized boron-containing compound.

[0041] The present invention also provides a preparation, which comprises the above-mentioned cyclic carbazole tetradentate metal platinum (II) complex having the structure shown in formula (I) to formula (V) or the above-mentioned composition and at least one solvent.

[0042] 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.

[0043] The present invention also provides a display or lighting device, which comprises one or more of the organic photoelectric devices described above.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] The present invention provides a method of introducing benzofuran or benzothiophene system at different positions of carbazole to increase the component ratio of localized state (LE) in excited triplet state of cyclotetradentate platinum (II) complex, so that it has a low shoulder peak and improves the luminescent color purity of material molecules. The materials involved in the present invention have good chemical stability and thermal stability, and are easy to prepare vapor deposition type OLED devices. After being combined with fluorescent doping materials, the transmission of holes and electrons can be balanced, making the energy transfer between the host and the guest more efficient. The organic electroluminescent device made by using the compound of the present invention as the light-emitting layer has obvious improvement in current efficiency and life, and significantly reduces the light-on voltage. In particular, the light color purity of the device can be improved by using it together with phosphorescence sensitized boron-containing compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 It is the room temperature emission spectrum of Pt150 and R1 in dichloromethane solution;

[0047] Figure 2 This is the room temperature emission spectrum of Pt162 and R1 in dichloromethane solution;

[0048] Figure 3 This is the room temperature emission spectrum of Pt166 and R1 in dichloromethane solution. DETAILED DESCRIPTION

[0049] 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.

[0050] 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).

[0051] In defining various terms, “R 1 ”-“R 9" 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.

[0052] 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.

[0053] 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.

[0054] The compounds disclosed herein can exhibit desired properties and have emission and / or absorption spectra that can be adjusted by selecting appropriate ligands. On the other hand, the present invention can exclude any one or more compounds, structures or portions thereof specifically described herein. The compounds of the present invention can be prepared using a variety of methods, including but not limited to those described in the examples provided herein.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] Synthesis Example

[0059] 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 done separately, the temperature is 25°C, or room temperature, and the pressure is close to normal pressure.

[0060] 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.

[0061] 1 H NMR (500MHz), 1 H NMR (400MHz), 13 C NMR (126 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. 1 When CDCl3 is used as the solvent, TMS (δ=0.00 ppm) is used as the internal standard in the HNMR spectrum; 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.

[0062] Synthetic route

[0063] Example 1: Tetradentate metal platinum (II) complex phosphorescent material Pt150

[0064] The synthetic route is as follows:

[0065]

[0066] Synthesis of intermediate dBr-tBuNH2: Add p-tert-butylaniline (15.0 g, 100 mmol, 1.0 equivalent) and dichloromethane (150 mL) to the reaction flask to dissolve N-bromosuccinimide (37.7 g, 210 mmol, 2.1 equivalent), and react at room temperature for 48 hours. Concentrate and perform silica gel column chromatography to obtain 25.6 g of red liquid with a yield of 80%. Use it directly in subsequent reactions.

[0067] Synthesis of intermediate dBr-tBuNO2: Add dBr-tBuNH2 (5 g, 16.3 mmol, 1.0 equivalent) to a reaction flask and dissolve it in N-methylpyrrolidone (50 mL), add sodium hydride (1.96 g, 49 mmol, 3.0 equivalent), add o-fluoronitrobenzene (3.45 g, 24.5 mmol, 1.5 equivalent), react at room temperature for 48 hours and stop the reaction. Concentrate and silica gel column chromatography to obtain 5.08 g of yellow solid, with a yield of 70%. Use it directly in subsequent reactions.

[0068] Synthesis of intermediate dBr-tBu2NH2: Add dBr-tBuNO2 (4.8 g, 11.2 mmol, 1.0 equivalent), stannous chloride (10.1 g, 44.8 mmol, 4.0 equivalent) to the reaction bottle, add ethyl acetate (50 mL) and ethanol (50 mL). ℃ The reaction was stopped after 24 hours, cooled to room temperature, concentrated, and subjected to silica gel column chromatography to obtain 3.43 g of a white solid with a yield of 90%, which was directly used in subsequent reactions.

[0069] Synthesis of intermediate dPh-tBuNH2: Add dBr-tBu2NH2 (3.2 g, 8 mmoL, 1.0 equivalent), phenylboronic acid (2.93 g, 24 mmoL, 3.0 equivalent), tetrakis(triphenylphosphine)palladium (185 mg, 0.16 mmoL, 0.02 equivalent), sodium carbonate (2.8 g, 20 mmoL, 2.5 equivalent), dioxane (40 mL) and water (15 mL) to the reaction flask. After reacting at 90°C for 24 hours, stop the reaction, cool to room temperature, concentrate, and obtain 2.66 g of white solid by silica gel column chromatography, with a yield of 90%. 1 H NMR(500MHz,DMSO)δ1.35(s,9H),4.4 4(s,2H),5.57(s,1H),6.05(dd,J=8.0,1.5Hz,1H),6.12(td,J=7.5,1.5Hz,1H),6.25(td,J=7.6,1.5Hz,1 H),6.31(dd,J=7.5,1.5Hz,1H),7.20–7.16(m,2H),7.25(t,J=7.5Hz,4H),7.28(s,2H),7.43–7.41(m,4H).

[0070]

[0071] Synthesis of intermediate 1O-NO2: Add A1 (13.55 g, 63.9 mmoL, 1.5 equivalents), B (8 g, 42.6 mmoL, 1.0 equivalents), tetrakis(triphenylphosphine)palladium (1.47 g, 1.28 mmoL, 3 mol%), and potassium carbonate (11.78 g, 85.2 mmoL, 2.0 equivalents) to a reaction flask, and add dioxane (80 mL) and water (20 mL). The reaction was stopped at 90°C for 24 hours, cooled to room temperature, concentrated, and subjected to silica gel column chromatography to obtain 10 g of a yellow solid with a yield of 74%. 1 H NMR (400MHz, DMSO-d6) δ3.97(s,3H),6.97(d,J=7.2Hz,1H),7.20(td,J=7.6,0.8Hz,2H),7.46–7.51(m,2H),7.56–7.60(m,2H),7.72–7.77(m,3H).

[0072] Synthesis of intermediate 1O-NH: Add 1O-NO2 (10 g, 31.3 mmol, 1.0 equivalent) and triphenylphosphine (32.84 g, 125.2 mmol, 3.0 equivalent) to a reaction flask, and add o-dichlorobenzene (60 mL). React at 110 ° C for 24 hours, cool to room temperature, concentrate, and obtain 6.89 g of brown solid by silica gel column chromatography, with a yield of 78%. Use it directly in subsequent reactions.

[0073] Synthesis of intermediate 1O-OMe: 1O-NH (5.3 g, 18.4 mmoL, 1.0 equivalent), 4-(tert-butyl)-2-chloropyridine (4.05 g, 23.9 mmoL, 1.3 equivalent), tris(dibenzylideneacetone)dipalladium (673 mg, 1.10 mmoL, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (JohnPhos) (603 mg, 2.2 mmoL, 6 mol%) and sodium tert-butoxide (3.54 g, 36.8 mmoL, 2.0 equivalent) were added to a reaction bottle, and toluene (50 mL) was added. The reaction was stopped in an oil bath at 110°C for 48 hours, cooled to room temperature, concentrated, and subjected to silica gel column chromatography to obtain 6.59 g of brown solid with a yield of 85%. It was directly used for subsequent reactions.

[0074] Synthesis of intermediate 1O-OH: Add 1O-OMe (6 g, 14.3 mmol, 1.0 equivalent), pyridine hydrochloride (16.53 g, 143 mmol, 10.0 equivalent) and 1,3-dimethyl-2-imidazolidinone (60 mL) to the reaction bottle. React in an oil bath at 180°C for 48 hours, cool to room temperature, concentrate, and obtain 5.43 g of brown solid by silica gel column chromatography with a yield of 88%. Use it directly in subsequent reactions.

[0075] Synthesis of intermediate tBu-1O-Cl: 1O-OH (1.6 g, 3.9 mmoL, 1.0 equivalent), 3-chloro-5-bromo tert-butylbenzene (1.25 g, 5.1 mmoL, 1.3 equivalent), 2-pyridinecarboxylic acid (96 mg, 0.78 mmoL, 20 mmoL%), cuprous iodide (74 mg, 0.39 mmoL, 10 mmoL%), and potassium phosphate (1.66 g, 7.8 mmoL, 2.0 equivalent) were added to the reaction flask, and dimethyl sulfoxide (10 mL) was added. The reaction was stopped at 100°C for 12 hours, cooled to room temperature, concentrated, and silica gel column chromatography was performed to obtain 566 mg of a white solid with a yield of 65%. 1 H NMR (500MHz, DMSO) δ1.24(s,9H),1.31(s,9H),6.99(t,J=2.0Hz,1H),7.15(t,J=2. 0Hz,1H),7.22–7.26(m,2H),7.30(d,J=2.5Hz,1H),7.54(dd,J=5.5,1.5Hz,1H),7.6 3–7.67(m,1H),7.58–7.61(m,1H),7.70(d,J=2.0Hz,1H),7.83–7.86(m,2H),7.91(d ,J=9.0Hz,1H),8.63(d,J=5.0Hz,1H),8.75(d,J=7.5Hz,1H),8.80(d,J=8.5Hz,1H).

[0076]

[0077] Synthesis of intermediate LNH-150: Add dPh-tBuNH2 (411 mg, 1.04 mmoL, 1.3 equivalents), tBu-1O-Cl (460 mg, 0.8 mmoL, 1.0 equivalents), tris(dibenzylideneacetone)dipalladium (22 mg, 0.03 mmoL, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (20 mg, 0.05 mmoL, 6 mol%) and sodium tert-butoxide (153 mg, 1.6 mmoL, 2.0 equivalents) to the reaction bottle, and add toluene (5 mL). The reaction was stopped at 85°C for 3 hours, cooled to room temperature, concentrated, and silica gel column chromatography to obtain 631 mg of a white solid with a yield of 85%. It was directly used for subsequent reactions.

[0078] Synthesis of ligand L-150: Add LNH-150 (631 mg, 0.68 mmol, 1.0 equivalent) to a reaction bottle, then add ammonium hexafluorophosphate (221 mg, 1.4 mmol, 2.0 equivalent) and triethyl orthoformate (5 mL). React at 80°C for 2 hours, cool to room temperature, concentrate, and perform silica gel column chromatography to obtain 435 mg of a white solid with a yield of 61%. 1 H NMR (500MHz, DMSO) δ1.28(s,9H),1.31(s,9H),1.43(s,9H),6.91(t,J=2.2Hz,1H),6.99(t,J =1.8Hz,1H),7.10–7.18(m,11H),7.33(dd,J=9.0,2.5Hz,1H),7.46–7.50(m,2H),7.52–7.57 (m,4H),7.59–7.62(m,1H),7.64–7.72(m,4H),7.75(s,1H),7.86–7.90(m,2H),7.93(d,J=9. 0Hz,1H),8.64(d,J=5.0Hz,1H),8.77(d,J=7.0Hz,1H),8.88(d,J=9.0Hz,1H),10.27(s,1H).

[0079] Synthesis of Pt150: Add L-150 (200 mg, 0.19 mmoL, 1.0 equivalent), (1,5-cyclooctadiene) platinum (II) dichloride (75 mg, 0.20 mmoL, 1.05 equivalent) and sodium acetate (47 mg, 0.57 mmoL, 3.0 equivalent) to a reaction flask, and add diethylene glycol dimethyl ether (10 mL). React at 120°C for 72 hours, cool to room temperature, concentrate, and obtain 250 mg of a light yellow solid by silica gel column chromatography, with a yield of 80%. 1H NMR(500MHz, CDCl3)δ1.20(s,9H),1.44(s,9H),1.47(s,9H),6.06–6.82(m,7H),6 .92(d,J=8.5Hz,1H),7.05(t,J=7.5Hz,1H),7.15–7.18(m,2H),7.24–7.48(m,4H) ,7.54–7.75(m,8H),7.93(d,J=2.0Hz,1H),7.98(d,J=8.5Hz,1H),8.03(d,J=9.0H z,1H),8.41(d,J=8.5Hz,1H),8.75(dd,J=7.0,4.0Hz,1H),9.07(d,J=6.5Hz,1H).

[0080] Example 2: Tetradentate metal platinum (II) complex phosphorescent material Pt166

[0081] The synthetic route is as follows:

[0082]

[0083] Synthesis of intermediate 2O-NO2: Add A2 (25 g, 119.9 mmoL, 1.5 equivalents), B (15 g, 79.7 mmoL, 1.0 equivalents), tetrakis(triphenylphosphine)palladium (2.77 g, 2.4 mmoL, 3 mol%), potassium carbonate (22.1 g, 159.9 mmoL, 2.0 equivalents), dioxane (160 mL) and water (40 mL) to the reaction flask. The reaction was stopped at 90°C for 12 hours, cooled to room temperature, concentrated, and subjected to silica gel column chromatography to obtain 19 g of a yellow solid with a yield of 76%, which was directly used in subsequent reactions.

[0084] Synthesis of intermediate 2O-NH: Add 2O-NO2 (19 g, 61.1 mmol, 1.0 equivalent) and triphenylphosphine (48.1 g, 183.4 mmol, 3.0 equivalent) and o-dichlorobenzene (60 mL) to a reaction flask. React at 180°C for 11 hours, cool to room temperature, concentrate, and obtain 10.5 g of brownish white solid by silica gel column chromatography, with a yield of 61%. 1 H NMR(400MHz, DMSO-d6)δ3.89(s,3H),6.88(dd,J=8.4,2.4Hz,1H),7.12(d,J=2.4Hz,1H),7.48–7.54(m, 3H),7.74–7.77(m,1H),8.07(d,J=8.4Hz,1H),8.17(d,J=8.4Hz,1H),8.59–8.61(m,1H),11.95(s,1H).

[0085] Synthesis of intermediate 2O-OMe: Add 2O-NH (10 g, 34.8 mmoL, 1.0 equivalent), 4-(tert-butyl)-2-chloropyridine (7.67 g, 45.2 mmoL, 1.3 equivalent), tris(dibenzylideneacetone)dipalladium (1.27 g, 1.4 mmoL, 4 mol%), 2-(di-tert-butylphosphine)biphenyl (830 mg, 2.8 mmoL, 8 mol%) and sodium tert-butoxide (6.69 g, 69.6 mmoL, 2.0 equivalent) to a reaction bottle, and add toluene (100 mL). The reaction was stopped at 110°C for 11 hours, cooled to room temperature, concentrated, and silica gel column chromatography to obtain 10 g of a white solid with a yield of 72%. It was directly used for subsequent reactions.

[0086] Synthesis of intermediate 2O-OH: Add 2O-OMe (566 mg, 1.35 mmoL, 1.0 equivalent), pyridine hydrochloride (1.56 g, 13.5 mmoL, 10.0 equivalent) and 1,3-dimethyl-2-imidazolidinone (6 mL) to the reaction bottle. After reacting at 180°C for 18 hours, stop the reaction, cool to room temperature, concentrate, and obtain 493 mg of white solid by silica gel column chromatography with a yield of 90%. Use it directly in subsequent reactions.

[0087] Synthesis of intermediate tBu-2O-Cl: Add 2O-OH (343 mg, 0.84 mmoL, 1.0 equivalent), 3-chloro-5-bromo tert-butylbenzene (272 mg, 1.1 mmoL, 1.3 equivalent), 2-pyridinecarboxylic acid (21 mg, 0.17 mmoL, 20 mmoL%), cuprous iodide (16 mg, 0.08 mmoL, 10 mmoL%), potassium phosphate (356 mg, 1.7 mmoL, 2.0 equivalent) and dimethyl sulfoxide (5 mL) to the reaction bottle. After reacting in an oil bath at 110°C for 12 hours, the reaction was stopped, cooled to room temperature, concentrated, and silica gel column chromatography was performed to obtain 418 mg of a white solid with a yield of 86%. It was directly used for subsequent reactions.

[0088]

[0089] Synthesis of intermediate LNH-166: Add dPh-tBuNH2 (211 mg, 0.54 mmoL, 1.2 equivalents) to the reaction bottle, then add tBu-2O-Cl (256 mg, 0.45 mmoL, 1.0 equivalents), tris(dibenzylideneacetone)dipalladium (24.7 mg, 0.03 mmoL, 6 mol%), 2-(di-tert-butylphosphine)biphenyl (16 mg, 0.05 mmoL, 12 mol%) and sodium tert-butoxide (129 mg, 1.3 mmoL, 3.0 equivalents), and add toluene (5 mL). After reacting at 85°C for 3 hours, stop the reaction, cool to room temperature, concentrate, and obtain 250 mg of green solid by silica gel column chromatography, with a yield of 60%, which is directly used in subsequent reactions.

[0090] Synthesis of ligand L-166: Add LNH-166 (237 mg, 0.26 mmol, 1.0 equivalent) to a reaction bottle, then add ammonium hexafluorophosphate (84.8 mg, 0.52 mmol, 2.0 equivalent) and triethyl orthoformate (5 mL). React at 75°C for 25 minutes, then stop the reaction, cool to room temperature, concentrate, and perform silica gel column chromatography to obtain 180 mg of a white solid with a yield of 75%.

[0091] Synthesis of Pt166: Add L-166 (27 mg, 0.025 mmoL, 1.0 equivalent) to the reaction flask, then add (1,5-cyclooctadiene) platinum (II) dichloride (10 mg, 0.026 mmoL, 1.05 equivalent) and sodium acetate (6.15 mg, 0.075 mmoL, 3.0 equivalent), and add diethylene glycol dimethyl ether (3 mL). After reacting at 120°C for 72 hours, stop the reaction, cool to room temperature, concentrate, and obtain 18 mg of light yellow solid by silica gel column chromatography, with a yield of 80%. 1 H NMR(500MHz,DMSO)δ0.78(s,9H),1.43(s,9H),1.58(s,9H),6.49(t,J=8.0Hz,2H),6.66(t,J=7 .5Hz,1H),6.81(dd,J=6.0,2.0Hz,1H),6.95–7.0(m,5H),7.14(d,J=2.0Hz,1H),7.20(td,J=7.5 ,3.0Hz,2H),7.26–7.37(m,5H),7.46(d,J=2.5Hz,1H),7.55(d,J=1.5Hz,1H),7.59(d,J=7.0Hz, 2H),7.65(t,J=6.0Hz,1H),8.13(d,J=8.5Hz,1H),8.43(d,J=8.0Hz,1H),9.08(d,J=6.0Hz,1H).

[0092] Example 3: Tetradentate metal platinum (II) complex phosphorescent material Pt162

[0093] The synthetic route is as follows:

[0094]

[0095] Synthesis of intermediate 3O-NO2: Add A3 (10 g, 43.8 mmoL, 1.5 equivalents), B (6.2 g, 29.2 mmoL, 1.0 equivalents), tetrakis(triphenylphosphine)palladium (1.01 g, 0.88 mmoL, 3 mol%), potassium carbonate (8.07 g, 58.4 mmoL, 2.0 equivalents), dioxane (60 mL) and water (15 mL) to a reaction flask. React at 90°C for 24 hours, cool to room temperature, concentrate, and obtain 7.34 g of a yellow solid by silica gel column chromatography, with a yield of 79%. 1 H NMR (500MHz, DMSO-d6) δ3.91(s,3H),7.30(dd,J=7.5,1.5Hz,1H),7.38(dd,J=8.5,2.5Hz,1H),7.44(td,J=7.5 ,0.5Hz,1H),7.59–7.61(m,2H),7.56(m,1H),7.69(d,J=1.0Hz,1H),7.73(d,J=8.0Hz,1H),8.18–8.20(m,2H).

[0096] Synthesis of intermediate 3O-NH: Add 3O-NO2 (7.3 g, 30.6 mmol, 1.0 equivalent) and triphenylphosphine (24.1 g, 91.8 mmol, 3.0 equivalent) and o-dichlorobenzene (60 mL) to a reaction flask. React at 180°C for 24 hours, cool to room temperature, concentrate, and obtain 6.03 g of brown solid by silica gel column chromatography, with a yield of 76%. Use it directly in subsequent reactions.

[0097] Synthesis of intermediate 3O-OMe: Add 3O-NH (4.8 g, 16.7 mmoL, 1.0 equivalent), 4-(tert-butyl)-2-chloropyridine (3.68 g, 21.7 mmoL, 1.3 equivalent), tris(dibenzylideneacetone)dipalladium (421 mg, 1.00 mmoL, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (822 mg, 2.0 mmoL, 6 mol%) and sodium tert-butoxide (3.2 g, 33.4 mmoL, 2.0 equivalent) to a reaction bottle, and add toluene (50 mL). The reaction was stopped at 110°C for 48 hours, cooled to room temperature, concentrated, and silica gel column chromatography to obtain 4.92 g of brown solid with a yield of 72%. It was directly used for subsequent reactions.

[0098] Synthesis of intermediate 3O-OH: Add 3O-OMe (4.9 g, 6.7 mmoL, 1.0 equivalent), pyridine hydrochloride (7.74 g, 67 mmoL, 10.0 equivalent), and 1,3-dimethyl-2-imidazolidinone (60 mL) to the reaction bottle. React at 180°C for 48 hours, cool to room temperature, concentrate, and obtain 3.4 g of brown solid by silica gel column chromatography with a yield of 87%. Use it directly in subsequent reactions.

[0099] Synthesis of intermediate tBu-3O-Cl: 3O-OH (1.0 g, 2.5 mmoL, 1.0 equivalent), 3-chloro-5-bromo tert-butylbenzene (804 mg, 3.25 mmoL, 1.3 equivalent), 2-picolinic acid (62 mg, 0.5 mmoL, 20 mmoL%), cuprous iodide (48 mg, 0.25 mmoL, 10 mmoL%), potassium phosphate (1.06 g, 5 mmoL, 2.0 equivalent), and dimethyl sulfoxide (10 mL) were added to the reaction bottle. The reaction was stopped at 100°C for 24 hours, cooled to room temperature, concentrated, and subjected to silica gel column chromatography to obtain 590 mg of a white solid with a yield of 68%. 1 HNMR(500MHz,DMSO)δ1.24(s,9H),1.37(s,9H),6.87(t,J=2.5Hz,1H),7.11(t,J=2.0Hz,1H),7 .14(dd,J=8.5,2.0Hz,1H),7.19(t,J=1.5Hz,1H),7.44(td,J=7.2,1.5Hz,1H),7.52–7.48(m,2H ),7.55(dd,J=5.5,2.0Hz,1H),7.58(d,J=2.0Hz,1H),7.80(d,J=2.0Hz,1H),8.12(d,J=8.5Hz, 1H), 8.24 (d, J = 7.5Hz, 1H), 8.30 (d, J = 8.0Hz, 1H), 8.38 (d, J = 8.5Hz, 1H), 8.57 (d, J = 4.5Hz, 1H).

[0100]

[0101] Synthesis of intermediate LNH-162: Add dPh-tBuNH2 (300 mg, 0.76 mmoL, 1.0 equivalent) to the reaction bottle, then add tBu-3O-Cl (458 mg, 0.8 mmoL, 1.05 equivalent), tris(dibenzylideneacetone)dipalladium (21 mg, 0.03 mmoL, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (14 mg, 0.06 mmoL, 6 mol%) and sodium tert-butoxide (146 mg, 1.5 mmoL, 2.0 equivalent), and add toluene (5 mL). React at 85°C for 3 hours to stop the reaction, cool to room temperature, concentrate, and obtain 271 mg of white solid by silica gel column chromatography, with a yield of 50%. Use it directly in subsequent reactions.

[0102] Synthesis of ligand L-162: Add LNH-162 (271 mg, 0.29 mmol, 1.0 equivalent) to a reaction bottle, then add ammonium hexafluorophosphate (94 mg, 0.58 mmol, 2.0 equivalent) and triethyl orthoformate (5 mL). After reacting at 80°C for 2 hours, stop the reaction, cool to room temperature, concentrate, and perform silica gel column chromatography to obtain 197 mg of a white solid with a yield of 63%. 1 H NMR (500MHz, DMSO) δ1.31 (s, 9H), 1.36 (s, 9H), 1.43 (s, 9H), 6.81 (t, J = 2.0Hz, 1H), 6. 95(t,J=1.5Hz,1H),7.11–7.16(m,10H),7.24(dd,J=8.5,2.5Hz,1H),7.44–7.58(m,8H ),7.72–7.75(m,4H),7.83(d,J=1.5Hz,1H),8.15(d,J=8.5Hz,1H),8.25(d,J=7.5Hz,1 H),8.35(d,J=8.0Hz,1H),8.46(d,J=8.5Hz,1H),8.58(d,J=5.5Hz,1H),10.24(s,1H).

[0103] Synthesis of Pt162: Add L-162 (153 mg, 0.15 mmoL, 1.0 equivalent), (1,5-cyclooctadiene) platinum (II) dichloride (55 mg, 0.16 mmoL, 1.05 equivalent) and sodium acetate (37 mg, 0.45 mmoL, 3.0 equivalent) to a reaction flask, and add diethylene glycol dimethyl ether (10 mL). React at 120 ° C for 72 hours, cool to room temperature, concentrate, and obtain 138 mg of light yellow solid by silica gel column chromatography, with a yield of 78%. 1H NMR (500MHz, CDCl3) δ1.13(s,9H),1.47(s,9H),1.53(s,9H),6.22(t,J=7.5Hz,2H),6.37(dd,J=6.0,1.5Hz,1H),6.48 (t,J=2.5Hz,1H),6.69(d,J=6.5Hz,2H),6.94(d,J=7.0Hz,1H),7.07–7.02(m,1H),7.12(d,J=1.5Hz,1H),7.21–7.25(m ,2H),7.28–7.32(m,2H),7.35–7.39(m,2H),7.44–7.51(m,4H),7.54(d,J=1.5Hz,1H),7.61(d,J=7.5Hz,2H),7.70(s, 1H),7.86(d,J=8.0Hz,1H),7.99(d,J=8.5Hz,1H),8.06(d,J=8.0Hz,1H),8.12(d,J=8.0Hz,2H),9.04(d,J=6.0Hz,1H).

[0104] Example 4: Tetradentate metal platinum (II) complex phosphorescent material Pt6

[0105] The synthetic route is as follows:

[0106]

[0107] Pt6 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product LNH-6 was synthesized, 680 mg of light green foamy solid, with a yield of 59%. The target product L-6 was synthesized, 377 mg of light green foamy solid, with a yield of 58%. Molecular weight [M] + :883.4. The target product Pt6 was synthesized as a yellow solid (180 mg) with a yield of 60%. Molecular weight [M+H] + :1076.3.

[0108] Example 5: Tetradentate metal platinum (II) complex phosphorescent material Pt13

[0109] The synthetic route is as follows:

[0110]

[0111] Pt13 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product LNH-13 was synthesized, 900g of light green foamy solid, with a yield of 64%. The target product L-13 was synthesized, 423mg of light green foamy solid, with a yield of 58%. Molecular weight [M] +:827.3. The target product Pt13 was synthesized as a yellow solid 30 mg with a yield of 26%. Molecular weight [M+H] + :1020.33.

[0112] Example 6: Tetradentate metal platinum (II) complex phosphorescent material Pt14

[0113] The synthetic route is as follows:

[0114]

[0115] Pt14 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product LNH-14 was synthesized, 1.5 g of light green foamy solid, with a yield of 70%. The target product L-14 was synthesized, 800 mg of light green foamy solid, with a yield of 62%. Molecular weight [M] + :883.4. The target product Pt14 was synthesized as a yellow solid 346 mg, with a yield of 59%. Molecular weight [M+H] + :1076.3.

[0116] Example 7: Tetradentate metal platinum (II) complex phosphorescent material Pt-154

[0117] The synthetic route is as follows:

[0118]

[0119] Pt154 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product LNH-154 was synthesized, 1.1 g of light green foamy solid, with a yield of 60%. The target product L-154 was synthesized, 504 mg of light green foamy solid, with a yield of 63%. Molecular weight [M] + :939.5. The target product Pt154 was synthesized as a yellow solid 178 mg. Yield 78%. Molecular weight [M+H] + :1132.4.

[0120] Example 8: Tetradentate metal platinum (II) complex phosphorescent material Pt197

[0121] The synthetic route is as follows:

[0122]

[0123] Pt197 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product LNH-197 was synthesized, 2.4 g of light green foamy solid, with a yield of 50%. The target product L-197 was synthesized, 1 g of light green foamy solid, with a yield of 60%. Molecular weight [M] +:843.3. The target product Pt197 was synthesized as a yellow solid 210 mg with a yield of 23%. Molecular weight [M+H] + :1036.3.

[0124] Example 9: Synthesis of Pt26

[0125] Pt26 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product Pt26 was obtained as a yellow solid (530 mg) with a yield of 58%. Molecular weight [M+H] + :1215.5.

[0126] Example 10: Synthesis of Pt63

[0127] Pt63 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product Pt63 was obtained as a yellow solid (432 mg) with a yield of 70%. Molecular weight [M+H] + :1264.5.

[0128] Example 11: Synthesis of Pt76

[0129] Pt76 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (801 mg) with a yield of 65%. Molecular weight [M+H] + :1474.7.

[0130] Example 12: Synthesis of Pt230

[0131] Pt230 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-162. The target product Pt230 was obtained as a yellow solid (56 mg) with a yield of 40%. Molecular weight [M+H] + :1510.7.

[0132] Example 13: Synthesis of Pt237

[0133] Pt237 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid of 730 mg with a yield of 43%. Molecular weight [M+H] + :1342.5.

[0134] Example 14: Synthesis of Pt244

[0135] Pt244 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid of 530 mg with a yield of 52%. Molecular weight [M+H] + :1490.6.

[0136] Example 15: Synthesis of Pt252

[0137] Pt252 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product Pt252 was obtained as a yellow solid (121 mg) with a yield of 61%. Molecular weight [M+H] + :1399.6.

[0138] Example 16: Synthesis of Pt257

[0139] Pt257 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product Pt257 was obtained as a yellow solid (158 mg) with a yield of 30%. Molecular weight [M+H] + :1260.4.

[0140] Example 17: Synthesis of Pt258

[0141] Pt258 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product Pt258 was obtained as a yellow solid (188 mg) with a yield of 60%. Molecular weight [M+H] + :1343.5.

[0142] Example 18: Synthesis of Pt263

[0143] Pt263 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. 472 mg of the target product was obtained as a yellow solid with a yield of 50%. Molecular weight [M+H] + :1461.5.

[0144] Example 19: Synthesis of Pt264

[0145] Pt264 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid of 545 mg with a yield of 49%. Molecular weight [M+H] + :1461.5.

[0146] Example 20: Synthesis of Pt328

[0147] Pt328 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid of 571 mg with a yield of 45%. Molecular weight [M+H] + :1378.5.

[0148] Example 21: Synthesis of Pt333

[0149] Pt333 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (418 mg) with a yield of 47%. Molecular weight [M+H] + :1126.3.

[0150] Example 22: Synthesis of Pt362

[0151] Pt362 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid of 590 mg with a yield of 63%. Molecular weight [M+H] + :1414.7.

[0152] Example 23: Synthesis of Pt364

[0153] Pt364 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (518 mg) with a yield of 53%. Molecular weight [M+H] + :1490.7.

[0154] Example 24: Synthesis of Pt365

[0155] Pt365 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (459 mg) with a yield of 61%. Molecular weight [M+H] + :1283.4.

[0156] Example 25: Synthesis of Pt372

[0157] Pt372 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (480 mg) with a yield of 63%. Molecular weight [M+H] + :1413.6.

[0158] Example 26: Synthesis of Pt378

[0159] Pt378 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid of 556 mg with a yield of 52%. Molecular weight [M+H] + :1307.4.

[0160] Example 27: Synthesis of Pt383

[0161] Pt383 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (458 mg) with a yield of 47%. Molecular weight [M+H] + :1471.7.

[0162] Theoretical calculation instructions

[0163] Density functional theory (DFT) was used to optimize the molecular geometry in the ground state (S0). DFT calculations were performed using the B3LYP functional with the 6-31G(d) basis set for C, H, O, and N atoms and the LANL2DZ basis set for Pt atoms.

[0164] Table 1. Electrons and holes in the T1 excited state of some metal complexes of the present invention

[0165]

[0166]

[0167]

[0168] As can be seen from Table 1, the present invention introduces cyclization at different positions of carbazole, expands the conjugated system, increases the distribution of local excited states, lowers the emission shoulder peak, narrows the half-peak width, has higher color purity, and can meet the needs of blue light materials.

[0169] Photophysical properties:

[0170] Table 2. Photophysical properties of some complexes in dichloromethane solution

[0171] Complex Maximum emission wavelength Half peak width Pt162 474.4nm 24.4nm Pt150 481.6nm 36.2nm Pt166 462.2nm 18.6nm

[0172] Figure 1-Figure 3 These are the room temperature emission spectra of Pt150, Pt162, Pt166 and R1 in dichloromethane solution. Figure 1-Figure 3 As shown in Table 2, by comparing the room temperature emission spectra of the platinum complex in dichloromethane solution, the introduction of cyclization at different positions of carbazole expands the conjugated system and increases the distribution of local excited states, making the emission shoulder lower and the half-peak width narrower, with higher color purity. The maximum emission wavelength of the platinum complex Pt166 is 462.2nm and its half-peak width is 18.6nm.

[0173] Fabrication of OLED devices:

[0174] As a reference preparation method for a device embodiment, the present invention evaporates 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, 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.

[0175] 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) (the mass ratio of Pt150:HTH-85:ETH-45 is 10:60:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0176] Device Examples 2 to 27 and Comparative Example 1 were prepared using a structure similar to that of Device Example 1, except that Pt166, Pt162, Pt6, Pt13, Pt14, Pt154, Pt197, Pt26, Pt63, Pt76, Pt230, Pt237, Pt63, Pt76, Pt244, Pt313, Pt327, Pt333, Pt338, Pt362, Pt364, Pt365, Pt367, Pt372, Pt378, Pt380, and R1 were used to replace Pt150 in Device Example 1. The luminescence characteristics of the comparative examples and device examples prepared above were tested by standard methods and are shown in Table 2. The device structure involved is as follows: wherein P-4 is HATCN and ET-14 is BPyTP.

[0177]

[0178] Table 3. Device luminescence characteristics data table

[0179]

[0180]

[0181] It can be seen from Table 3 that compared with Comparative Example 1, Device Examples 1 to 27 prepared in the present application all show good device performance in terms of driving voltage, current efficiency and device life; in addition, the color purity of the device is also greatly improved. The improvement in the performance of each device example is based on the fact that the specific compound material of the present invention has a small emission shoulder peak and 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, device life and color purity while reducing the driving voltage. It shows that the compound provided by the present invention has certain commercial application value. 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.

[0182] In a preferred specific embodiment, the structure of device example 28 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) (the mass ratio of Pt150:BN1-8:HTH-85:ETH-45 is 10:1:59:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0183] Device Examples 29 to 34 were prepared using structures similar to those of Device Example 28, except that the platinum (II) complex and the boron-containing compound in Device Example 29 were replaced by the compounds listed in Table 4. The device structures involved are as follows, and the device structures and luminescence characteristics data are shown in

[0184] Table 4.

[0185]

[0186] Table 4. Device structure and luminescence characteristics data table

[0187]

[0188]

[0189] As can be seen from Table 4, 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. After adding boron-containing compounds to sensitize the device structure, the CIEy value can be further reduced, thereby improving the color purity of the device luminescence.

[0190] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A tetradentate metal platinum (II) complex of cyclic carbazole, characterized in that: The complex has a general structure as shown in formula (I) to formula (V): In formula (I) to formula (V), X is selected from C, O or S; R 1 -R 9 Each independently represents a single substitution to the maximum amount of substitution, or no substitution; R 1 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, halogen, CN, C1-C30 alkyl, C1-C30 deuterated alkyl, C1-C30 haloalkyl, C1-C30 cycloalkyl, C1-C30 heterocycloalkyl, C6-C60 aryl or condensed aromatic hydrocarbon group, C6-C60 heteroaryl or condensed heteroaromatic hydrocarbon group, C6-C60 aromatic amine group and combinations thereof; when containing heteroatoms, the heteroatoms are selected from N and O.

2. The tetradentate metal platinum (II) complex of cyclic carbazole according to claim 1, characterized in that: R 1 , R 6 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, phenyl and combinations thereof.

3. The tetradentate metal platinum (II) complex of cyclic carbazole according to claim 1, characterized in that: R 1 , R 6 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, and combinations thereof.

4. The tetradentate metal platinum (II) complex of cyclic carbazole according to claim 1, characterized in that: R 2 -R 5 Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, CF3, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, naphthyl, pyridyl, quinolyl, cyclopentane, cyclohexane, a five-membered heterocycle, diphenylamine, and combinations thereof.

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

6. Use of the tetradentate metal platinum (II) complex of the cyclic carbazole according to any one of claims 1 to 5 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.

7. 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 of the cyclic carbazole according to any one of claims 1 to 5.

8. 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 of the cyclic carbazole according to any one of claims 1 to 5.

9. The organic electroluminescent device according to claim 8, characterized in that: The light-emitting layer also contains a fluorescent doping material, and the fluorescent doping material is a boron-containing compound.

10. 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 of the cyclic carbazole according to any one of claims 1 to 5.

11. The organic optoelectronic device according to claim 10, characterized in that: The organic light-emitting functional layer further comprises a fluorescent doping material, and the fluorescent doping material is a boron-containing compound.

12. A composition, characterized in that The composition comprises the tetradentate metal platinum (II) complex of cyclic carbazole according to any one of claims 1 to 5.

13. A preparation, characterized in that The preparation comprises the tetradentate metal platinum (II) complex of cyclic carbazole according to any one of claims 1 to 5.

14. 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 7 to 9.

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