Fused-ring carbazole tetradentate platinum(II) complexes and their uses.

Abstract

SOLUTION: To relate to the field of organic electroluminescence, and specifically relate to fused-ring carbazole tetradentate platinum(II) complexes and uses thereof, and provide a phosphorescent material of tetradentate platinum(II) complex by introducing a five-membered heterocyclic ring system such as benzofuran or benzothiophene into the 5,6-positions of carbazole.EFFECT: A ratio of components excited to a localized triplet state (LE) by the cyclotetradentate platinum(II) complex is improved, and the purity of the emission color of the material molecules is improved. Furthermore, the service life of the device is improved. The materials provided in the present invention all have good chemical and thermal stability, making it easy to manufacture deposition-type OLED devices. The organic electroluminescence device manufactured using the compound of the present invention as the light-emitting layer has both obvious improvements in current efficiency and service life, and significantly reduces the light-emitting voltage.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention is in the field of organic electroluminescence, and in particular relates to fused ring carbazole tetradentate metal platinum(II) complexes and uses thereof. [Background technology]

[0002] Organic light-emitting diodes (OLEDs) are a next-generation full-color display and lighting technology. Compared to LCDs, which suffer from the drawbacks of slow response times, narrow viewing angles, the need for backlighting, and high energy consumption, OLEDs are self-contained light-emitting devices that do not require backlighting, saving energy. They also offer low driving voltages, fast response times, high resolution and contrast, wide viewing angles, and excellent low-temperature performance. OLED devices can be made thinner and flexible. Other advantages include low production costs, simple manufacturing processes, and the ability to produce large areas. Therefore, OLEDs have broad and promising applications in the fields of high-end electronics and aerospace. With gradual increases in investment, further research advancements, and upgrades in production equipment, OLEDs have a very broad range of applications and development prospects in the future.

[0003] The development of OLEDs is centered on the design and development of emissive materials. Currently applied OLED devices almost always use a host-guest emissive system mechanism in the emissive layer, i.e., a guest emissive material is doped into a host material. The host material typically has a larger energy content than the guest emissive material, and energy is transferred from the host material to the guest material, exciting the guest material to emit light. Commonly used organic phosphorescent guest materials are heavy metal atoms such as iridium(III), platinum(II), and palladium(II). 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 an organic material, they can efficiently transfer triplet energy from the emissive organic material to the guest phosphorescent material. However, mCBP has the advantage of easy hole transport but poor electron transport, resulting in poor hole transport in 2,6-mCPy, which leads to charge imbalance in the emissive layer and reduced device current efficiency. Currently, the only heavy metal phosphorescent organic complex molecules used are cyclometalated iridium(III) complex molecules, which are limited in number. The content of metallic platinum in the earth's crust and the global annual production volume are both approximately 10 times that of metallic iridium. The price of IrCl3·H2O, used to produce iridium(III) complex phosphorescent materials, is also much higher than that of PtCl2, used to produce platinum(II) complex phosphorescent materials. In addition, the four-step reaction process for producing iridium(III) complex phosphorescent materials—including iridium(III) dimer incorporation, iridium(III) intermediate ligand exchange, mer-iridium(III) complex synthesis, and isomer conversion from mer- to fac-iridium(III) complex—significantly reduces the overall yield, significantly reduces the utilization rate of the raw material IrCl3·H2O, and increases the production cost of iridium(III) complex phosphorescent materials. In contrast, the production of platinum(II) complex phosphorescent materials only requires the final step of ligand metallization to engineer the reaction of platinum salts, resulting in a high utilization rate of platinum element, further reducing the production cost of platinum(II) complex phosphorescent materials.To summarize, the production cost of platinum(II) complex phosphorescent materials is much lower than that of iridium(III) complex phosphorescent materials. However, the development of current platinum complex materials and devices still faces several technical challenges. The problem of how to reduce the height of the shoulder peak in the emission spectrum to improve the color purity of the material molecules is particularly important for blue and deep blue emitting materials, because it significantly affects the efficiency and energy utilization rate of commercially applicable top-emitting devices. Therefore, the development of new phosphorescent metal platinum(II) complexes is highly desired. Summary of the Invention [Problem to be solved by the invention]

[0004] In view of the above, the present invention provides a fused-ring carbazole tetradentate platinum(II) complex and its use. The present invention introduces a five-membered heterocyclic ring system, such as benzofuran or benzothiophene, into the 5- and 6-positions of the carbazole ring, thereby increasing the proportion of triplet localized states (LEs) excited by the cyclotetradentate platinum(II) complex, providing a low shoulder peak and improving the purity of the emitted color of the material molecule. When the provided complex is used as an emissive layer in an organic electroluminescent device, the device can achieve excellent performance. It can improve the current efficiency of the organic electroluminescent device, extend the device's service life, and reduce the operating voltage of the component. [Means for solving the problem]

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

[0006] The present invention provides a fused ring carbazole tetradentate platinum(II) complex having a structure represented by formula (I). JPEG0007827785000001.jpg1928 (wherein X is selected from O or S, and R 1 ~R9 each independently represents mono-substitution to maximal substitution or no substitution; R 1 ~R 9 are each independently selected from the group consisting of hydrogen, deuterium, halogen, CN, a C1-C30 alkyl group, a C1-C30 haloalkyl group, a C1-C30 deuterated alkyl group, a C6-C60 aryl group, a C6-C60 arylsilane, and combinations thereof.

[0007] Furthermore, R 1 ~R 9 are each independently selected from the group consisting of hydrogen, deuterium, CD3, F, CF3, CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-amyl, 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, biphenyl, triphenylsilane, and combinations thereof.

[0008] Furthermore, R 3 , R 4 , R 9 are each independently selected from the group consisting of hydrogen, deuterium, F, CN, a methyl group, a tert-butyl group, a phenyl group, and combinations thereof.

[0009] Preferably, the fused ring carbazole tetradentate metal platinum(II) complex has any one of the following chemical structures, where "D" represents deuterium: JPEG0007827785000002.jpg9169JPEG0007827785000003.jpg9167JPEG0007827785000004.jpg8767JPEG0007827785 000005.jpg8667JPEG0007827785000006.jpg8563JPEG0007827785000007.jpg8767JPEG0007827785000008.jpg8665 JPEG0007827785000009.jpg8868JPEG0007827785000010.jpg8965JPEG0007827785000011.jpg8766JPEG0007827785 000012.jpg8870JPEG0007827785000013.jpg8968JPEG0007827785000014.jpg8668JPEG0007827785000015.jpg8568

[0010] Furthermore, the present invention further provides the use of a fused ring carbazole tetradentate metal platinum(II) complex having the structure represented by formula (I) as described above in an electronic device.

[0011] 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 photodetectors, organic photoreceptors, organic field-quenching devices (O-FQDs), light-emitting electrochemical cells (LECs), and organic laser diodes (O-lasers).

[0012] In another aspect, the present invention further provides an organic electroluminescent device comprising a fused ring carbazole tetradentate metal platinum(II) complex having the structure represented by formula (I), as shown above.

[0013] The organic electroluminescent device further comprises a cathode, an anode, and an organic functional layer interposed between the cathode and the anode, the organic functional layer containing a fused ring carbazole tetradentate metal platinum(II) complex having the structure represented by formula (I) as described above.

[0014] Preferably, the organic functional layer comprises a light-emitting layer containing a fused ring carbazole tetradentate metal platinum(II) complex having the structure represented by formula (I) as described above.

[0015] Furthermore, the light-emitting layer preferably further contains a fluorescent dopant material, and the fluorescent dopant material is preferably a boron-containing organic molecular light-emitting material.

[0016] In another aspect, the present invention provides an organic photovoltaic device, further comprising: a substrate layer; a first electrode on the substrate; an organic light-emitting functional layer on the first electrode, the organic light-emitting functional layer containing a fused ring carbazole tetradentate metal platinum(II) complex having the structure represented by formula (I) as described above; and a second electrode on the organic light-emitting functional layer. For example, the platinum(II) complex may be included in the organic light-emitting functional layer as a light-emitting material.

[0017] Furthermore, the organic light-emitting functional layer further comprises one or more fluorescent dopant materials, and the fluorescent dopant materials are preferably boron-containing organic molecular light-emitting materials, and more preferably phosphorescence-sensitizable boron-containing compounds.

[0018] In the present invention, an organic photoelectric device is fabricated by depositing a metal or conductive oxide or their alloy on a substrate using methods such as sputtering, electron beam evaporation, or vacuum evaporation to form an anode. A hole injection layer, a hole transport layer, an emitting layer, an air barrier layer, and an electron transport layer are sequentially deposited on the surface of the fabricated anode, and then a cathode is deposited. Alternatively, an organic electroluminescent device can be fabricated by sequentially depositing a cathode, an organic layer, and an anode on a substrate. The organic layer may have a multilayer structure, including a hole injection layer, a hole transport layer, an emitting layer, a hole barrier layer, and an electron transport layer. In the present invention, the organic layer can be fabricated using polymer materials and solvent engineering (e.g., spin coating, tape casting, doctor blading, screen printing, inkjet printing, or thermal imaging) instead of deposition, thereby reducing the number of layers in the device.

[0019] The present invention further provides a composition containing a fused-ring carbazole tetradentate platinum(II) complex having the structure represented by formula (I) as described above. Preferably, the composition further contains a fluorescent dopant material, which is preferably a boron-containing organic molecular luminescent material, and more preferably a phosphorescence-sensitizable boron-containing compound.

[0020] The present invention further provides a formulation containing a fused ring carbazole tetradentate metal platinum(II) complex having a structure represented by formula (I) as described above or a composition as described above, and at least one solvent.

[0021] The solvent is not particularly limited, and examples of the solvent that are well known to those skilled in the art include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene; halogenated saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, and bromocyclohexane; halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene; ether solvents such as tetrahydrofuran and tetrahydropyran; and ester solvents such as alkyl benzoates.

[0022] The present invention further provides a display or lighting device comprising one or more of the organic photovoltaic devices as described above. [Effects of the Invention]

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention provides a tetradentate platinum(II) complex phosphorescent material by introducing a five-membered heterocyclic ring system, such as benzofuran or benzothiophene, into the 5,6-positions of carbazole. The cyclotetradentate platinum(II) complex increases the proportion of triplet localized states (LEs) excited, resulting in a low shoulder peak, improving the purity of the emitted light color of the material molecules. Furthermore, it also improves the device's service life. The materials provided in the present invention all have excellent chemical and thermal stability, facilitating the fabrication of vapor-deposited OLED devices. Organic electroluminescent devices fabricated using the compounds of the present invention as the emitting layer exhibit significantly improved current efficiency and service life, as well as significantly reduced emission voltage. When combined with a fluorescent dopant material (a boron-containing compound), the hole and electron transport is balanced, resulting in more efficient energy transfer between the host and guest, and improved device light color purity. [Brief explanation of the drawings]

[0024] [Figure 1] This is a room temperature emission spectrum of R1 and PtO2 in dichloromethane solution. [Figure 2] This is a room temperature emission spectrum of R1 and PtO6 in dichloromethane solution. [Figure 3] 1 is a diagram showing the room temperature emission spectra of R1 and PtS1 in dichloromethane solution. [Figure 4] This is a room temperature emission spectrum of R1 and PtS2 in dichloromethane solution. [Figure 5] This is a room temperature emission spectrum of R1 and PtS6 in dichloromethane solution. [Figure 6] This is a room temperature emission spectrum of R1 and PtO37 in dichloromethane solution. [Figure 7] This is a room temperature emission spectrum of R1 and PtO38 in dichloromethane solution. [Figure 8] This is a room temperature emission spectrum of R1 and PtO107 in dichloromethane solution. [Figure 9] This is a room temperature emission spectrum of R1 and PtO33 in dichloromethane solution. [Figure 10] This is a room temperature emission spectrum of R1 and PtO34 in dichloromethane solution. [Figure 11] This is a room temperature emission spectrum of R1 and PtO5 in dichloromethane solution. [Figure 12] This is a room temperature emission spectrum of R1 and PtS5 in dichloromethane solution. [Figure 13] This is a room temperature emission spectrum of R1 and PtO109 in dichloromethane solution. DETAILED DESCRIPTION OF THE INVENTION

[0025] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment or specific example of the present invention, but the present invention is not limited to this embodiment or specific example.

[0026] As used herein, the term "substituted" is contemplated to encompass all permissible substituents of organic compounds. Broadly defined, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. For appropriate organic compounds, the permissible substituents can be one or more and the same or different. For purposes of this invention, it is not intended to be limited in any manner by the permissible substituents of organic compounds. Similarly, the terms "substituted" or "substituted" include the implicit proviso that such substitution is consistent with the substituted atom and the permissible valence bonds of the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously transform (e.g., by rearrangement, cyclization, elimination, etc.)). In some embodiments, unless expressly stated to the contrary, a single substituent can be contemplated to be further optionally substituted (i.e., further substituted or unsubstituted).

[0027] In defining various terms, the present invention uses "R 1 " ~ "R 9 " is used as a general symbol to represent various specific substituents. These symbols are not limited to those disclosed in the present invention and may represent any substituent, and when limited to some substituents in some circumstances, they may be limited to any number of other substituents in other circumstances. The "R" symbols used in the present invention are not limited to those disclosed in the present invention and may represent any substituent. 1 "," "R 2 " ... "R n " (where n is an integer) can independently have one or more of the groups listed above. For example, R 1 is a straight chain alkyl group, one hydrogen atom of the alkyl group is optionally replaced by a hydroxy group, an alkoxy group, an alkyl group, a halogen, etc. Whether the first group is embedded within the second group, or optionally, the first group is pendant, i.e., linked to the second group, is determined by the group selected.

[0028] The term "alkyl group" as used herein refers to a branched or unbranched saturated hydrocarbon group of 1 to 60 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, semi-pentyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, or tetracosyl. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups, including, but not limited to, an optionally substituted alkyl group, cycloalkyl group, alkoxy group, amino group, halogen, hydroxy group, nitro group, silyl group, sulfo-oxo group, or sulfhydryl group, as described herein.

[0029] As used herein, the term "aryl group" refers to a group containing any carbon-based aromatic group of 5 to 60 carbon atoms, including, but not limited to, phenyl, naphthyl, biphenyl, phenoxyphenyl, anthracenyl, and phenanthrenyl. The term "aryl group" also includes "heteroaryl groups," which are defined as groups containing an aromatic group, wherein the aromatic group has at least one heteroatom incorporated 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 group" (which is also included in the term "aryl group") defines a group containing an aromatic group without a heteroatom. Aryl groups can be substituted or unsubstituted. The aryl group may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxy, carbonyl, azide, nitro, silyl, sulfo-oxo, or sulfhydryl groups described herein.

[0030] The compounds disclosed herein can exhibit desirable properties and have emission and / or absorption spectra that can be tuned by the selection of appropriate ligands. In alternative aspects, the invention may exclude any one or more compounds, structures, or portions thereof specifically described herein.

[0031] The compounds of the present invention can be prepared using several methods, including but not limited to those described in the examples provided herein.

[0032] It should be noted that the above general description and the following detailed description are both illustrative and interpretive, and are not limiting. The present application can be more easily understood by referring to the following specific embodiments and examples included therein.

[0033] Before the present compounds, devices, and / or methods are disclosed and described, it is to be understood that they are not limited to specific synthetic methods (unless otherwise specified) or specific reagents (unless otherwise specified), as these may, of course, vary. It is also to be understood that the terminology used herein is not intended to be limiting, but is used only for the purpose of describing specific embodiments. Any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, and exemplary methods and materials are described below. All raw materials and solvents in the synthetic examples are commercially available unless otherwise specified, and solvents are used directly without further treatment.

[0034] The substrate of the present invention can be any substrate used in typical organic photovoltaic devices. It can be a glass or transparent plastic substrate, a substrate made of an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness, and waterproofness, and the substrates can be used in different directions depending on their properties. Materials for the hole injection layer, hole transport layer, and electron injection layer can be selected from any known related materials used in OLED devices, and the present invention does not specifically limit the materials used. Synthesis Example

[0035] The following examples of compound synthesis, components, devices, or methods are merely general methods provided in the relevant industrial field and are not intended to limit the scope of protection of the relevant patent. The data (numbers, temperatures, etc.) referred to in the patent are guaranteed to be as accurate as possible, but some errors may exist. Unless otherwise specified, all weighings are performed separately, temperatures are in °C or at room temperature, and pressures are close to normal pressure.

[0036] The following examples provide methods for preparing novel compounds, but the preparation of compounds of this type is not limited to these methods. The compounds protected by the present invention are easily modified and prepared in the art, so the methods listed below or other methods can be used for their preparation. The following examples are for illustrative purposes only and do not limit the scope of protection of the patent. The temperature, catalyst, concentration, reactants, and reaction process can all be changed, and different conditions can be selected for different reactants to prepare the compounds.

[0037] 1 H NMR (500 MHz), 1 H NMR (400 MHz), 13 C NMR (126 MHz) spectra were measured on a ANANCE3 (500 M) nuclear magnetic resonance spectrometer. Unless otherwise specified, the solvent used for nuclear magnetic resonance was either DMSO-d or CDCl containing 0.1% TMS. 1 For H NMR spectra using CDCl3 as the solvent, the internal standard was TMS (δ = 0.00 ppm). For DMSO-d6 as the solvent, the internal standard was TMS (δ = 0.00 ppm), the residual DMSO peak (δ = 2.50 ppm), or the residual water peak (δ = 3.33 ppm). 13 C NMR spectra were measured using CDCl (δ = 77.00 ppm) or DMSO-d (δ = 39.52 ppm) as the internal standard. HPLC-MS and HRMS spectra were measured using an Agilent 6210 TOF LC / MS liquid chromatography-time-of-flight mass spectrometer. 1 In the H NMR spectral data, s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad. (Synthetic Route)

[0038] The synthetic route to the intermediate dPh-tBuNH2 is as follows: JPEG0007827785000016.jpg2759 Synthesis of intermediate dBr-tBuNH2: 4-tert-butylaniline (15.0 g, 100 mmol, 1.0 equiv.) and dichloromethane (150 mL) were dissolved in a reaction flask, and N-bromosuccinimide (37.7 g, 210 mmol, 2.1 equiv.) was added. The reaction was allowed to proceed at room temperature for 48 hours, after which the reaction was stopped. The mixture was concentrated and purified by silica gel column chromatography to obtain 25.6 g of a red liquid, a yield of 84%. This was used directly in the subsequent reaction.

[0039] Synthesis of intermediate dBr-tBuNO: dBr-tBuNH (5 g, 16.3 mmol, 1.0 equiv.) was added to a reaction flask and dissolved in N-methylpyrrolidone (50 mL). Sodium hydride (1.96 g, 49 mmol, 3.0 equiv.) and o-fluoronitrobenzene (3.45 g, 24.5 mmol, 1.5 equiv.) were added. The reaction was allowed to proceed at room temperature for 48 hours, after which the reaction was stopped. The mixture was concentrated and purified by silica gel column chromatography to give 5.08 g of a yellow solid, a yield of 73%, which was used directly in the subsequent reaction.

[0040] Synthesis of intermediate dBr-tBuNH: dBr-tBuNO (4.8 g, 11.2 mmol, 1.0 equiv.), stannous chloride (10.1 g, 44.8 mmol, 4.0 equiv.), ethyl acetate (50 mL), and ethanol (50 mL) were added to a reaction flask. The reaction was quenched in an oil bath at 78 °C for 24 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 3.43 g of a white solid in 82% yield. This was used directly in the subsequent reaction.

[0041] Synthesis of intermediate dPh-tBuNH: A reaction flask was charged with dBr-tBuNH (3.2 g, 8 mmol, 1.0 equiv.), phenylboronic acid (2.93 g, 24 mmol, 3.0 equiv.), tetrakis(triphenylphosphine)palladium (185 mg, 0.16 mmol, 0.02 equiv.), potassium carbonate (2.8 g, 20 mmol, 2.5 equiv.), dioxane (40 mL), and water (15 mL). After 24 h at 90 °C, the reaction was stopped, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 2.66 g of a white solid in 84% yield. 1 H NMR (500 MHz, DMSO) δ 1.35 (s, 9H), 4.44 (s, 2H), 5.57 (s, 1H), 6.05 (dd, J=8.0, 1.5 Hz, 1H), 6.12 (td, J=7.5, 1.5Hz, 1H), 6.25 (td, J=7.5, 1.5 Hz, 1H), 6.31 (dd, J=7.5, 1.5 Hz, 1H), 7.16−7.20(m, 2H), 7.23 −7.26 (m, 4H), 7.28 (s, 2H), 7.41 −7.43 (m, 4H).

[0042] The synthetic route to the intermediate dPh-5tBuNH2 is as follows: Synthesis of intermediate dPh-5tBuNH2: A reaction flask was charged with dBr-tBuNH2 (1.0 g, 2.5 mmol, 1 equiv.), 2-(3,5-di-tert-butylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.37 g, 7.5 mmol, 3 equiv.), tetrakis(triphenylphosphine)palladium (87 mg, 0.075 mmol, 3 mmol.), potassium carbonate (691 mg, 5 mmol, 2 equiv.), dioxane (40 mL), and water (10 mL). After 24 h at 90 °C, the reaction was stopped, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 1.54 g of a white solid in 92% yield. 1H NMR (500 MHz, DMSO) δ 1.17 (s, 36H), 1.37 (s, 9H), 4.35 (s, 2H), 5.50 (s, 1H), 6.03 (dd, J=8.0, 1.5 Hz, 1H), 6.14 (td, J=7.5, 1.5 Hz, 1H), 6.26 (td, J=7.0, 1.0 Hz, 1H), 6.34 (dd, J=7.5, 1.5 Hz, 1H), 7.19 (t, J=1.5 Hz, 2H), 7.22 (d, J=2.0 Hz, 4H), 7.29 (s, 2H).

[0043] The synthetic route to the intermediate dPh-NH2 is as follows: JPEG0007827785000018.jpg2560 Synthesis of intermediate dBr-NO2: dBr-NH2 (20 g, 80 mmol, 1.0 equiv.) and N-methylpyrrolidone (150 mL) were dissolved in a reaction flask, and sodium hydride (9.6 g, 240 mmol, 3.0 equiv.) and o-fluoronitrobenzene (16.9 g, 120 mmol, 1.5 equiv.) were added. The reaction was allowed to proceed at room temperature for 24 hours before quenching. The mixture was concentrated and purified by silica gel column chromatography to yield 21.6 g of a yellow solid, a 73% yield. This was used directly in the subsequent reaction.

[0044] Synthesis of intermediate dBr-2NH: dBr-NO (21.6 g, 58 mmol, 1.0 equiv.), stannous chloride (52.4 g, 232 mmol, 4.0 equiv.), ethyl acetate (150 mL), and ethanol (150 mL) were added to a reaction flask. The reaction was continued at 78 °C for 24 hours, after which the reaction was stopped. The mixture was concentrated and purified by silica gel column chromatography to obtain 18.2 g of a white solid, with a yield of 91%. This was used directly in the subsequent reaction.

[0045] Synthesis of intermediate dPh-NH2: A reaction flask was charged with dBr-2NH2 (12 g, 35 mmol, 1.0 equiv.), phenylboronic acid (12.7 g, 105 mmol, 3.0 equiv.), tetrakis(triphenylphosphine)palladium (809 mg, 0.75 mmol, 0.02 equiv.), sodium carbonate (12.1 g, 87.5 mmol, 2.5 equiv.), dioxane (120 mL), and water (30 mL). The reaction was continued at 90 °C for 24 hours and then quenched. The resulting mixture was concentrated and purified by silica gel column chromatography to give 10.1 g of a white solid in 86% yield. This was used directly in the subsequent reaction.

[0046] The synthetic route for the intermediate dPh-4tBuNH2 is as follows: Synthesis of intermediate dPh-4tBuNH2: A reaction flask was charged with dBr-2NH2 (9.92 g, 29 mmol, 1.0 equiv.), 2-(3,5-di-tert-butylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (27.5 g, 86.9 mmol, 3.0 equiv.), tetrakis(triphenylphosphine)palladium (1.0 g, 0.87 mmol, 3 mol%), potassium carbonate (10.0 g, 72.5 mmol, 2.5 equiv.), dioxane (40 mL), and water (10 mL). After 24 h at 90 °C, the reaction was stopped, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 14.8 g of a white solid in 91% yield. It was used directly in the subsequent reaction.

[0047] Example 1 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtO6 is as follows. Synthesis of intermediate 4O-NO: A-4O-B(OH) (5.8 g, 25.4 mmol, 1.2 equiv.), B (4.5 g, 21.2 mmol, 1.0 equiv.), tetrakis(triphenylphosphine)palladium (734 g, 0.64 mmol, 3 mol%), potassium carbonate (5.86 g, 85.2 mmol, 2.0 equiv.), dioxane (40 mL), and water (10 mL) were added to a reaction flask. The reaction was then heated at 90 °C for 24 h, quenched, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 4.5 g of a yellow solid in 68% yield. 1 H NMR (500 MHz, DMSO) δ 3.95 (s, 3H), 7.42 (td, J=7.5, 1.0 Hz, 1H), 7.47 (dd, J=8.5, 2.5 Hz, 1H), 7.49 ― 7.54 (m, 3H), 7.59 (d, J=8.5 Hz, 1H), 7.67 (d, J=8.65Hz, 1H), 7.71 (d, J=3.0 Hz, 1H), 8.18 (dd, J=6.5, 2.0 Hz, 2H).

[0048] Synthesis of intermediate 4O-NH: 4O-NO (4.5 g, 14.1 mmol, 1.0 equiv.) and triphenylphosphine (11.1 g, 42.3 mmol, 3.0 equiv.) were added to a reaction flask, followed by the addition of o-dichlorobenzene (60 mL). The reaction was then stopped at 110 °C for 24 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 2.61 g of a brown solid in 65% yield. This was used directly in the subsequent reaction.

[0049] Synthesis of intermediate 4O-OMe: A reaction flask was charged with 4O-NH (2.4 g, 8 mmol, 1.0 equiv.), 4-(tert-butyl)-2-chloropyridine (1.63 g, 9.6 mmol, 1.2 equiv.), tris(dibenzylideneacetone)dipalladium (220 mg, 0.24 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (143 mg, 0.48 mmol, 6 mol%), and sodium tert-butoxide (1.54 g, 16 mmol, 2.0 equiv.), and toluene (50 mL) was added. The reaction was then quenched at 110 °C for 48 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 1.75 g of a brown solid in 74% yield. This was used directly in the subsequent reaction.

[0050] Synthesis of intermediate 4O-OH: 4O-OMe (1.05 g, 2.5 mmol, 1.0 equiv.), pyridine hydrochloride (4.5 g, 25 mmol, 10 equiv.), and 1,3-dimethyl-2-imidazolidinone (60 mL) were added to a reaction flask. The reaction was then stopped at 180 °C for 48 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 862 g of a brown solid in 85% yield. This was used directly in the subsequent reaction.

[0051] Synthesis of intermediate tBu-4O-Cl: 4O-OH (500 mg, 1.23 mmol, 1.0 equiv.), 3-chloro-5-bromo-tert-butylbenzene (455 mg, 1.84 mmol, 1.5 equiv.), 2-picolinic acid (30 mg, 0.25 mmol, 20 mmol), copper iodide (23 mg, 0.125 mmol, 10 mmol), and potassium phosphate (522 mg, 2.46 mmol, 2.0 equiv.) were added to a reaction flask, and dimethyl sulfoxide (10 mL) was added. The reaction was then quenched at 110 °C for 12 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 540 mg of a white solid in 70% yield. 1H NMR (500 MHz, DMSO) δ 1.24 (s, 9H) ,1.31 (s, 9H), 6.96 (t, J=2.0 Hz, 1H), 7.13 (t, J=1.5 Hz, 1H), 7.21 (t, J=2.0 Hz, 1H), 7.24 (dd, J=8.5, 2.0 Hz, 1H), 7.32 (d, J=2.0 Hz, 1H), 7.44 - 7.47 (m, 1 H), 7.51 - 7.54 (m, 2H), 7.71 (d, J=2.0 Hz, 1H), 7.78 (d, J=8.5 Hz, 1H), 7.87 (d, J=8.0 Hz, 1H), 8.16 - 8.19 (m, 2H), 8.44 (d, J=8.5 Hz, 1H), 8.62 (d, J=5.5 Hz, 1H).

[0052] Synthesis of intermediate LNH-PtO6: dPh-tBuNH2 (409 mg, 1.04 mmol, 1.2 equiv.) was added to a reaction flask, followed by tBu-4O-Cl (500 mg, 0.87 mmol, 1.0 equiv.), tris(dibenzylideneacetone)dipalladium (24 mg, 0.03 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (16 mg, 0.06 mmol, 6 mol%), and sodium tert-butoxide (167 mg, 1.74 mmol, 2.0 equiv.). Toluene (5 mL) was added. The reaction was quenched at 85 °C for 3 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 460 mg of a white solid in 57% yield. It was used directly in the subsequent reaction.

[0053] Synthesis of the ligand L-PtO6: LNH-PtO6 (370 mg, 0.4 mmol, 1.0 equiv.) was added to a reaction flask, followed by ammonium hexafluorophosphate (130 mg, 0.8 mmol, 2.0 equiv.) and triethyl orthoformate (5 mL). The reaction was then stopped at 80 °C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 287 mg of a white solid in 66% yield. 1H NMR (500 MHz, DMSO) δ 1.30 (s, 9H), 1.31 (s, 9H), 1.43 (s, 9H), 6.88 (t, J=2.5 Hz, 1H), 6.97 (t, J=2.0 Hz, 1H), 7.11 ― 7.17 (m, 10H), 7.33 (dd, J=8.5, 2.0 Hz, 1H), 7.45 ― 7.59 (m, 8H), 7.70 ― 7.72 (m, 3H), 7.78 (d, J=1.5 Hz, 1H), 7.80 (d, J=9.0 Hz, 1H), 7.87 (d, J=7.5 Hz, 1H), 8.19 ― 8.22 (m, 2H), 8.52 (d, J=8.0 Hz, 1H), 8.65 (d, J=5.0 Hz, 1H), 10.26 (s, 1H).

[0054] Synthesis of PtO6: A reaction flask was charged with L-PtO6 (220 mg, 0.2 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (73 mg, 0.21 mmol, 1.05 equiv.), and sodium acetate (50 mg, 0.57 mmol, 3.0 equiv.), and diethylene glycol dimethyl ether (10 mL) was added. The reaction was continued at 120 °C for 72 h, then the mixture was cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 178 mg of a pale yellow solid (78% yield). 1H NMR (400 MHz, DMSO-d6) δ1.23 (s, 9H), 1.43 (s, 18H), 6.64 (dd, J=6.4, 1.6 Hz, 2H), 6.95 -7.05 (m, 5H), 7.16 (t, J=8.0 Hz, 2H), 7.28 -7.37 (m, 5H), 7.46 -7.60 (m, 6H), 7.77 (d, J=9.2 Hz, 1H), 7.91 (d, J=8.0 Hz, 1H), 8.04 (d, J=8.0 Hz, 2H), 8.13 (t, J=7.2 Hz, 2H), 8.27 (d, J=7.2 Hz, 1H), 8.35 (d, J=8.4 Hz, 1H), 8.95 (d, J=6.4 Hz, 1H).

[0055] Example 2 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtO2 is as follows: Synthesis of intermediate LNH-PtO2: To a reaction flask was added dPh-NH2 (200 mg, 0.6 mmol, 1.0 equiv.), followed by tBu-4O-Cl (361 mg, 0.63 mmol, 1.05 equiv.), tris(dibenzylideneacetone)dipalladium (16 mg, 0.02 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (10 mg, 0.04 mmol, 6 mol%), and sodium tert-butoxide (115 mg, 1.2 mmol, 2.0 equiv.), followed by toluene (5 mL). The reaction was quenched at 85 °C for 3 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 419 mg of a white solid in 85% yield. It was used directly in the subsequent reaction.

[0056] Synthesis of the ligand L-PtO2: LNH-PtO2 (500 mg, 0.57 mmol, 1.0 equiv.), ammonium hexafluorophosphate (185 mg, 1.14 mmol, 2.0 equiv.), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was then stopped at 80 °C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 500 mg of a white solid in 80% yield. 1H NMR (500 MHz, DMSO) δ 1.29 (s, 9H) ,1.31 (s, 9H), 6.92 (t, J=2.0 Hz, 1H), 6.95 (t, J=1.5 Hz, 1H), 6.95 (t, J=1.5 Hz, 1H), 7.11 ― 7.15 (m, 10H), 7.33 (dd, J=8.5, 2.0 Hz, 1H), 7.45 - 7.51 (m, 4H), 7.52 - 7.59 (m, 4H), 7.69 - 7.70 (m, 1H), 7.75 - 7.81 (m, 4H), 7.87 (d, J=8.0 Hz, 1H), 7.94 (t, J=8.0 Hz, 1H), 8.19 ― 8.22 (m, 2H), 8.52 (d, J=8.5 Hz, 1H), 8.64 (d, J=5.0 Hz, 1H), 10.33 (s, 1H).

[0057] Synthesis of PtPtO: A reaction flask was charged with L-PtO (450 mg, 0.44 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (160 mg, 0.46 mmol, 1.05 equiv.), and sodium acetate (108 mg, 1.32 mmol, 3.0 equiv.). Diethylene glycol dimethyl ether (10 mL) was added and nitrogen was bubbled through for 30 min to remove oxygen. The reaction was then quenched at 120 °C for 72 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 368 mg of a pale yellow solid in 78% yield. 1H NMR (500 MHz, CDCl3) δ 1.31 (s, 9H) ,1.47 (s, 9H), 6.24 (dd, J=6.5, 2.0 Hz, 2H), 6.75 ― 7.34 (m, 5H), 6.89 (d, J=7.5 Hz, 2H), 7.06 (t, 8.10 (d, J=8.5 Hz, 1H), 8.18 (d, J=2.5 Hz, 1H), 8.21 (d, J=8.5 Hz, 1H), 9.02 (d, J=6.0 Hz, 1H).

[0058] Example 3 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtO5 is as follows. Synthesis of intermediate LNH-PtO: dPh-tBuNH (502 mg, 1.28 mmol, 1.1 equiv.), 4O-Cl (600 mg, 1.16 mmol, 1.0 equiv.), tris(dibenzylideneacetone)dipalladium (32 mg, 0.035 mmol, 3 mol%), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (29 mg, 0.070 mmol, 6 mol%), and sodium tert-butoxide (223 mg, 2.32 mmol, 2.0 equiv.) were added to a reaction flask, and toluene (5 mL) was added. The reaction was quenched in an oil bath at 110 °C for 12 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 1.04 g of a pale green solid in 96% yield. It was used directly in the subsequent reaction.

[0059] Synthesis of the ligand L-PtO5: LNH-PtO5 (1.04 g, 1.2 mmol, 1.0 equiv.), ammonium hexafluorophosphate (391 mg, 2.4 mmol, 2.0 equiv.), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was then stopped at 70 °C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 961 mg of a white solid in 78% yield. 1 H NMR (500 MHz, CDCl3) δ 1.42 (s, 9H), 1.45 (s, 9H), 6.66 (t, J=2.0 Hz, 1H), 6.95 (dd, J=8.0, 2.0 Hz, 1H), 7.05 ― 7.08(m, 2H), 7.10 ― 7.16 (m, 8H), 7.22 (dd, J=8.5, 2.0 Hz, 1H), 7.25 (s, 1H), 7.27 (d, J=2.0 Hz, 1H), 7.37 - 7.44 (m, 3H), 7.46 - 7.49 (m, 2H), 7.52 ― 7.55 (m, 2H), 7.59 (s, 2H), 7.64 (d, J=2.0 Hz, 1H), 7.68 ― 7.72 (m, 2H), 7.77 (d, J=8.0 Hz, 1H), 8.00 (t, J=7.5 Hz, 2H), 8.59 (d, J=8.5 Hz, 1H), 8.64 (d, J=5.5 Hz, 1H), 9.09 (s, 1H).

[0060] Synthesis of PtO5: A reaction flask was charged with L-PtO5 (890 mg, 0.86 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (337 mg, 0.90 mmol, 1.05 equiv.), and sodium acetate (212 mg, 2.58 mmol, 3.0 equiv.), and diethylene glycol dimethyl ether (10 mL) was added. The reaction was continued at 120 °C for 72 h, then the reaction was stopped. The mixture was cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 283 mg of a pale yellow solid (31% yield). 1H NMR (500 MHz, Chloroform-d) δ 1.22 (s, 9H), 1.44 (s, 9H), 6.33 ― 7.09 (m, 11H), 7.23 ― 7.24 (m, 2H), 7.27 (s, 1H), 7.42 ― 7.53 (m, 7H), 7.79 (d, J=9.0 Hz, 1H), 7.92 (d, J=8.5 Hz, 1H), 8.00 - 8.07 (m, 4H), 8.26 (d, J=8.0 Hz, 1H), 9.12 (d, J=6.5 Hz, 1H).

[0061] Example 4 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtO27 is as follows. JPEG0007827785000024.jpg3556 PtO27 was synthesized by referring to the synthesis steps and reaction conditions of compound PtO6 in Example 5. The synthesized target product LNH-PtO27 was 1.24 g of a light green foam-like solid, with a yield of 85%. The synthesized target product L-PtO27 was 881 mg of a light green foam-like solid, with a yield of 78%. Molecular weight [M] + The molecular weight [M+H] was 1100.5. The target product PtO27 was a yellow solid, 425 mg, with a yield of 56%. + :1294.5.

[0062] Example 5 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtO33 is as follows. JPEG0007827785000025.jpg1354

[0063] Synthesis of intermediate 4O-Cl: 4O-OH (200 mg, 0.49 mmol, 1.0 equiv.), m-chlorobromobenzene (140 mg, 0.73 mmol, 1.5 equiv.), 2-picolinic acid (12 mg, 0.098 mmol, 20 mmol%), copper iodide (9 mg, 0.049 mmol, 10 mmol%), and potassium phosphate (208 mg, 0.98 mmol, 2.0 equiv.) were added to a reaction flask, and dimethyl sulfoxide (5 mL) was added. The reaction was then quenched at 100 °C for 12 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 164 mg of a white solid in 65% yield. 1 H NMR (500 MHz, DMSO) δ 1.32 (s, 9H), 7.09−7.12(m, 1H), 7.20 −7.26 (m, 3H), 7.33 (d, J=2.0 Hz, 1H), 7.40−7.48 (m, 2H), 7.51―7.55(m, 2H), 7.74 (d, J=2.0 Hz, 1H), 7.80 (d, J=8.5 Hz, 1H), 7.88 (d, J=8.0 Hz, 1H), 8.18―8.20 (m, 2H), 8.45 (d, J=8.5 Hz, 1H), 8.64 (d, J=5.45Hz, 1H).

[0064] JPEG0007827785000026.jpg2854 Synthesis of intermediate LNH-PtO33: A reaction flask was charged with dPh-4tBuNH2 (477 mg, 0.85 mmol, 1.1 equiv), 4O-Cl (400 mg, 0.77 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (21 mg, 0.02 mmol, 3 mol%), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (19 mg, 0.04 mmol, 6 mol%), and sodium tert-butoxide (149 mg, 1.4 mmol, 2.0 equiv) and toluene (5 mL). The reaction was stopped by reacting in an oil bath at 110°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 660 mg of a white solid in 82% yield, which was directly used in the subsequent reaction.

[0065] Synthesis of the ligand L-PtO33: LNH-PtO33 (660 mg, 0.63 mmol, 1.0 equiv.), ammonium hexafluorophosphate (206 mg, 1.27 mmol, 2.0 equiv.), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was then stopped at 70 °C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 542 mg of a white solid in 71% yield. 1 H NMR (500 MHz, DMSO-d6) δ 0.92 (s, 36H), 1.34 (s, 9H), 6.55 (t, J=2.5 Hz, 1H), 6.68 (ddd, J=8.5, 2.5, 1.0 Hz, 1H), 6.91 (d, J=1.5 Hz, 4H), 7.14 (t, J=2.0 Hz, 2H), 7.32 (dd, J=8.0, 2.0 Hz, 1H), 7.46 ― 7.59 (m, 8H), 7.69 ― 7.73 (m, 2H), 7.75 (d, J=1.0 Hz, 1H), 7.79 ― 7.89 (m, 4H), 7.94 ― 7.97 (m, 1H), 8.19 - 8.24 (m, 2H), 8.49 (d, J=8.5 Hz, 1H), 8.65 (dd, J=5.0, 0.5 Hz, 1H), 10.01 (s, 1H).

[0066] Synthesis of PtO3: A reaction flask was charged with L-PtO3 (500 mg, 0.42 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (156 mg, 0.42 mmol, 1.05 equiv.), and sodium acetate (103 mg, 1.25 mmol, 3.0 equiv.), and diethylene glycol dimethyl ether (10 mL) was added. The reaction was continued at 120 °C for 72 h, then the mixture was cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 108 mg of a pale yellow solid (34% yield). 1H NMR (500 MHz, DMSO-d6) δ 0.26 - 1.19 (br, 36H), 1.32 (s, 9H), 6.53 - 7.37 (m, 14H), 7.47 - 7.61 (m, 5H), 7.90 (d, J=8.0 Hz, 1H), 8.06 (d, J=8.0 Hz, 1H), 8.15 - 8.20 (m, 2H), 8.21 - 8.30 (m, 3H), 9.04 (d, J=6.5 Hz, 1H).

[0067] Example 6 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtO34 is as follows. Synthesis of intermediate LNH-PtO34: A reaction flask was charged with dPh-4tBuNH2 (430 mg, 0.77 mmol, 1.1 equiv.), tBu-4O-Cl (400 mg, 0.70 mmol, 1.0 equiv.), tris(dibenzylideneacetone)dipalladium (19 mg, 0.02 mmol, 3 mol%), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (17 mg, 0.04 mmol, 6 mol%), and sodium tert-butoxide (134 mg, 1.40 mmol, 2.0 equiv.), and toluene (5 mL) was added. The reaction was quenched in an oil bath at 110 °C for 3 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 591 mg of a white solid in 78% yield. It was used directly in the subsequent reaction.

[0068] Synthesis of the ligand L-PtO34: LNH-PtO34 (591 mg, 0.54 mmol, 1.0 equiv.), ammonium hexafluorophosphate (175 mg, 1.07 mmol, 2.0 equiv.), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was then stopped at 70 °C for 2 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 415 mg of a white solid in 61% yield. 1H NMR (500 MHz, DMSO-d6) δ 0.87 (s, 36H), 1.29 (s, 9H), 1.35 (s, 9H), 6.40 (t, J=2.0 Hz, 1H), 6.69 (t, J=2.0 Hz, 1H), 6.89 (d, J=2.0 Hz, 4H), 7.07 (t, J=1.5 Hz, 2H), 7.34 (dd, J=8.5, 2.5 Hz, 1H), 7.44 - 7.59 (m, 8H), 7.68 (d, J=8.5 Hz, 1H), 7.74 (d, J=1.0 Hz, 1H), 7.77 - 7.82 (m, 2H), 7.83 (s, 1H), 7.86 ― 7.89 (m, 1H), 7.93 ― 7.96 (m, 1H), 8.19 ― 8.24 (m, 2H), 8.49 (d, J=8.0 Hz, 1H), 8.65 (d, J=5.5 Hz, 1H), 10.07 (s, 1H).

[0069] Synthesis of PtO34: A reaction flask was charged with L-PtO34 (350 mg, 0.28 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (104 mg, 0.29 mmol, 1.05 equiv.), and sodium acetate (69 mg, 0.84 mmol, 3.0 equiv.), and diethylene glycol dimethyl ether (10 mL) was added. The reaction was continued at 120 °C for 72 h, then the reaction was stopped. The mixture was cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 152 mg of a pale yellow solid (41% yield). 1H NMR (500 MHz, DMSO-d6) δ 0.75 (s, 36H), 1.32 (s, 9H), 1.40 (s, 9H), 6.64 (dd, J=6.0, 2.0 Hz, 1H), 6.80 ― 7.12 (m, 9H), 7.28 ― 7.33 (m, 2H), 7.45 (s, 1H), 7.50 (t, J=7.5 Hz, 1H), 7.57 (t, J=7.5 Hz, 3H), 7.90 (d, J=8.0 Hz, 1H), 8.05 (d, J=8.0 Hz, 2H), 8.17 (s, 1H), 8.21 (d, J=8.5 Hz, 1H), 8.25 - 8.28 (m, 2H), 9.00 (d, J=6.0 Hz, 1H).

[0070] Example 7 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtO37 is as follows. JPEG0007827785000028.jpg2853 Synthesis of intermediate LNH-PtO37: A reaction flask was charged with dPh-5tBuNH2 (666 mg, 1.08 mmol, 1.1 equiv), 4O-Cl (500 mg, 0.98 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (28 mg, 0.03 mmol, 3 mol%), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (25 mg, 0.06 mmol, 6 mol%), and sodium tert-butoxide (188 mg, 1.96 mmol, 2.0 equiv) and toluene (5 mL). The reaction was stopped by reacting in an oil bath at 110°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 896 mg of a white solid in 83% yield, which was directly used in the subsequent reaction.

[0071] Synthesis of the ligand L-PtO37: LNH-PtO37 (896 mg, 0.82 mmol, 1.0 equiv.), ammonium hexafluorophosphate (267 mg, 1.64 mmol, 2.0 equiv.), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was then stopped at 70 °C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 770 mg of a white solid in 75% yield. 1 H NMR (500 MHz, DMSO) δ 0.92 (s, 36H), 1.34 (s, 9H), 1.47 (s, 9H), 6.54 (s, 1H), 6.67 (d, J=7.0 Hz, 1H), 6.91 (s, 4H), 7.14 (s, 2H), 7.32 (dd, J=8.0, 2.0 Hz, 1H), 7.45 - 7.57 (m, 8H), 7.68 - 7.72 (m, 2H), 7.75 (s, 1H), 7.81 (d, J=7.5 Hz, 3H), 7.87 (d, J=8.0 Hz, 1H), 8.21 (t, J=8.5 Hz, 2H), 8.49 (d, J=8.0 Hz, 1H), 8.65 (d, J=5.5 Hz, 1H), 9.93 (s, 1H).

[0072] Synthesis of PtO37: A reaction flask was charged with L-PtO37 (700 mg, 0.56 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (221 mg, 0.59 mmol, 1.05 equiv.), and sodium acetate (138 mg, 1.68 mmol, 3.0 equiv.), and diethylene glycol dimethyl ether (5 mL) was added. The reaction was continued at 120 °C for 72 h, then the mixture was cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 124 mg of a pale yellow solid (17% yield). 1H NMR (500 MHz, CDCl3) δ 0.05 ― 1.18 (m, 36H), 1.20 (s, 9H), 1.40 (s, 9H), 6.45 (dd, J=6.5, 2.0Hz, 1H), 6.86 (d, J=8.0 Hz, 3H), 6.95 ― 7.05 (m, 4H), 7.20 (t, J=8.0 Hz, 3H), 7.37 - 7.59 (m, 7H), 7.79 (dd, J=8.0, 2.0 Hz, 2H), 7.92 - 8.00 (m, 3H), 8.05 (d, J=7.5 Hz, 1H), 8.25 (d, J=8.5 Hz, 1H), 9.25 (d, J=6.5 Hz, 1H).

[0073] Example 8 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtO38 is as follows. JPEG0007827785000029.jpg3156 Synthesis of intermediate LNH-PtO38: A reaction flask was charged with dPh-5tBuNH2 (592 mg, 0.96 mmol, 1.1 equiv), tBu-4O-Cl (500 mg, 0.87 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (24 mg, 0.03 mmol, 3 mol%), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (26 mg, 0.06 mmol, 6 mol%), and sodium tert-butoxide (167 mg, 1.74 mmol, 2.0 equiv) and toluene (5 mL). The reaction was stopped by reacting in an oil bath at 110°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 887 mg of a white solid in 88% yield, which was directly used in the subsequent reaction.

[0074] Synthesis of the ligand L-PtO38: LNH-PtO38 (887 mg, 0.77 mmol, 1.0 equiv.), ammonium hexafluorophosphate (251 mg, 1.54 mmol, 2.0 equiv.), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was then stopped at 70 °C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 700 mg of a white solid in 70% yield. 1 H NMR (500 MHz, DMSO) δ 0.87 (s, 36H) ,1.28 (s, 9H), 1.34 (s, 9H), 1.46 (s, 9H), 6.38 (t, J=2.5 Hz, 1H), 6.70 (t, J=2.0 Hz, 1H), 6.89 (d, J=2.0 Hz, 4H), 7.06 (t, J=1.5 Hz, 2H), 7.34 (dd, J=8.5, 2.0 Hz, 1H), 7.42 - 7.50 (m, 3H), 7.52 - 7.58(m, 5H), 7.67 (d, J=8.5 Hz, 1H), 7.74 (d, J=2.5 Hz, 1H), 7.78 ― 7.80 (m, 3H), 7.86 (d, J=8.0 Hz, 1H), 8.21 (t, J=9.0 Hz, 2H), 8.49 (d, J=8.5 Hz, 1H), 8.65 (d, J=5.5 Hz, 1H), 10.00 (s, 1H).

[0075] Synthesis of PtO38: A reaction flask was charged with L-PtO38 (622 mg, 0.48 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (189 mg, 0.54 mmol, 1.05 equiv.), and sodium acetate (118 mg, 1.44 mmol, 3.0 equiv.), and diethylene glycol dimethyl ether (5 mL) was added. The reaction was continued at 120 °C for 72 h, then the reaction was stopped, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 400 mg of a pale yellow solid in 61% yield. 1H NMR (500 MHz, DMSO) δ 1.23 (s, 45H), 1.40 (s, 18H), 6.68 (d, J=8.0 Hz, 2H), 6.83 ― 6.97 (m, 4H), 7.08 (t, J=7.5 Hz, 3H), 7.24 ― 7.35 (m, 3H), 7.43 - 7.60 (m, 5H), 7.87(d, J=8.5 Hz, 1H), 7.91(d, J=8.0 Hz, 1H),8.01 (d, J=2.0 Hz, 1H), 8.07 (dd, J=11.5, 8.0 Hz, 2H), 8.24 (d, J=8.0 Hz, 1H), 8.28 (d, J=8.5 Hz, 1H), 9.09 (d, J=6.5 Hz, 1H).

[0076] Example 9 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtO93 is as follows. JPEG0007827785000030.jpg3258 PtS93 was synthesized by referring to the synthesis steps and reaction conditions of compound PtS6 in Example 12. The synthesized target product LNH-PtO93 was 1.19 g of a light green foam-like solid, with a yield of 77%. The synthesized target product L-PtO93 was 891 mg of a light green foam-like solid, with a yield of 78%. Molecular weight [M] + The molecular weight [M+H] was 881.2. The target product PtO93 was a yellow solid, 325 mg, with a yield of 36%. + :1072.2.

[0077] Example 10 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtO107 is as follows. JPEG0007827785000031.jpg2759 Synthesis of intermediate dtBu-Me-4O-OMe: 4O-NH (1.0 g, 3.5 mmol, 1.0 equiv.), dtBu-Me-Cl (1.34 g, 4.2 mmol, 1.2 equiv.), tris(dibenzylideneacetone)dipalladium (128 mg, 0.14 mmol, 4 mol%), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (115 mg, 0.28 mmol, 8 mol%), and sodium tert-butoxide (673 mg, 7 mmol, 2.0 equiv.) were added to a reaction flask, and toluene (5 mL) was added. The reaction was then quenched at 110 °C for 48 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 1.92 g of a brown solid in 95% yield. This was used directly in the subsequent reaction.

[0078] Synthesis of intermediate dtBu-Me-4O-OH: dtBu-Me-4O-OMe (1.84 g, 3.2 mmol, 1.0 equiv.) and hydrogen bromide (2.59 g, 32 mmol, 10.0 equiv.) were added to a reaction flask. The reaction was then heated at 120 °C for 48 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 1.58 g of a brown solid in 89% yield. This was used directly in the subsequent reaction.

[0079] Synthesis of intermediate dtBu-Me-4O-Cl: A reaction flask was charged with dtBu-Me-4O-OH (600 mg, 1.09 mmol, 1.0 equiv.), m-chlorobromobenzene (314 mg, 1.64 mmol, 1.5 equiv.), 2-picolinic acid (134 mg, 1.10 mmol, 100 mmol), copper iodide (105 mg, 0.55 mmol, 10 mmol), and potassium phosphate (463 mg, 2.18 mmol, 2.0 equiv.), and dimethyl sulfoxide (10 mL). The reaction was quenched at 110 °C for 12 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 566 mg of a white solid in 78% yield. 1H NMR (500 MHz, DMSO) δ 1.36 (s, 18H), 2.44 (s, 3H), 7.04 (dd, J=8.0, 2.0 Hz, 1H), 7.13 (t, J=2.5 Hz, 1H), 7.18 ― 7.23 (m, 2H), 7.35 (d, J=2.0 Hz, 2H), 7.41 (t, J=8.0 Hz, 1H), 7.45 - 7.49 (m, 2H), 7.51 - 7.55 (m, 1H), 7.63 (d, J=2.0 Hz, 1H), 7.82 (s, 1H), 7.88 (t, J=9.0 Hz, 1H), 8.21 (d, J=11.0 Hz, 2H), 8.46 (d, J=8.5 Hz, 1H), 8.57 (s, 1H).

[0080] JPEG0007827785000032.jpg2856 Synthesis of intermediate LNH-PtO107: A reaction flask was charged with dPh-tBuNH2 (341 mg, 0.87 mmol, 1.1 equiv), dtBu-Me-4O-Cl (524 mg, 0.79 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (22 mg, 0.024 mmol, 3 mol%), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (20 mg, 0.048 mmol, 6 mol%), and sodium tert-butoxide (152 mg, 1.58 mmol, 2.0 equiv) and toluene (5 mL). The reaction was stopped by reacting in an oil bath at 110°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 687 mg of a white solid in 85% yield, which was directly used in the subsequent reaction.

[0081] Synthesis of the ligand L-PtO107: LNH-PtO107 (687 mg, 0.67 mmol, 1.0 equiv.), ammonium hexafluorophosphate (218 mg, 1.34 mmol, 2.0 equiv.), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was then stopped at 70 °C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 755 mg of a white solid in 96% yield. This was used directly in the subsequent reaction.

[0082] Synthesis of PtO107: A reaction flask was charged with L-PtO107 (675 mg, 0.57 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (224 mg, 0.60 mmol, 1.05 equiv.), and sodium acetate (140 mg, 1.71 mmol, 3.0 equiv.), and diethylene glycol dimethyl ether (5 mL) was added. The reaction was continued at 120 °C for 72 h, then the reaction was stopped. The mixture was cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 183 mg of a pale yellow solid (26% yield). 1 H NMR (500 MHz, CDCl3) δ 1.17 (s, 18H), 1.55 (s, 9H), 2.05 (s, 3H), 6.05 (t, J=8.5 Hz, 2H), 6.43 (tt, J=8.0, 1.5 Hz, 1H), 6.50 (s, 2H), 6.73 (d, J=8.0 Hz, 1H), 6.78 (d, J=2.0 Hz, 2H), 6.87 ― 6.96 (m, 4H), 7.05 ― 7.10 (m, 2H), 7.16 ― 7.25 (m, 4H), 7.39 ―7.54 (m, 6H), 7.80 (d, J=8.0 Hz, 1H), 7.95 - 7.97 (m, 2H), 8.02 (d, J=8.5 Hz, 1H), 8.06 - 8.09 (m, 2H), 8.27 (d, J=8.0 Hz, 1H), 9.19 (s, 1H).

[0083] Example 11 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtO109 is as follows. Synthesis of intermediate PhF-Me-NH: A reaction flask was charged with p-fluorobenzeneboronic acid (2.7 g, 19.2 mmol, 1.2 equiv.), Br-Me-NH (3.0 g, 16 mmol, 1.0 equiv.), tetrakis(triphenylphosphine)palladium (371 mg, 0.32 mmol, 2 mol%), potassium carbonate (4.4 g, 32 mmol, 2 equiv.), dioxane (160 mL), and water (40 mL). The reaction was quenched at 90 °C for 12 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 3.1 g of a yellow solid in 95% yield. This was used directly in the subsequent reaction.

[0084] Synthesis of intermediate PhF-Me-Cl: PhF-Me-NH (3.1 g, 15.3 mmol, 1.0 equiv.), tert-butyl nitrite (15.7 g, 69 mmol, 5.0 equiv.), benzyltriethylammonium chloride (7.9 g, 76.6 mmol, 4.5 equiv.), dichloromethane (100 mL), and water (40 mL) were added to a reaction flask. The reaction was allowed to proceed at room temperature for 12 hours, then the mixture was cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 3.1 g of a yellow solid in 60% yield. This was used directly in the subsequent reaction.

[0085] Synthesis of intermediate PhF-Me-4O-OMe: 4O-NH (1.0 g, 3.5 mmol, 1.0 equiv.), PhF-Me-Cl (931 g, 3.5 mmol, 1.2 equiv.), tris(dibenzylideneacetone)dipalladium (128 mg, 0.14 mmol, 4 mol%), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (115 mg, 0.28 mmol, 8 mol%), and sodium tert-butoxide (673 mg, 7 mmol, 2.0 equiv.) were added to a reaction flask, and toluene (5 mL) was added. The reaction was then heated at 110 °C for 48 h, quenched, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 1.42 g of a brown solid in 86% yield. It was used directly in the subsequent reaction.

[0086] Synthesis of intermediate PhF-Me-4O-OH: PhF-Me-4O-OMe (1.42 g, 3.2 mmol, 1.0 equiv.) and hydrogen bromide (2.59 g, 32 mmol, 10.0 equiv.) were added to a reaction flask. The reaction was then heated at 120 °C for 48 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 1.21 g of a brown solid in 85% yield. This was used directly in the subsequent reaction.

[0087] Synthesis of intermediate PhF-Me-4O-Cl: PhF-Me-4O-OH (3.0 g, 6.5 mmol, 1.0 equiv.), m-chlorobromobenzene (1.88 g, 9.8 mmol, 1.5 equiv.), 2-picolinic acid (800 mg, 6.5 mmol, 100 mmol), copper iodide (619 mg, 3.3 mmol, 50 mmol), and potassium phosphate (2.7 g, 13 mmol, 2.0 equiv.) were added to a reaction flask, and dimethyl sulfoxide (20 mL) was added. The reaction was then quenched at 120 °C for 12 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 644 mg of a white solid in 49% yield. This was used directly in the subsequent reaction.

[0088] JPEG0007827785000035.jpg2962 Synthesis of intermediate LNH-PtO109: A reaction flask was charged with dPh-4tBuNH2 (470 mg, 1.2 mmol, 1.2 equiv), PhF-Me-4O-Cl (620 mg, 1.09 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (30 mg, 0.03 mmol, 3 mol%), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (27 mg, 0.06 mmol, 6 mol%), and sodium tert-butoxide (210 mg, 2.18 mmol, 2.0 equiv) and toluene (8 mL). The reaction was stopped by reacting in an oil bath at 110°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 925 mg of a white solid (yield: 92%), which was directly used in the subsequent reaction.

[0089] Synthesis of the ligand L-PtO109: LNH-PtO109 (925 mg, 1 mmol, 1.0 equiv.), ammonium hexafluorophosphate (326 mg, 2 mmol, 2.0 equiv.), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was then stopped at 70 °C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 629 mg of a white solid in 58% yield. 1 H NMR (500 MHz, DMSO-d6) δ 1.43 (s, 9H), 2.42 (s, 3H), 6.97 (t, J=2.0 Hz, 1H), 7.11 ― 7.17 (m, 11H), 7.32 (dd, J=8.5, 2.5 Hz, 1H), 7.36 ― 7.43 (m, 3H), 7.45 ― 7.51 (m, 2H), 7.52 ― 7.61 (m, 5H), 7.70 ― 7.78 (m, 5H), 7.87 ― 7.93 (m, 3H), 8.21 ― 8.26 (m, 2H), 8.53 ― 8.56 (m, 2H), 10.26 (s, 1H).

[0090] Synthesis of PtO109: A reaction flask was charged with L-PtO109 (591 mg, 0.55 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (205 mg, 0.58 mmol, 1.05 equiv.), and sodium acetate (135 mg, 1.64 mmol, 3.0 equiv.), and diethylene glycol dimethyl ether (5 mL) was added. The reaction was continued at 120 °C for 72 h, then cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 254 mg of a pale yellow solid (41% yield). 1H NMR (500 MHz, DMSO-d6) δ 1.48 (s, 9H), 2.22 (s, 3H), 6.10 (t, J=7.5 Hz, 2H), 6.47 (t, J=7.5 Hz, 1H), 6.52 (d, J=7.5 Hz, 2H), 6.79 (d, J=8.0 Hz, 1H), 6.83 (t, J=9.0 Hz, 2H), 6.94 (dd, J=8.0, 1.0 Hz, 1H), 7.05 - 7.13 (m, 4H), 7.16 - 7.32 (m, 8H), 7.40 (d, J=2.5 Hz, 1H), 7.52 (td, J=7.5, 1.0 Hz, 1H), 7.59 (ddd, J=8.0, 7.0, 1.5 Hz, 1H), 7.64 (d, J=7.5 Hz, 1H), 7.92 (d, J=8.0 Hz, 1H), 8.06 - 8.10 (m, 2H), 8.17 (d, J=8.5 Hz, 1H), 8.22 (d, J=8.5 Hz, 1H), 8.29 (dd, J=7.5, 1.5 Hz, 1H), 8.37 (d, J=8.5 Hz, 1H), 9.05 (s, 1H).

[0091] Example 12 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtS6 is as follows. Synthesis of intermediate 4S-NO2: A-4S-B(OH)2 (8.76 g, 38.4 mmol, 1.2 equiv.), B (6 g, 32 mmol, 1.0 equiv.), tetrakis(triphenylphosphine)palladium (1.11 g, 0.96 mmol, 3 mol%), and potassium carbonate (8.86 g, 64 mmol, 2.0 equiv.) were added to a reaction flask, followed by dioxane (80 mL) and water (20 mL). The reaction was quenched at 90 °C for 24 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 9.23 g of a yellow solid in 80% yield. This was used directly in the subsequent reaction.

[0092] Synthesis of intermediate 4S-NH: 4S-NO (6 g, 17.9 mmol, 1.0 equiv.) and triphenylphosphine (14.08 g, 53.7 mmol, 3.0 equiv.) were added to a reaction flask, followed by o-dichlorobenzene (60 mL). The reaction was quenched at 110 °C for 24 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 4.45 g of a brown solid in 82% yield. This was used directly in the subsequent reaction.

[0093] Synthesis of intermediate 4S-OMe: A reaction flask was charged with 4S-NH (3 g, 10 mmol, 1.0 equiv.), 4-(tert-butyl)-2-chloropyridine (2.04 g, 12 mmol, 1.2 equiv.), tris(dibenzylideneacetone)dipalladium (275 mg, 0.3 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (179 mg, 0.6 mmol, 6 mol%), and sodium tert-butoxide (1.92 g, 20 mmol, 2.0 equiv.), and toluene (50 mL) was added. The reaction was then quenched at 110 °C for 48 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 3.12 g of a brown solid in 73% yield. This was used directly in the subsequent reaction.

[0094] Synthesis of intermediate 4S-OH: 4S-OMe (3.12 g, 7.1 mmol, 1.0 equiv.), pyridine hydrochloride (8.53 g, 71 mmol, 10.0 equiv.), and 1,3-dimethyl-2-imidazolidinone (60 mL) were added to a reaction flask. The reaction was then stopped at 180 °C for 48 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 2.68 g of a brown solid in 87% yield. This was used directly in the subsequent reaction.

[0095] Synthesis of intermediate tBu-4S-Cl: 4S-OH (1 g, 2.4 mmol, 1.0 equiv.), 3-chloro-5-bromo-tert-butylbenzene (1.78 g, 3.12 mmol, 1.3 equiv.), 2-picolinic acid (60 mg, 0.48 mmol, 20 mmol%), copper iodide (46 mg, 0.24 mmol, 10 mmol%), and potassium phosphate (1.02 g, 4.8 mmol, 2.0 equiv.) were added to a reaction flask, and dimethyl sulfoxide (10 mL) was added. The reaction was then quenched at 110 °C for 12 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 1.05 g of a white solid in 75% yield. 1 H NMR (500 MHz, DMSO) δ 1.24 (s, 9H), 1.32 (s, 9H), 6.95 (t, J=2.0 Hz, 1H), 7.14 (t, J=2.5 Hz, 1H), 7.21 (t, J=1.5 Hz, 1H), 7.28 (dd, J=11.0, 2.5 Hz, 1H), 7.38 (d, J=2.0 Hz, 1H), 7.52 - 7.60 (m, 3H), 7.72 (d, J=1.5 Hz, 1H), 7.91 (d, J=9.0 Hz, 1H), 8.17 (d, J=6.5 Hz, 1H), 8.23 ​​(d, J=8.5 Hz, 1H), 8.42 - 8.45 (m, 2H), 8.63 (d, J=5.5 Hz, 1H).

[0096] Synthesis of intermediate LNH-PtS6: dPh-tBuNH2 (125 mg, 0.32 mmol, 1.0 equiv.) was added to a reaction flask, followed by tBu-4O-Cl (200 mg, 0.34 mmol, 1.05 equiv.), tris(dibenzylideneacetone)dipalladium (9 mg, 0.001 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (6 mg, 0.002 mmol, 6 mol%), and sodium tert-butoxide (61 mg, 0.64 mmol, 2.0 equiv.). Toluene (5 mL) was added. The reaction was then heated at 110 °C for 12 h, quenched, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 187 mg of a white solid in 67% yield. It was used directly in the subsequent reaction.

[0097] Synthesis of the ligand L-PtS6: LNH-PtS6 (228 mg, 0.24 mmol, 1.0 equiv.) was added to a reaction flask, followed by the addition of ammonium hexafluorophosphate (31 mg, 0.48 mmol, 2.0 equiv.) and triethyl orthoformate (5 mL). The reaction was then stopped at 80 °C for 2 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 184 mg of a white solid in 74% yield. 1 H NMR (500 MHz, DMSO) δ 1.30 (s, 9H), 1.31 (s, 9H), 1.42 (s, 9H), 6.86 (t, J=2.0 Hz, 1H), 6.97 (t, J=1.5 Hz, 1H), 7.10 -7.16(m, 10H), 7.37 (dd, J=8.5, 2.5 Hz, 1H), 7.47-7.60(m, 8H), 7.70 -7.71(m, 3H), 7.78 (d, J=2.0 Hz, 1H), 7.93 (d, J=8.5 Hz, 1H), 8.18 (d, J=7.0 Hz, 1H), 8.31 (d, J=8.5 Hz, 1H), 8.44 (d, J=7.0 Hz, 1H), 8.48 (d, J=9.0 Hz, 1H), 8.65 (d, J=5.5 Hz, 1H), 10.26 (s, 1H).

[0098] Synthesis of PtS6: A reaction flask was charged with PtS6 (140 mg, 0.13 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (48 mg, 0.14 mmol, 1.05 equiv.), and sodium acetate (32 mg, 0.39 mmol, 3.0 equiv.), and diethylene glycol dimethyl ether (10 mL) was added. The reaction was continued at 120 °C for 72 h, then the reaction was stopped. The mixture was cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 97 mg of a pale yellow solid (65% yield). 1 H NMR (500 MHz, CDCl3) δ 1.22 (s, 9H), 1.44 (s, 9H), 1.47 (s, 9H), 6.33 (dd, J=6.0 , 2.0 Hz, 2H), 6.67 -7.18(m, 10H), 7.36-7.68(m, 9H), 7.95−8.01(m, 3H), 8.05 (dd, J=8.5, 3.5 Hz, 2H), 8.29 (dd, J=8.5, 5.0 Hz, 2H), 9.09 (d, J=6.0 Hz, 1H).

[0099] Example 13 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtS2 is as follows. Synthesis of intermediate LNH-PtS2: dPh-NH2 (200 mg, 0.6 mmol, 1.0 equiv.) was added to a reaction flask, followed by tBu-4S-Cl (371 mg, 0.63 mmol, 1.05 equiv.), tris(dibenzylideneacetone)dipalladium (34 mg, 0.04 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (22 mg, 0.08 mmol, 6 mol%), and sodium tert-butoxide (115 mg, 1.2 mmol, 2.0 equiv.). Toluene (5 mL) was added. The reaction was quenched in an oil bath at 85 °C for 3 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to give 374 mg of a white solid in 65% yield. It was used directly in the subsequent reaction.

[0100] Synthesis of the ligand L-PtS2: LNH-2 (374 mg, 0.42 mmol, 1.0 equiv.) was added to a reaction flask, followed by ammonium hexafluorophosphate (137 mg, 0.84 mmol, 2.0 equiv.) and triethyl orthoformate (5 mL). The reaction was then stopped at 80 °C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 372 mg of a white solid in 83% yield. 1 H NMR (500 MHz, DMSO) δ 1.30 (s, 9H), 1.32 (s, 9H), 6.91 (t, J=2.0 Hz, 1H), 6.97 (t, J=2.0 Hz, 1H), 7.12 ― 7.15 (m, 9H), 7.38 (dd, J=8.5, 2.0 Hz, 1H), 7.47−7.49 (m, 1H), 7.52−7.61(m, 7H), 7.70−7.72(m, 1H), 7.76 (d, J=8.0 Hz, 2H), 7.79 (d, J=1.5 Hz, 1H), 7.84 (s, 1H), 7.92―7.96(m, 2H), 8.18 (d, J=7.0 Hz, 1H), 8.31 (d, J=8.5 Hz, 1H), 8.44 (d, J=7.0 Hz, 1H), 8.49 (d, J=9.0 Hz, 1H), 8.65 (d, J=5.5 Hz, 1H), 10.34 (s, 1H).

[0101] Synthesis of PtS2: L-PtS2 (250 mg, 0.24 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (87 mg, 0.25 mmol, 1.05 equiv.), and sodium acetate (60 mg, 0.72 mmol, 3.0 equiv.) were added to a reaction flask, and diethylene glycol dimethyl ether (10 mL) was added. The reaction was continued at 120 °C for 72 hours to terminate the reaction. The mixture was then cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 136 mg of a pale yellow solid, a yield of 52%. 1H NMR (500 MHz, DMSO) δ 1.33 (s, 9H), 1.43 (s, 9H), 6.25−6.90 (m, 6H), 6.97−7.51 (m, 10H), 7.53−7.90 (m, 7H), 8.15 (d, J=8.5 Hz, 2H), 8.21 (d, J=8.0 Hz, 1H), 8.54 (dd, J=8.0, 4.0 Hz, 2H), 8.61 (d, J=9.0 Hz, 1H), 8.84 (d, J=6.0 Hz, 1H).

[0102] Example 14 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtS1 is as follows. Synthesis of intermediate 4S-Cl: 4S-OH (1.0 g, 2.4 mmol, 1.0 equiv.), m-chlorobromobenzene (689 mg, 3.6 mmol, 1.5 equiv.), 2-picolinic acid (60 mg, 0.48 mmol, 20 mmol), copper iodide (45 mg, 0.24 mmol, 10 mmol), and potassium phosphate (1.02 g, 4.8 mmol, 2.0 equiv.) were added to a reaction flask, and dimethyl sulfoxide (10 mL) was added. The reaction was then quenched at 110 °C for 12 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 868 mg of a white solid in 71% yield. 1 H NMR (500 MHz, DMSO) δ 1.32 (s, 9H), 7.08 ―7.10 (m, 2H), 7.19―7.24(m, 2H), 7.29 (dd, J=8.5, 2.0 Hz, 1H), 7.39 ―7.44(m, 2H), 7.52-7.60(m, 3H), 7.74 (d, J=1.0 Hz, 1H), 7.92 (d, J=9.0 Hz, 1H), 8.16-8.18 (m, 1H), 8.23 ​​(d, J=8.5 Hz, 1H), 8.42 -8.46(m, 2H), 8.64 -8.65 (m, 1H).

[0103] Synthesis of intermediate LNH-PtS1: A reaction flask was charged with dPh-NH2 (242 mg, 0.72 mmol, 1.0 equiv.), 4S-Cl (400 mg, 0.75 mmol, 1.03 equiv.), tris(dibenzylideneacetone)dipalladium (66 mg, 0.072 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (43 mg, 0.14 mmol, 6 mol%), and sodium tert-butoxide (119 mg, 1.44 mmol, 2.0 equiv.), and toluene (5 mL) was added. The reaction was quenched in an oil bath at 85 °C for 3 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 505 mg of a white solid in 78% yield. It was used directly in the subsequent reaction.

[0104] Synthesis of ligand L-PtS1: LNH-PtS1 (505 mg, 0.61 mmol, 1.0 equiv.), ammonium hexafluorophosphate (199 mg, 1.22 mmol, 2.0 equiv.), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was then stopped at 80 °C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 416 mg of a white solid in 63% yield. 1 H NMR (500 MHz, DMSO) δ 1.32 (s, 9H), 7.04 (t, J=2.0 Hz, 1H), 7.10 -7.18(m, 11H), 7.37 (dd, J=8.5, 2.0 Hz, 1H), 7.44-7.48(m, 2H), 7.53-7.61(m, 6H), 7.71-7.77(m, 4H), 7.80 (d, J=2.5 Hz, 1H), 7.93-7.96(m, 2H), 8.18 (d, J=7.0 Hz, 1H), 8.32 (d, J=8.5 Hz, 1H), 8.43-8.50(m, 2H), 8.66 (d, J=6.0 Hz, 1H), 10.35 (s, 1H).

[0105] Synthesis of PtS1: A reaction flask was charged with L-PtS1 (310 mg, 0.31 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (115 mg, 0.33 mmol, 1.05 equiv.), and sodium acetate (76 mg, 0.93 mmol, 3.0 equiv.), and diethylene glycol dimethyl ether (10 mL) was added. The reaction was continued at 120 °C for 72 h, then the mixture was cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 108 mg of a pale yellow solid (34% yield). 1 H NMR (500 MHz, CDCl3) δ 1.31 (s, 9H), 6.25 (dd, J=6.0, 1.5 Hz, 1H), 6.30 - 6.97 (m, 8H), 6.99 - 7.15 (m, 4H), 7.18 - 7.24 (m, 1H), 7.26 - 7.31 (m, 2H), 7.47 - 7.57 (m, 7H), 7.96 (d, J=8.0 Hz, 1H), 8.00 (d, J=8.5 Hz, 1H), 8.04 (d, J=8.0Hz, 1H), 8.17 (d, J=2.0 Hz, 1H), 8.23 ​​(d, J=8.5 Hz, 1H), 8.29 - 8.31(m, 2H), 9.04 (d, J=6.0 Hz, 1H).

[0106] Example 15 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtS5 is as follows. Synthesis of intermediate LNH-PtS5: A reaction flask was charged with dPh-NH2 (281 mg, 0.72 mmol, 1.1 equiv.), 4S-Cl (344 mg, 0.65 mmol, 1.0 equiv.), tris(dibenzylideneacetone)dipalladium (24 mg, 0.03 mmol, 3 mol%), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (21 mg, 0.06 mmol, 6 mol%), and sodium tert-butoxide (125 mg, 1.30 mmol, 2.0 equiv.), followed by addition of toluene (5 mL). The reaction was quenched in an oil bath at 110 °C for 3 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 480 mg of a white solid in 83% yield. It was used directly in the subsequent reaction.

[0107] Synthesis of ligand L-PtS5: LNH-PtS5 (480 mg, 0.54 mmol, 1.0 equiv.), ammonium hexafluorophosphate (176 mg, 1.08 mmol, 2.0 equiv.), and triethyl orthoformate (5 mL) were added to a reaction flask. The reaction was then stopped at 70 °C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 187 mg of a white solid in 33% yield. 1 H NMR (500 MHz, DMSO) δ 1.32 (s, 9H), 1.43 (s, 9H), 7.01 (t, J=2.0 Hz, 1H), 7.05 - 7.2 1 (m, 11H), 7.37 (dd, J=8.5, 2.0 Hz, 1H), 7.42 - 7.48 (m, 2H), 7.51 - 7.61 (m, 6H), 7.68 - 7.77 (m, 4H), 7.80 (d, J=1.5 Hz, 1H), 7.94 (d, J=9.0 Hz, 1H), 8.18 (d, J=7.5 Hz, 1H), 8.32 (d, J=8.5 Hz, 1H), 8.44 (d, J=6.5 Hz, 1H), 8.49 (d, J=9.0 Hz, 1H), 8.66 (d, J=6.0 Hz, 1H), 10.27 (s, 1H).

[0108] Synthesis of PtS5: A reaction flask was charged with L-PtS5 (168 mg, 0.16 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (58 mg, 0.17 mmol, 1.05 equiv.), and sodium acetate (39 mg, 0.48 mmol, 3.0 equiv.), and diethylene glycol dimethyl ether (10 mL) was added. The reaction was continued at 120 °C for 72 h, then the mixture was cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 44 mg of a pale yellow solid (25% yield). 1 H NMR (500 MHz, DMSO-d6) δ 1.22 (s, 9H), 1.44 (s, 9H), 6.34 (dd, J=6.5, 2.0 Hz, 1H), 6.90 (d, J=8.0 Hz, 7H), 7.04 - 7.09 (m, 4H), 7.24 (d, J=7.5 Hz, 2H), 7.27 (s, 1H), 7.46 - 7.57 (m, 7H), 7.99 - 8.01 (m, 3H), 8.05 (d, J=8.5 Hz, 2H), 8.28 - 8.31 (m, 2H), 9.11 (d, J=5.0 Hz, 1H).

[0109] Example 16 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtS27 is as follows. PtS27 was synthesized by following the synthesis steps and reaction conditions of compound PtS06 in Example 12. The synthesized target product, LNH-PtS27, was 1.07 g of a light green foam-like solid, with a yield of 71%. The synthesized target product, L-PtS27, was 861 mg of a light green foam-like solid, with a yield of 75%. Molecular weight [M] + The molecular weight [M+H] of the target product PtS27 was 325 mg of a yellow solid, with a yield of 66%. + :1310.7.

[0110] Example 17 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtS28 is as follows. PtS28 was synthesized by following the synthesis steps and reaction conditions of compound PtS06 in Example 12. The synthesized target product, LNH-PtS28, was 1.19 g of a light green foam-like solid, with a yield of 78%. The synthesized target product, L-PtS28, was 841 mg of a light green foam-like solid, with a yield of 74%. Molecular weight [M] + The molecular weight [M+H] was 1145.6. The target product PtS28 was a yellow solid, 385 mg, with a yield of 46%. + :1338.7.

[0111] Example 18 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtS13 is as follows. JPEG0007827785000044.jpg3357 PtS13 was synthesized by referring to the synthesis steps and reaction conditions of compound PtS06 in Example 12. The synthesized target product LNH-PtS13 was 1.19 g of a light green foam-like solid, with a yield of 76%. The synthesized target product L-PtS13 was 891 mg of a light green foam-like solid, with a yield of 78%. Molecular weight [M] + The molecular weight [M+H] was 929.2. The target product PtS28 was a yellow solid, 325 mg, with a yield of 36%. + :1122.3.

[0112] Example 19 The synthesis route of the tetradentate platinum(II) complex phosphorescent material PtS17 is as follows. JPEG0007827785000045.jpg3158 PtS17 was synthesized by referring to the synthesis steps and reaction conditions of compound PtS06 in Example 12. The synthesized target product LNH-PtS17 was 1.19 g of a light green foam-like solid, with a yield of 77%. The synthesized target product L-PtS17 was 891 mg of a light green foam-like solid, with a yield of 78%. Molecular weight [M] +The molecular weight [M+H] was 1041.5. The target product PtS17 was a yellow solid, 325 mg, with a yield of 36%. + :1232.5.

[0113] Example 20 Synthesis of PtO52 PtO52 was synthesized by following the synthesis steps and reaction conditions of compound PtO6 in Example 1. The target product was obtained as a yellow solid (562 mg) with a yield of 35%. Molecular weight [M+H] + :1472.6.

[0114] Example 21 Synthesis of PtO74 PtO74 was synthesized by following the synthesis steps and reaction conditions of compound PtO6 in Example 1. The target product was obtained as a yellow solid (604 mg) with a yield of 58%. Molecular weight [M+H] + :1362.6.

[0115] Example 22 Synthesis of PtO88 PtO88 was synthesized by following the synthesis steps and reaction conditions of compound PtO6 in Example 1. The target product was obtained as a yellow solid (624 mg) with a yield of 58%. Molecular weight [M+H] + :1474.7.

[0116] Example 23 Synthesis of PtO89 PtO89 was synthesized by following the synthesis steps and reaction conditions of compound PtO6 in Example 1. The target product was obtained as a yellow solid (661 mg) with a yield of 72%. Molecular weight [M+H] + :1316.5.

[0117] Example 24 Synthesis of PtO140 PtO140 was synthesized by following the synthesis steps and reaction conditions of compound PtO6 in Example 1. The target product was obtained as a yellow solid (455 mg) with a yield of 69%. Molecular weight [M+H] + :1236.5.

[0118] Example 25 Synthesis of PtO144 PtO144 was synthesized by following the synthesis steps and reaction conditions of compound PtO6 in Example 1. The target product was obtained as a yellow solid (471 mg) with a yield of 80%. Molecular weight [M+H] + :1280.5.

[0119] Example 26 Synthesis of PtO150 PtO150 was synthesized by following the synthesis steps and reaction conditions of compound PtO6 in Example 1. The target product obtained was a yellow solid (596 mg) with a yield of 56%. Molecular weight [M+H] + :1187.4.

[0120] Example 27 Synthesis of PtO158 PtO158 was synthesized by following the synthesis steps and reaction conditions of compound PtO6 in Example 1. The target product was obtained as a yellow solid (369 mg) with a yield of 58%. Molecular weight [M+H] + :1205.4.

[0121] Example 28 Synthesis of PtS47 PtS47 was synthesized by following the synthesis steps and reaction conditions of compound PtS6 in Example 12. The target product was obtained as a yellow solid (492 mg) with a yield of 82%. Molecular weight [M+H] + :1369.6.

[0122] Example 29 Synthesis of PtS87 PtS87 was synthesized by following the synthesis steps and reaction conditions of compound PtS6 in Example 12. The target product was obtained as a yellow solid (596 mg) with a yield of 74%. Molecular weight [M+H] + :1518.7.

[0123] Example 30 Synthesis of PtS93 PtS93 was synthesized by following the synthesis steps and reaction conditions of compound PtS6 in Example 12. The target product was obtained as a yellow solid (615 mg) with a yield of 68%. Molecular weight [M+H] + :1088.4.

[0124] Example 31 Synthesis of PtS135 PtS135 was synthesized by following the synthesis steps and reaction conditions of compound PtS6 in Example 12. The target product was obtained as a yellow solid (582 mg) with a yield of 66%. Molecular weight [M+H] + :1279.6.

[0125] Theoretical calculations were performed using density functional theory (DFT) to optimize the ground-state (S0) molecular geometry. DFT calculations were performed using the B3LYP functional, where C, H, O, and N atoms use the 6-31G(d) basis set and Pt atoms use the LANL2DZ basis set.

[0126] JPEG0007827785000046.jpg6359JPEG0007827785000047.jpg8160JPEG0007827785000048.jpg7962From the calculation data in Table 1, it can be seen that by introducing fused rings at different positions of carbazole, the conjugated system is expanded and the distribution of local excited states is increased, which results in a lower emission shoulder peak and narrower half-peak width, resulting in higher color purity and meeting the requirements for blue materials.

[0127] photophysical properties JPEG0007827785000049.jpg4260

[0128] Figures 1 to 13 show the room temperature emission spectra of R1 and some compounds of the present invention in dichloromethane solution, respectively. As can be seen from Figures 1 to 13 and Table 2, the complexes provided by the present invention have an expanded conjugated system due to the introduction of fused rings at different positions of carbazole, which increases the distribution of local excited states. This results in a significantly lower emission shoulder peak, a narrower half-peak width, and higher color purity.

[0129] OLED device manufacturing In the present invention, a reference fabrication method for device examples is to fabricate an OLED device by depositing a p-dopant material on the surface or anode of an ITO glass sheet with a light-emitting area of ​​2 mm x 2 mm, or by co-depositing a p-dopant material with a hole-injection material at a concentration of 1% to 50% to form a 5-100 nm hole-injection layer (HIL) and a 5-200 nm hole-transport layer (HTL). Subsequently, a 10-100 nm light-emitting layer (EML) (which may contain a compound described in this invention) is formed on the hole-transport layer. A 20-200 nm electron-transport layer (ETL) and a 50-200 nm cathode are then formed. If necessary, an electron barrier layer (EBL) is added between the HTL and the EML, and an electron-injection layer (EIL) is added between the ETL and the cathode. The OLED device is then tested using standard methods. Unless otherwise specified, all of the device materials of the present invention can be obtained by known synthetic methods.

[0130] In a preferred specific embodiment, the structure of the device example 1 provided by the present invention is ITO / P-4 (10 nm) / NPD (60 nm) / HTH-85 (5 nm) / platinum(II) complex: HTH-85:ETH-45 (25 nm) (PtO6:HTH-85:ETH-45 mass ratio is 10:60:30) / ETH-5 (5 nm) / ET-14 (40 nm) / LiQ (1 nm) / Al (100 nm).

[0131] Device Examples 2 to 31 and Comparative Example 1 were each fabricated using a structure similar to Device Example 1, with the only difference being that PtO2, PtO5, PtO27, PtO33, PtO34, PtO37, PtO38, PtO93, PtO107, PtO109, PtS6, PtS2, PtS1, PtS5, PtS27, PtS28, PtS13, PtS17, PtO52, PtO74, PtO88, PtO89, PO140, PtO144, PtO150, PtO158, PtS47, PtS87, PtS93, PtS135, and R1 were used to replace PO6 in Device Example 1. The luminescence characteristics of the fabricated Comparative Example and each Device Example were tested using standard methods, and the data are shown in Table 3. The structural formula of such a device is as follows, where P-4 is HATCN and ET-14 is BPyTP: JPEG0007827785000050.jpg1263JPEG0007827785000051.jpg2346

[0132] JPEG0007827785000052.jpg5959JPEG0007827785000053.jpg8661JPEG0007827785000054.jpg8660JPEG0007827785000055.jpg1258

[0133] As can be seen from Table 3, compared to Comparative Example 1, Device Examples 1 to 31 produced in the present invention exhibited favorable device performance in terms of driving voltage, current efficiency, and device service life, and also significantly improved device color purity. The performance of each device example was improved based on the fact that the specific compound material of the present invention has a small emission shoulder peak and better electron transport ability. As can be seen from this, when it is used as an emitting layer material in an electronic device, it reduces the driving voltage and provides higher current efficiency, device service life, and color purity. This indicates that the compound provided by the present invention has certain commercial value. Furthermore, all of the devices produced by the present invention are deep blue devices.

[0134] In a preferred embodiment, the structure of device example 32 provided by the present invention is ITO / P-4 (10 nm) / NPD (60 nm) / HTH-85 (5 nm) / platinum(II) complex:boron-containing compound:HTH-85:ETH-45 (25 nm) (PtO6:BN1-8:HTH-85:ETH-45 mass ratio is 10:1:59:30) / ETH-5 (5 nm) / ET-14 (40 nm) / LiQ (1 nm) / Al (100 nm).

[0135] Device Examples 33 to 39 were each fabricated using a structure similar to Device Example 32, with the only difference being that the platinum(II) complex and boron-containing compound in Device Example 32 were replaced with the compounds listed in Table 4. The structural formulas of the devices are as follows, and Table 4 can be referenced for device structure and luminescence property data. JPEG0007827785000056.jpg2561

[0136] JPEG0007827785000057.jpg5759JPEG0007827785000058.jpg4863

[0137] As can be seen from Table 4, when the compounds of the present invention were used as sensitizers in devices together with boron-containing compounds as luminescent materials, the performance of each device was significantly improved. This further demonstrates that the compounds provided by the present invention have certain commercial value. By adding a boron-containing compound and then sensitizing the device structure, the CIEy value can be reduced and the purity of the device's luminescent color can be improved.

[0138] A top-emission device D1 with PtO37 was also fabricated and compared with PtON-TBBI. The device structure was ITO / HT-1:P-5 (97:3) / HT-1 (126 nm) / p-host (5 nm) / p-host:ETH-45:PtO37 (60:32:8, 350 nm) / mSiTRz (5 nm) / ET-1:Liq (50:50, 30 nm) / Yb (1 nm) / Ag (14 nm) / CPL (60 nm). Comparative device D-R1 was fabricated by substituting PtON-TBBI for PtO37 in device D1. The data are shown in Table 5. The structural formulas of the device materials are as follows: JPEG0007827785000059.jpg4168

[0139] JPEG0007827785000060.jpg3659JPEG0007827785000061.jpg3162

[0140] As can be seen from Table 5, when the compound PtO37 of the present invention is used as a deep blue luminescent material together with PtON-TBBI as an luminescent material in a device, the half-peak width of the emission spectrum, color purity, external quantum efficiency, blue index and service life are all significantly improved, and at the same time, a high brightness of 1000 cd / m 2 The driving voltage at 1000 Hz was also significantly reduced. As can be seen from the above data, the deep blue light-emitting material of the present invention has great application prospects.

[0141] The applicant asserts that the above description is merely a specific embodiment of the present invention, and the protection scope of the present invention is not limited thereto. Those skilled in the art will understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed in the present invention will fall within the protection scope and disclosure scope of the present invention.

Claims

1. A fused-ring carbazole tetradentate platinum(II) complex characterized by having a general structure represented by formula (I), and a light-emitting material characterized by having a full width at half peak (FWHM) around the maximum emission in a dichloromethane (DCM) solution at room temperature of 19 nm or less. (In formula (I), X is selected from O or S, and R １ ~R ９ each independently represents mono-substitution to maximal substitution or no substitution; R １ ~R ９ are each independently selected from the group consisting of hydrogen, deuterium, halogen, CN, a C1-C30 alkyl group, a C1-C30 haloalkyl group, a C1-C30 deuterated alkyl group, a C6-C60 aryl group, a C6-C60 arylsilane, and combinations thereof.

2. R １ ~R ９ are independently hydrogen, deuterium, and CD ３ , F, C.F. ３ CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-amyl, 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, biphenyl, triphenylsilane, and combinations thereof.

3. R ３ , R ４ , R ９ are each independently selected from the group consisting of hydrogen, deuterium, F, CN, a methyl group, an isopropyl group, a tert-butyl group, a phenyl group, and combinations thereof.

4. R ６ , R ７ , R ８ are each independently selected from the group consisting of hydrogen, deuterium, a methyl group, a tert-butyl group, a phenyl group, and combinations thereof.

5. The fused ring carbazole tetradentate platinum(II) complex according to claim 1, characterized in that it has any one of the following chemical structures selected from the following: wherein "D" represents deuterium and Ph represents a phenyl group.

6. 6. Use of the fused ring carbazole tetradentate metal platinum(II) complex according to any one of claims 1 to 5 in an electronic device comprising 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 photodetector, an organic photoreceptor, an organic field quenching device, a light emitting electrochemical cell or an organic laser diode.

7. An organic electroluminescence device comprising a cathode, an anode, and an organic functional layer interposed between the cathode and the anode, the organic functional layer containing the fused ring carbazole tetradentate metal platinum(II) complex according to any one of claims 1 to 5.

8. 8. An organic electroluminescent device, wherein the organic functional layer comprises a light-emitting layer containing the fused ring carbazole tetradentate metal platinum(II) complex according to claim 7.

9. 9. The organic electroluminescent device according to claim 8, wherein the light-emitting layer further contains a fluorescent dopant material that is a boron-containing compound.

10. 10. An organic photoelectric device comprising: a substrate layer; a first electrode on the substrate layer; an organic light-emitting functional layer on the first electrode, the organic light-emitting functional layer containing the fused ring carbazole tetradentate metal platinum(II) complex according to claim 1; and a second electrode on the organic light-emitting functional layer.

11. 11. The organic photoelectric device according to claim 10, wherein the organic light-emitting functional layer further contains a fluorescent dopant material which is a boron-containing compound.

12. A composition comprising the fused ring carbazole tetradentate platinum(II) complex according to any one of claims 1 to 5.

13. A preparation comprising the fused ring carbazole tetradentate platinum(II) complex according to any one of claims 1 to 5.

14. 10. A display or lighting device comprising one or more organic electroluminescent devices according to claim 9.

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