Fluorine-containing tetradentate cyclometalated platinum(II) complexes, electronic devices, and their applications

Abstract

To provide a fluorine-containing tetradentate cyclometalated platinum (II) complex, an electronic device and application thereof.SOLUTION: A fluorine-containing tetradentate cyclometalated platinum (II) complex has a structure shown in formula (I) or formula (II). [In the formula (I) or formula (II), Fn indicates that there are one or more F substitutions on a benzene ring where it is located, where n is a positive integer from 1 to 5].SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention belongs to the field of organic electroluminescence, and more particularly to fluorine-containing tetradentate cyclometalated platinum(II) complexes, electronic devices, and their applications. [Background technology]

[0002] Organic light-emitting diodes (OLEDs) are a new generation of full-color display and lighting technology. Compared to liquid crystal displays (LCDs), which have drawbacks such as slow response speed, narrow viewing angle, the need for a backlight, and high power consumption, OLEDs are self-emissive devices that do not require a backlight, are energy-efficient, have low driving voltage, fast response speed, high resolution and contrast, wide viewing angle, and outstanding low-temperature characteristics. OLED devices can be made into thinner and more flexible structures. They also have the advantages of low manufacturing costs, simple manufacturing processes, and the ability to be manufactured in large areas. Therefore, OLEDs have enormous potential for a wide range of applications in high-end electronic products and the aerospace sector. As investment gradually increases, research and development deepens, and manufacturing equipment is upgraded and improved, OLEDs will have a very wide range of application scenarios and development prospects in the future.

[0003] The core of OLED development lies in the design and development of light-emitting materials. Many of the light-emitting layers in currently applied OLED devices use a host-guest light-emitting system mechanism in which a guest light-emitting material is doped into a host material. Generally, the energy gap of the host material is larger than that of the guest light-emitting material, transferring energy from the host material to the guest material, exciting the guest material and causing it to emit light. Commonly used organic phosphorescent guest materials are heavy metal atoms such as iridium(III), platinum(II), and Pd(II). Commonly used phosphorescent organic materials mCBP(3,3'-bIs(9-carbazolyl)-bIphenyl) and 2,6-mCPy(2,6-bIs(9-carbazolyl)-pyrIdIne) possess high efficiency and high triplet energy levels, and when used as organic materials, they can efficiently transfer triplet energy from the organic light-emitting material to the guest phosphorescent light-emitting material. However, due to the characteristics of mCBP, which allows for easy hole transport but poor electron flow, and the fact that 2,6-mCPy has poor hole transport, the charge balance of the luminescent layer is disrupted, and the current efficiency of the luminescent layer decreases. Furthermore, the number of heavy metal phosphorescent organic complex molecules, specifically iridium(III) cyclometalate complex molecules, currently in use is limited. The abundance of metallic platinum in the Earth's crust and the total annual global production are about 10 times that of metallic iridium, and IrCl3 is used to prepare iridium(III) complex phosphorescent materials. . The price of H2O is also far higher than the price of PtCl2, which is used in the preparation of platinum(II) complex phosphorescent materials. Furthermore, the preparation of iridium(III) complex phosphorescent materials involves four-step reactions: ligand exchange of iridium(III)-containing dimers and iridium(III) intermediates, synthesis of mer-iridium(III) complexes, and conversion from mer- to fac-iridium(III) complex isomers, which significantly reduces the overall yield. .The utilization rate of H2O is significantly reduced, increasing the preparation cost of iridium(III) complex phosphorescent materials. In contrast, the preparation of platinum(II) complex phosphorescent materials only requires the final stage reaction of ligand metallization and design platinum salt, resulting in a high utilization rate of platinum elements and further reducing the preparation cost of platinum(II) complex phosphorescent materials. In short, the preparation cost of platinum(II) complex phosphorescent materials is far lower than that of iridium(III) complex phosphorescent materials. However, there are still technical difficulties in the development of platinum complex materials and devices, and improving the efficiency and lifespan of devices remains a crucial research topic. Therefore, the development of new phosphorescent metallic platinum(II) complexes is urgently needed. [Overview of the project] [Problems that the invention aims to solve]

[0004] The present invention has been made in view of the above circumstances and aims to provide fluorine-containing tetradentate cyclometalated platinum(II) complexes, electronic devices, and applications thereof. The fluorine-containing tetradentate cyclometalated platinum(II) complexes of the present invention can provide excellent performance to devices as guest phosphorescent materials for light-emitting layers. Furthermore, when tetradentate cyclometalated platinum(II) complexes are combined with specific host materials, it is possible to improve the current efficiency of electronic devices, particularly organic electroluminescent devices, extend the device life, and reduce the operating voltage of the components. [Means for solving the problem]

[0005] The present invention provides a fluorine-containing tetradentate cyclometalated platinum(II) complex having a structure represented by formula (I) or formula (II).

[0006] [ka] [In formula (I) or formula (II), F n This indicates that there is one or more F substitutions on the benzene ring where it is located, and n is a positive integer from 1 to 5. R aThis represents a mono, dya, tia, quaternary substitution or no substitution, and R a is selected from H or C1-C30 alkyl groups. R1, R2, and R3 are each independently selected from the group consisting of hydrogen, F, N, O, S, CN, C1-C30 alkyl groups, C1-C30 cycloalkyl groups, C1-C30 cycloheteroalkyl groups, C1-C30 haloalkyl groups, C6-C60 aryl groups, and C6-C60 heteroaryl groups.

[0007] Preferably, at least one of the hydrogen atoms among R1, R2, and R3 may be replaced with deuterium or F.

[0008] Preferably, R1 and R3 are each independently selected from hydrogen or a C1-C30 alkyl group.

[0009] More preferably, R2 is independently selected from hydrogen, deuterium, CN, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 heteroalkyl group, a substituted or unsubstituted C1-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 cycloheteralkyl group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C6-C60 heteroaryl group, wherein the heteroatom on the heteroalkyl group, cycloheteralkyl group, or heteroaryl group is selected from one or more of O, S, and / or N.

[0010] More preferably, the fluorine-containing tetradentate cyclometalated platinum(II) complex is selected from any one of the following chemical structural formulas, where "D" represents deuterium.

[0011] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0012] Furthermore, the present invention also provides applications of fluorine-containing tetradentate cyclometalated platinum(II) complexes having the structure represented by formula (I) or formula (II) in electronic devices.

[0013] Furthermore, examples of the aforementioned 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 electric field quenching devices (O-FQDs), light-emitting electrochemical cells (LECs), and organic laser diodes (O-lasers).

[0014] In another aspect, the present invention also provides an organic electroluminescent device comprising a fluorine-containing four-coordinate cyclometalated platinum(II) complex having a structure represented by the above formula (I) or formula (II).

[0015] Further, the organic electroluminescent device includes a cathode, an anode, and an organic functional layer interposed between the anode and the cathode, and the organic functional layer contains a fluorine-containing four-coordinate cyclometalated platinum(II) complex having a structure represented by formula (I) or formula (II) as described above.

[0016] Preferably, the organic functional layer includes a light-emitting layer, and the light-emitting layer contains a four-coordinate cyclometalated platinum(II) complex having a structure represented by the above formula (I) or formula (II).

[0017] Further, the light-emitting layer also contains a fluorescent doping material selected from any one or more of the compounds represented by formulas (BN1) to (BN5).

[0018] [Chemical formula] [In the formula, X is O, S, Se or NR 300 and X 1 , X 2 , X 3 , X 4 are each independently represented by O, S, Se or N, R b ~R e each independently represents mono-, di-, tri-, tetra-substituted or unsubstituted. R b ~R e are each independently selected from the group consisting of hydrogen, deuterium, N, a C1-C30 alkyl group, and a C6-C60 aryl group, and R4~R 11 each independently represents the group consisting of hydrogen, deuterium, N, a C1-C30 alkyl group, and a C6-C60 aryl group.]

[0019] Preferably, R4, R5, R6, and R9 are each independently selected from substituted or unsubstituted diphenylamines and substituted or unsubstituted carbazolyl groups, and the substitution may be multiple substitutions. If substituents are present, the substituents are selected from deuterium, C1-C30 alkyl groups, and C6-C30 aryl groups.

[0020] Preferably, R7 to R8, R 10 ~R 11 Each of these is independently selected from the group consisting of hydrogen, C1-C30 alkyl groups, and C6-C60 aryl groups.

[0021] More preferably, R4~R 11 At least one of the hydrogen atoms may be replaced by deuterium.

[0022] Furthermore, the fluorescent doping material is selected from one of the following chemical structural formulas, where Ph represents a phenyl group and D4 and D5 are substituted with 4 and 5 deuterium atoms, respectively.

[0023] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0024] In another embodiment, the present invention also provides an organic optoelectronic device comprising a substrate layer, a first electrode on the substrate, an organic light-emitting functional layer on the first electrode, and a second electrode on the organic light-emitting functional layer, wherein the organic light-emitting functional layer contains a fluorine-containing tetradentate cyclometalated platinum(II) complex having the structure represented by formula (I) or formula (II). For example, the platinum(II) complex may be included in the organic light-emitting functional layer as a light-emitting material.

[0025] Furthermore, the organic light-emitting functional layer also contains a fluorescent doping material having one or more compounds represented by formulas (BN1) to (BN5) above.

[0026] The present invention also provides compositions containing a tetradentate cyclometalated platinum(II) complex having the structure represented by formula (I) or formula (II) above. Preferably, the compositions also contain a fluorescent doping material having one or more compounds represented by formulas (BN1) to (BN5) above.

[0027] The present invention also provides a fluorine-containing tetradentate cyclometalated platinum(II) complex having the structure represented by formula (I) or formula (II) above, or a formulation containing the above composition and at least one solvent. The solvent is not particularly limited, and any solvent well known to those skilled in the art can be used, such as unsaturated hydrocarbon solvents like toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene; halogenated saturated hydrocarbon solvents like carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, and bromocyclohexane; halogenated unsaturated hydrocarbon solvents like chlorobenzene, dichlorobenzene, and trichlorobenzene; ether-type solvents like tetrahydrofuran and tetrahydropyran; and ester-type solvents like alkyl benzoate.

[0028] Preferably, the composition also contains a fluorescent doping material selected from one or more compounds represented by formulas (BN1) to (BN5).

[0029] The present invention also provides a display or lighting device that includes one or more of the above-mentioned organic optoelectronic devices. [Effects of the Invention]

[0030] Compared to the prior art, the advantageous effects of the present invention include: This invention provides a phosphorescent material of a fluorine-containing tetradentate cyclometalated platinum(II) complex. By introducing fluorine atoms to appropriate positions in the ligand, the charge distribution of the excited state is improved, and more charge transfer states from metal to pyridocarbene are introduced into the excited state of the material. 3 The material possesses MLCT (Multiple Cellular Coherence Tolerance), which improves emissivity and is beneficial for extending device life. The material according to the present invention has good chemical and thermal stability, making it easy to manufacture vapor-deposited OLED devices. After being combined with a fluorescent doping material, the transport of holes and electrons is balanced, and energy transfer between the host and guest becomes more efficient. Organic electroluminescent devices manufactured using the compound of the present invention as the light-emitting layer show clear improvements in current efficiency and lifespan, and the ignition voltage is significantly reduced. In particular, when used in combination with a phosphorescent boron-containing compound, the color purity of the light of the device can be improved. [Brief explanation of the drawing]

[0031] [Figure 1] This figure shows the room-temperature emission spectra of prepared platinum complexes Pt1 to Pt6 in a dichloromethane solution. [Modes for carrying out the invention]

[0032] The present invention will now be described in detail. The following descriptions of constituent elements may be based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.

[0033] As used herein, the term “substituted” includes all acceptable substituents of an organic compound. In broader embodiments, acceptable substituents include cyclic and acyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of an organic compound. Illustrative substituents are, for example, listed below. There may be one or more acceptable substituents, which may be the same or different for a given organic compound. For the purposes of the present invention, a heteroatom (e.g., nitrogen) may have a hydrogen substituent and / or any acceptable substituent of the organic compound described herein that satisfies the valence of the heteroatom. The present invention is not intended to limit in any sense with respect to the acceptable substituents of an organic compound. Similarly, the terms “substituted” or “substituted with” imply that such substitution is subject to the acceptable valence of the atom being substituted and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously transform, e.g., rearrange, cyclize, or eliminate). Furthermore, in certain embodiments, it is intended that individual substituents may be further substituted (i.e., may be further substituted or not) unless a clear contradiction is demonstrated.

[0034] In the definitions of various terms, "R1" to "R 11 In this specification, is used as a general symbol to represent various specific substituents. These symbols can be any substituent and are not limited to the substituents disclosed herein, and when defined in one example as a certain substituent, they may be defined in another example as a different substituent.

[0035] When used herein, "R 1 "R 2 "R 3 "..."R n The formula (where n is an integer) can independently contain one or more of the elements listed above. For example, R 1If the group is a linear alkyl group, one of the hydrogen atoms of the alkyl group may be substituted by a hydroxyl group, an alkoxy group, an alkyl group, a halogen, etc. Depending on the selected group, the first group may be incorporated into the second group, or the first group may be suspended (i.e., bonded) to the second group. For example, in the phrase “alkyl group containing an amino group”, the amino group may be bonded to the main chain of the alkyl group. The amino group may also be bonded to the main chain of the alkyl group. The properties of the selected group determine whether the first group is incorporated into or bonded to the second group.

[0036] As used herein, the term "alkyl" refers to a branched or unbranched saturated hydrocarbon group having 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, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, and tetracosyl. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups, including, but not limited to, substituted alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxy, nitro, silyl, sulfo-oxo, or mercapto groups as described herein.

[0037] As used herein, the term "aryl" refers to a group having 5 to 60 carbon atoms containing any carbon-based aromatic group, including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, anthryl, and phenantrenyl. The term "aryl" also includes "heteroaryl," which is defined as a group containing an aromatic group in which one heteroatom is 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 "nonheteroaryl" is also included in the term "aryl" and is defined as a group containing an aromatic group that does not contain a heteroatom. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with one or more groups, including, but is not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, halogen, hydroxy, carbonyl, azide, nitro, silyl, sulfo-oxo, or mercapto, as described herein.

[0038] As used herein, the terms "amine" or "amino" refer to formula -NR 1 R 2 It is expressed by, in the formula, R 1 and R 2 This group can be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl groups.

[0039] The compounds of the present invention may contain "optionally substituted" moieties. Generally, the term "substituted," whether preceded by the term "optionally," means that one or more hydrogens of a given moiety are substituted with appropriate substituents. Unless otherwise indicated, an "optionally substituted" group may have appropriate substituents at each of its substitutable positions, and the substituents may be the same or different at all positions when one or more positions of any given structure are substitutable with one or more substituents selected from a particular group. The substituent combinations envisioned in the present invention are preferably combinations that result in the formation of stable or chemically feasible compounds. Furthermore, in certain embodiments, it is intended that individual substituents may be optionally further substituted (i.e., further substituted or not substituted), unless it is clearly shown to be inconsistent.

[0040] The structure of the compound can be represented by the following formula.

[0041] [ka]

[0042] This equation is understood to be equivalent to the following equation.

[0043] [ka] [In the formula, n is usually an integer. That is, R n It consists of five independent substituents R a(1) , R a(2) , R a(3) , R a(4) , R a(5) This is understood to mean that "independent substituents" means that each R substituent can be defined independently. For example, in one example, R a(m) If R is a halogen, a(n) In that example, it does not necessarily have to be a halogen.

[0044] The compounds disclosed herein can exhibit desired properties and may have emission and / or absorption spectra that can be adjusted by selecting appropriate ligands. Furthermore, the present invention may exclude any one or more compounds, structures, or parts thereof specifically described herein.

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

[0046] Please note that the above summary and the following detailed description are merely illustrative and explanatory, and do not limit the invention.

[0047] This application can be more readily understood by referring to the following specific embodiments and examples contained herein.

[0048] Before disclosing and describing the compounds, apparatus and / or methods of the present invention, it should be understood that, unless otherwise specified, the invention is not limited to specific synthesis methods (as shown separately) or specific reagents (as shown separately), and is therefore naturally subject to variation. Furthermore, it should be understood that the terms used herein are for the purpose of describing specific embodiments only and are not intended to be limiting. Methods and materials similar to or equivalent to those described herein may be used in carrying out or testing the present invention, but exemplary methods and materials are described herein. All raw materials and solvents in the synthesis examples are commercially available unless otherwise specified, and the solvents were used without further treatment.

[0049] The substrate of the present invention can be any substrate used in typical organic optoelectronic devices, and may be a glass or transparent plastic substrate, an opaque material substrate such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and waterproofness, and their usage direction differs depending on the properties of the substrate. Any material can be selected from known materials used in OLED devices as the material for the hole injection layer, hole transport layer, and electron injection layer, and the present invention is not particularly limited thereto.

[0050] (Synthesis Examples) The following examples of compound synthesis, components, devices, or methods are intended solely to provide a general approach to the industry and are not intended to limit the scope of patent protection. While the data (quantities, temperatures, etc.) described in the patents are as accurate as possible, there may be some margin of error. Unless otherwise specified, weighing is performed separately, temperatures are in °C or room temperature, and pressures are close to atmospheric pressure.

[0051] The following examples provide methods for producing novel compounds, but the preparation of such compounds is not limited to these methods. In this technical field, the compounds for which protection is sought in the present invention are easily modified and prepared, and can therefore be prepared by the methods listed below or by other methods. The following examples are merely illustrative and are not intended to limit the scope of protection of this patent. Temperature, catalyst, concentration, reactants, and reaction process can be changed and used to prepare the compounds by selecting different conditions for different reactants.

[0052] 1 1H NMR (500 MHz), 1 1H NMR (400 MHz), 13 ¹³C NMR (126 MHz) spectra were measured using an ANANCE III (500 M) nuclear magnetic resonance spectrometer. Unless otherwise specified, nuclear magnetic fields were measured using either DMSO-d6 or CDCl3 containing 0.1% TMS as the solvent. 1When using CDCl3 as the solvent for the 1H NMR spectrum, TMS (δ=0.00 ppm) is used as the internal standard. When using DMSO-d6 as the solvent, TMS (δ=0.00 ppm), the residual DMSO peak (δ=2.50 ppm), or the residual water peak (δ=3.33 ppm) is used as the internal standard. 13 In the 13C NMR spectrum, either CDCl3 (δ=77.00 ppm) or DMSO-d6 (δ=39.52 ppm) was used as an internal standard. HPLC-MS was measured using an AgIlent 6210 TOF LC / MS mass spectrometer, and HRMS spectra were measured using an AgIlent 6210 TOF LC / MS liquid chromatograph-time-of-flight mass spectrometer. 1 1H NMR spectral data: s=sInglet, d=doublet, t=trIplet, q=quartet, p=quIntet, m=multIplet, br = broad.

[0053] (Synthesis of Intermediate 1) The synthesis route for intermediate 1 is as follows:

[0054] [ka]

[0055] (1) Equipped with a magnetic stirring rod, A (256 mg, 1.0 mmol, 1.0 equivalent), B (210 mg, 1.5 mmol, 1.5 equivalent), tetrakis(triphenylphosphine)palladium (29 mg, 0.025 mmol, 0.025 equivalent), and tripotassium phosphate (425 mg, 2.0 mmol, 2.0 equivalent) were sequentially added to a dry sealed tube. After three nitrogen purgings, dioxane (8 mL) and water (2 mL) were added under nitrogen protection. The mixture was placed in an oil bath at 60°C and stirred, reacting for 12 hours. After cooling to room temperature, the solvent was removed under reduced pressure. The resulting crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 2:1) to obtain product C as a red liquid of 183 mg (yield 88%). This was used directly in the next step.

[0056] (2) Equipped with a magnetic stirring rod, C (180 mg, 0.71 mmol, 1.0 equivalent), D (130 mg, 0.65 mmol, 1.1 equivalent), tris(dibenzylideneacetone)dipalladium (6 mg, 0.065 mmol, 0.01 equivalent), 2,2'-bis(diphenylphosphin)-1,1'-binaphthyl (16 mg, 0.026 mmol, 0.04 equivalent), and cesium carbonate (263 mg, 0.81 mmol, 1.25 equivalent) were sequentially added to a dry sealed tube, and after three nitrogen purgings, toluene (5 mL) was added under nitrogen protection, and the mixture was stirred in an oil bath at 120°C and reacted for 12 hours, after which it was cooled to room temperature and the solvent was removed by distillation under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 10:1) to obtain product E as a yellow solid of 981 mg (yield 84%). This was then used directly in the next step.

[0057] (3) E (6.52 g, 17.4 mmol, 1.0 equivalent) and stannous chloride dihydrate (16 g, 69.6 mmol, 4.0 equivalents) were sequentially added to a dry sealed tube equipped with a magnetic stirring rod, and after three nitrogen purgings, ethanol (60 mL) and ethyl acetate (60 mL) were added under nitrogen protection, and the mixture was placed in an oil bath at 78°C and stirred, reacting for 9 hours, then cooled to room temperature, and the solvent was removed under reduced pressure. The resulting crude product was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 5:1) to obtain intermediate 1 as 5.7 g of purple solid (yield 90%).

[0058] (Synthesis of intermediate 1-Cl) The synthesis route for intermediate 1-Cl is as follows:

[0059] [ka]

[0060] (1) Equipped with a magnetic stirring rod, F (10 g, 50.7 mmol, 1.0 equivalent), G (13 g, 60.8 mmol, 1.2 equivalents), Tris(dibenzylideneacetone)dipalladium (464 mg, 0.5 mmol, 0.01 equivalents), 2-(di-tert-butylphosphino)biphenyl (303 mg, 1.0 mmol, 0.02 equivalents), and sodium tert-butoxide (9.7 g, 101 mmol, 2.0 equivalents) were sequentially added to a dry sealed tube, and after three nitrogen purgings, toluene (80 mL) was added under nitrogen protection, and the mixture was placed in an oil bath at 110°C and stirred, reacting for 12 hours, then cooled to room temperature, and the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 30:1) to obtain product H as 15 g of a yellow oily liquid (yield 91%).

[0061] (2) Equipped with a magnetic stirring rod, H (28 g, 84.7 mmol, 1.0 equivalent) and hydrobromic acid (69 g, 0.847 mmol, 10.0 equivalent) were sequentially added to a dry sealed tube, and the mixture was stirred in an oil bath at 120°C and reacted for 12 hours. After cooling to room temperature, the solvent was removed under reduced pressure. The resulting crude product was made into a paste and filtered to obtain Product I as a white solid of 26 g (yield 97%).

[0062] (3) Equipped with a magnetic stirring rod, I (5 g, 15.8 mmol, 1.0 equivalent), J (3.3 g, 17.4 mmol, 1.1 equivalent), cuprous iodide (300 mg, 1.58 mmol, 0.1 equivalent), 2-picolinic acid (389 mg, 3.16 mmol, 0.2 equivalent), and tripotassium phosphate (6.7 g, 31.6 mmol, 2.0 equivalent) were sequentially added to a dry sealed tube, and after three nitrogen purgings, dimethyl sulfoxide (50 mL) was added under nitrogen protection. The mixture was placed in an oil bath at 100°C and stirred, reacted for 12 hours, then cooled to room temperature, and the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 20:1) to obtain the product intermediate 1-Cl as a white solid of 5.3 g (yield 79%).

[0063] The above provides only one feasible preparation scheme for the intermediates of the present invention, and it should be noted that the intermediates required for each example can be prepared by referring to the synthesis processes of intermediate 1 and intermediate 1-Cl. The preparation of these intermediate compounds is not limited to this method. Their preparation can be carried out by the methods listed above or by other methods commonly known in the art, and this does not limit the scope of protection of the present invention.

[0064] (Example 1: Synthesis of Pt1) The synthesis route for the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt1 is as follows:

[0065] [ka]

[0066] Synthesis of intermediate (1-NH): Equipped with a magnetic stirring rod, 1 (363 mg, 1.0 mmol, 1.0 equivalent), 1-Cl (470 mg, 1.1 mmol, 1.1 equivalent), tris(dibenzylideneacetone)dipalladium (27 mg, 0.03 mmol, 0.03 equivalent), 2-(di-tert-butylphosphino)biphenyl (18 mg, 0.06 mmol, 0.06 equivalent), and sodium tert-butoxide (192 mg, 2.0 mmol, 2.0 equivalent) were sequentially added to a dry sealed tube, followed by three nitrogen purging cycles. Toluene (5 mL) was added under nitrogen protection, and the mixture was stirred in a 100°C oil bath. After reacting for 12 hours, it was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 30:1) to obtain product 1-NH as a pale green foamy solid of 580 mg (yield 77%). This was used directly in the next step.

[0067] Synthesis of ligand L1: Equipped with a magnetic stirring rod, 1-NH (580 mg, 0.77 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (251 mg, 1.54 mmol, 2.0 equivalents) were sequentially added to a dry sealed tube, followed by three nitrogen purgings. Under nitrogen protection, triethyl orthoformate (10 mL) was added, and the mixture was placed in an oil bath at 80°C and stirred. After reacting for 10 hours, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The resulting crude product was separated and purified by silica gel chromatography (eluent: dichloromethane) to obtain product L1 as a pale green foamy solid of 483 mg (yield 69%). 1 H NMR (500 MHz, DMSO-d6): δ 1.09 (d, J = 7.0 Hz, 6H), 1.19 (d, J = 7.0 Hz, 6H), 1.32 (s, 9H), 2.36-2.42 (m, 2H), 7.24 (dd, J = 8.5, 6.0 Hz, 1H), 7.33 - 7.40 (m, 3H), 7.45 - 7.51 (m, 3H), 7.55 (d, J = 2.5 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H), 7.69 - 7.76 (m, 5H), 7.79 (q, J = 3.0Hz, 4H), 7.88 - 7.93 (m, 2H), 8.01 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 8.0 Hz, 1H), 8.35 (d, J = 8.5 Hz, 1H), 8.60 (d, J = 5.5 Hz, 1H), 10.62 (s, 1H).

[0068] Synthesis of Pt1: Equipped with a magnetic stirring rod, L1 (483 mg, 0.53 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum dichloride (198 mg, 0.53 mmol, 1.0 equivalent), and sodium acetate (216 mg, 1.59 mmol, 3.0 equivalents) were sequentially added to a dry sealed tube, followed by three nitrogen purgings. Under nitrogen protection, diethylene glycol dimethyl ether (30 mL) was added, and the mixture was bubbling with nitrogen gas for 30 minutes. The mixture was then wrapped in tin foil to prevent light from entering, and the mixture was stirred in an oil bath at 120°C. After reacting for 3 days, it was cooled to room temperature, deionized water was added and stirred for 5-10 minutes to quench, and dichloromethane was added for extraction. The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 2:1) to obtain product Pt1 as a yellow solid of 162 mg (yield 32%). 1 H NMR (500 MHz, DMSO-d6): δ 0.97 (s, 9H), 1.14 (d, J = 6.5 Hz, 6H), 1.17 (d, J = 6.5 Hz, 6H), 2.84 - 2.92 (m, 2H), 6.36 (dd, J = 6.5, 4.5 Hz, 1H), 6.78 (d, J =1.0 Hz, 1H), 7.14 (d, J = 8.0 Hz, 1H), 7.27 (d, J = 8.0 Hz, 1H),7.30 (d, J = 7.5 Hz, 2H), 7.37-7.41 (m, 5H), 7.46-7.52 (m, 2H), 7.54(s, 1H), 7.86 (d, J = 8.0 Hz, 2H), 7.89 (d, J = 8.5 Hz, 1H), 7.97 (dd, J = 9.0, 5.5 Hz, 2H), 8.14 (d, J = 7.0 Hz, 1H), 8.27 (d, J = 8.5 Hz, 1H), 8.65 (d, J = 6.0 Hz, 1H).

[0069] (Example 2: Synthesis of Pt2) The synthesis route for the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt2 is as follows:

[0070] [ka]

[0071] Synthesis of intermediate (2-NH): Equipped with a magnetic stirring rod, 1 (363 mg, 1.0 mmol, 1.0 equivalent), 2-Cl (531 mg, 1.1 mmol, 1.1 equivalent), tris(dibenzylideneacetone)dipalladium (27 mg, 0.03 mmol, 0.03 equivalent), 2-(di-tert-butylphosphino)biphenyl (18 mg, 0.06 mmol, 0.06 equivalent), and sodium tert-butoxide (192 mg, 2.0 mmol, 2.0 equivalent) were sequentially added to a dry sealed tube, followed by three nitrogen purging cycles. Toluene (5 mL) was added under nitrogen protection, and the mixture was stirred in a 100°C oil bath. After reacting for 12 hours, it was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 30:1) to obtain product 2-NH as a pale green foamy solid of 530 mg (yield 87%). This was then used directly in the next step.

[0072] Synthesis of ligand L2: Equipped with a magnetic stirring rod, 2-NH (702 mg, 0.64 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (203 mg, 1.84 mmol, 2.0 equivalents) were sequentially added to a dry sealed tube, followed by three nitrogen purgings. Under nitrogen protection, triethyl orthoformate (10 mL) was added, and the mixture was placed in an oil bath at 80°C and stirred. After reacting for 10 hours, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The resulting crude product was separated and purified by silica gel chromatography (eluent: dichloromethane) to obtain product L2 as 600 mg of pale green foamy solid (yield 72%). 1H NMR (500 MHz, DMSO): δ 1.15 (d, J = 5.0 Hz, 6H), 1.24 (d, J = 5.0 Hz, 6H), 1.37 (s, 9 H), 1.43 (s, 9 H), 2.39 - 2.48 (m, 2H), 7.29 (dd, J = 8.0, 6.0 Hz, 1H), 7.37 - 7.47 (m, 3H), 7.49 - 7.58 (m, 3H), 7.58 (t, J = 2.5 Hz, 1H), 7.59 (d, J = 2.5 Hz, 1H), 7.69 (d, J = 8.0 Hz, 1H), 7.74 (q, J = 2.0 Hz, 2H), 7.77-7.82 (m, 3H), 7.84 (s, 2H), 7.94-7.98 (m, 2H), 8.02 (d, J = 8.0 Hz, 1H), 8.30 (d, J = 8.0 Hz, 1H), 8.39 (d, J = 8.5 Hz, 1H), 8.64 (d, J = 5.0 Hz, 1H), 10.70 (s, 1H).

[0073] Synthesis of Pt2: Equipped with a magnetic stirring rod, L2 (600 mg, 0.62 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum dichloride (221 mg, 0.59 mmol, 1.0 equivalent), and sodium acetate (153 mg, 1.87 mmol, 3.0 equivalents) were sequentially added to a dry sealed tube, followed by three nitrogen purgings. Under nitrogen protection, 30 mL of diethylene glycol dimethyl ether was added, and the mixture was bubbling with nitrogen gas for 30 minutes. The mixture was then wrapped in tin foil to prevent light from entering, placed in an oil bath at 120°C, stirred, and reacted for 3 days. After cooling to room temperature, deionized water was added and stirred for 5-10 minutes to quench, dichloromethane was added for extraction, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 2:1) to obtain product Pt2 as 100 mg of yellow solid (yield 84%). 1H NMR (500 MHz, DMSO-d6): δ 0.94 - 1.29 (m, 21H), 1.49 (s, 9H), 2.70-3.01 (m, 2H), 6.34 (dd, J = 6.0, 4.0 Hz, 1H), 7.06 (d, J = 1.5 Hz, 1H), 7.14 (d, J = 8.5 Hz, 1H), 7.26 (d, J = 8.5 Hz, 1H), 7.35-7.45 (m, 5H), 7.49 (t, J = 6.0 Hz, 1H), 7.59 (t, J = 8.5 Hz, 1H), 7.66 (s, 1H), 7.73 (d, J = 1.5 Hz, 1H), 7.84 (d, J = 8.5 Hz, 2H), 7.87 (d, J = 8.5 Hz, 1H), 7.93 - 8.01 (m, 2H), 8.13 (d, J = 8.0 Hz, 1H), 8.36 (d, J = 8.5 Hz, 1H), 8.59 (d, J = 6.5 Hz, 1H).

[0074] (Example 3: Synthesis of Pt3) The synthesis route for the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt3 is as follows:

[0075] [ka]

[0076] Synthesis of intermediate (3-NH): Equipped with a magnetic stirring rod, 1 (363 mg, 1.0 mmol, 1.0 equivalent), 3-Cl (646 mg, 1.1 mmol, 1.1 equivalent), tris(dibenzylideneacetone)dipalladium (27 mg, 0.03 mmol, 0.03 equivalent), 2-(di-tert-butylphosphino)biphenyl (18 mg, 0.06 mmol, 0.06 equivalent), and sodium tert-butoxide (192 mg, 2.0 mmol, 2.0 equivalent) were sequentially added to a dry sealed tube, followed by three nitrogen purging cycles. Toluene (5 mL) was added under nitrogen protection, and the mixture was stirred in a 100°C oil bath. After reacting for 12 hours, it was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 30:1) to obtain product 3-NH as a pale green foamy solid of 730 mg (yield 80%). This was then used directly in the next step.

[0077] Synthesis of ligand L3: Equipped with a magnetic stirring rod, 3-NH (730 mg, 0.64 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (261 mg, 1.60 mmol, 2.0 equivalents) were sequentially added to a dry sealed tube, followed by three nitrogen purgings. Under nitrogen protection, triethyl orthoformate (10 mL) was added, and the mixture was placed in an oil bath at 80°C and stirred. After reacting for 10 hours, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The resulting crude product was separated and purified by silica gel chromatography (eluent: dichloromethane) to obtain product L3 as a pale green foamy solid of 633 mg (yield 74%). 1H NMR (500 MHz, DMSO-d6): δ 0.93 (d, J = 4.5 Hz, 6H), 1.10 (t, J = 6.5 Hz, 12H), 1.20 (d, J = 6.5 Hz, 6H), 1.34 (s, 9H), 2.39-2.45 (m, 2H), 2.58-2.64 (m, 2H), 7.09 (dd, J = 2.0, 1.0 Hz, 1H), 7.22 (d, J =7.5 Hz, 2H), 7.28 (dd, J = 8.5, 6.0 Hz, 1H), 7.33-7.40 (m, 4H), 7.46-7.53 (m, 3H), 7.57 (d, J = 2.5 Hz, 1H), 7.66 (d, J = 8.5 Hz, 1H), 7.71-7.79 (m, 3H), 7.80 (s, 2H), 7.83 (t, J = 8.5 Hz, 1H), 7.87 (t, J = 2.5 Hz, 1H), 7.89-7.93 (m, 2H), 8.02 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 7.5 Hz, 1H), 8.36 (d, J = 8.5 Hz, 1H), 8.60 (d, J = 5.5 Hz, 1H), 10.65 (s, 1H)。

[0078] Synthesis of Pt3: Equipped with a magnetic stirring rod, L3 (633 mg, 0.59 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum dichloride (222 mg, 0.59 mmol, 1.0 equivalent), and sodium acetate (241 mg, 1.78 mmol, 3.0 equivalents) were sequentially added to a dry sealed tube, followed by three nitrogen purgings. Under nitrogen protection, 30 mL of diethylene glycol dimethyl ether was added, and the mixture was bubbling with nitrogen gas for 30 minutes. The mixture was then wrapped in tin foil to prevent light from entering, placed in an oil bath at 120°C, stirred, and reacted for 3 days. After cooling to room temperature, deionized water was added and stirred for 5-10 minutes to quench, dichloromethane was added for extraction, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 2:1) to obtain product Pt3 as a yellow solid of 476 mg (yield 72%). 1 H NMR (500 MHz, DMSO-d6): δ 0.70 - 1.64 (m, 33H), 2.77 - 3.21 (m, 4H), 6.34 (dd, J = 6.0, 4.0 Hz, 1H), 7.06 (d, J = 8.0 Hz, 1H), 7.13 (d, J = 8.0 Hz, 1H), 7.26 (d, J = 8.0 Hz, 1H), 7.31-7.79 (m, 11H), 7.80-7.91 (m, 4H), 7.97 (dd, J = 5.5, 3.0 Hz, 2H), 8.13 (d, J = 6.5 Hz, 1H), 8.45 (d, J =8.0 Hz, 1H), 8.61 (d, J = 5.0 Hz, 1H).

[0079] (Example 4: Synthesis of Pt4) The synthesis route for the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt4 is as follows:

[0080] [ka]

[0081] Synthesis of intermediate 4-NH: Equipped with a magnetic stirring rod, 2 (413 mg, 1.0 mmol, 1.0 equivalent), 2-Cl (531 mg, 1.1 mmol, 1.1 equivalent), tris(dibenzylideneacetone)dipalladium (27 mg, 0.03 mmol, 0.03 equivalent), 2-(di-tert-butylphosphino)biphenyl (18 mg, 0.06 mmol, 0.06 equivalent), and sodium tert-butoxide (192 mg, 2.0 mmol, 2.0 equivalent) were sequentially added to a dry sealed tube, followed by three nitrogen purging cycles. Toluene (5 mL) was added under nitrogen protection, and the mixture was stirred in a 100°C oil bath. After reacting for 12 hours, it was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 30:1) to obtain product 4-NH as a pale green foamy solid of 661 mg (yield 77%). Due to its high oxidation rate and low stability, it was used directly in the next reaction.

[0082] Synthesis of ligand L4: Equipped with a magnetic stirring rod, 4-NH (661 mg, 0.77 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (251 mg, 1.54 mmol, 2.0 equivalents) were sequentially added to a dry sealed tube, followed by three nitrogen purgings. Under nitrogen protection, triethyl orthoformate (10 mL) was added, and the mixture was placed in an oil bath at 80°C and stirred. After reacting for 10 hours, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The resulting crude product was separated and purified by silica gel chromatography (eluent: dichloromethane) to obtain product L4 as 500 mg of pale green foamy solid (yield 64%). 1H NMR (500 MHz, DMSO-d6): δ 1.10 (d, J = 7.0 Hz, 6H), 1.19 (d, J = 6.5 Hz, 6H), 1.30 (s, 9H), 1.36 (s, 9H), 2.36-2.43 (m, 2H), 7.24 (dd, J = 8.5, 6.5 Hz,1H), 7.34 (t, J = 8.0 Hz, 1H), 7.45 - 7.54 (m, 5H), 7.65 (d, J =7.5 Hz, 1H),7.66 - 7.69 (m, 2H), 7.72 - 7.78 (m, 3H), 7.87 (s, 2H), 7.89 (d, J = 8.5 Hz, 2H), 7.96 (dd, J =8.0, 6.5 Hz,1H), 8.07 (d, J = 8.0 Hz, 2H), 8.24 (d, J = 7.5 Hz, 1H), 8.33 (d, J = 8.5 Hz, 1H), 8.58 (d, J = 5.5 Hz, 1H), 10.65 (s, 1H).

[0083] Synthesis of Pt4: Equipped with a magnetic stirring rod, L4 (500 mg, 0.49 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum dichloride (184 mg, 0.49 mmol, 1.0 equivalent), and sodium acetate (201 mg, 1.48 mmol, 3.0 equivalents) were sequentially added to a dry sealed tube, followed by three nitrogen purgings. Under nitrogen protection, diethylene glycol dimethyl ether (30 mL) was added, and the mixture was bubbling with nitrogen gas for 30 minutes. The mixture was then wrapped in tin foil to prevent light from entering, placed in an oil bath at 120°C, stirred, and reacted for 3 days. After cooling to room temperature, deionized water was added and stirred for 5-10 minutes to quench, dichloromethane was added for extraction, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 2:1) to obtain product Pt4 as a yellow solid of 466 mg (yield 89%). 1H NMR (500 MHz, DMSO-d6): δ 0.92-1.25 (m, 21H), 1.48 (s, 9H), 2.9-3.15 (m, 2H), 6.34 (dd, J = 4.0, 2.0 Hz, 1H), 7.06 (d, J = 1.5 Hz, 1H), 7.15 (d, J = 8.5 Hz, 1H), 7.25 (d, J = 8.5 Hz, 1H), 7.36 (t, J = 7.5 Hz, 1H), 7.43 (t, J = 7.5 Hz, 1H), 7.44-7.51 (m, 1H), 7.59 (t, J = 7.5 Hz, 1H), 7.67-7.84 (m, 5H), 7.87 (d, J = 8.5 Hz, 1H), 7.90 (d, J = 8.0 Hz, 2H), 8.11 (d, J = 7.5 Hz, 1H), 8.15 (d, J = 8.5 Hz, 2H), 8.36 (d, J = 8.0 Hz, 1H), 8.57 (d, J = 6.5 Hz, 1H).

[0084] (Example 5: Synthesis of Pt5) The synthesis route for the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt5 is as follows:

[0085] [ka]

[0086] Synthesis of intermediate 5-NH: Equipped with a magnetic stirring rod, 1 (363 mg, 1.0 mmol, 1.0 equivalent), 4-Cl (545 mg, 1.1 mmol, 1.1 equivalent), tris(dibenzylideneacetone)dipalladium (27 mg, 0.03 mmol, 0.03 equivalent), 2-(di-tert-butylphosphino)biphenyl (18 mg, 0.06 mmol, 0.06 equivalent), and sodium tert-butoxide (192 mg, 2.0 mmol, 2.0 equivalent) were sequentially added to a dry sealed tube. After three nitrogen purgings, toluene (5 mL) was added under nitrogen protection, and the mixture was stirred in an oil bath at 100°C and reacted for 12 hours. After cooling to room temperature, the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 30:1) to obtain product 5-NH as a pale green foamy solid of 525 mg (yield 64%). This was then used directly in the next reaction.

[0087] Synthesis of ligand L5: Equipped with a magnetic stirring rod, 5-NH (525 mg, 0.64 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (208 mg, 1.28 mmol, 2.0 equivalents) were sequentially added to a dry sealed tube, followed by three nitrogen purgings. Under nitrogen protection, triethyl orthoformate (10 mL) was added, and the mixture was placed in an oil bath at 80°C and stirred. After reacting for 10 hours, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The resulting crude product was separated and purified by silica gel chromatography (eluent: dichloromethane) to obtain product L5 as 325 mg (yield 52%) of a pale green foamy solid. 1H NMR (500 MHz, DMSO-d6): δ 1.08 (d, J = 6.5 Hz, 6H), 1.18 (d, J = 7.0 Hz, 6H), 1.33 (s, 9H), 2.40-2.46 (m, 2H), 7.31 (dd, J = 8.0, 6.0 Hz, 1H), 7.36 (dd, J =5.0, 3.0 Hz, 1H), 7.39 (d, J = 2.0 Hz, 2H), 7.47-7.50 (m, 1H), 7.52 (dd, J =5.5, 4.0 Hz, 1H), 7.64 (t, J =3.5 Hz, 2H), 7.72 (d, J = 8.5 Hz, 2H), 7.74 - 7.79 (m, 2H), 7.80 (s, 2H), 7.83 (s, 1H), 7.88-7.95 (m, 2H), 8.03 (d, J = 8.5 Hz, 1H), 8.07 (t, J = 2.0 Hz, 1H), 8.19 (s, 1H), 8.28 (d, J = 8.0 Hz, 1H), 8.39 (d, J = 8.5 Hz, 1H), 8.61 (d, J =5.0 Hz, 1H), 10.64 (s, 1H).

[0088] Synthesis of Pt5: Equipped with a magnetic stirring rod, L5 (325 mg, 0.33 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum dichloride (124 mg, 0.33 mmol, 1.0 equivalent), and sodium acetate (136 mg, 1.0 mmol, 3.0 equivalents) were sequentially added to a dry sealed tube, followed by three nitrogen purgings. Under nitrogen protection, 30 mL of diethylene glycol dimethyl ether was added, and the mixture was bubbling with nitrogen gas for 30 minutes. The mixture was then wrapped in tin foil to prevent light from entering, placed in an oil bath at 120°C, stirred, and reacted for 3 days. After cooling to room temperature, deionized water was added and stirred for 5-10 minutes to quench, dichloromethane was added for extraction, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 2:1) to obtain product Pt5 as a yellow solid of 205 mg (yield 60%). 1H NMR (500 MHz, DMSO-d6): δ 0.96-1.27 (m, 21H), 2.81-3.01 (m, 2H), 6.37 (dd, J = 6.0, 2.0 Hz, 1H), 7.17 (d, J = 8.5 Hz, 1H), 7.29 (d, J =8.5 Hz, 1H), 7.33 - 7.41 (m, 6H), 7.46 (t, J = 7.5 Hz, 1H), 7.51 (td, J = 8.5, 7.0 Hz, 1H), 7.59 (td, J =7.0, 6.0 Hz, 1H), 7.86 (d, J = 2.0 Hz, 1H), 7.88 (d, J =8.0 Hz, 2H), 7.95 - 7.99 (m, 3H), 8.15 (d, J = 6.5 Hz, 1H), 8.42 (d, J = 8.5 Hz, 1H), 8.59 (d, J = 6.0 Hz, 1H).

[0089] (Example 6: Synthesis of Pt6) The synthesis route for the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt6 is as follows:

[0090] [ka]

[0091] Synthesis of intermediate 6-NH: Equipped with a magnetic stirring rod, 3 (380 mg, 1.0 mmol, 1.0 equivalent), 2-Cl (531 mg, 1.1 mmol, 1.1 equivalent), tris(dibenzylideneacetone)dipalladium (27 mg, 0.03 mmol, 0.03 equivalent), 2-(di-tert-butylphosphino)biphenyl (18 mg, 0.06 mmol, 0.06 equivalent), and sodium tert-butoxide (192 mg, 2.0 mmol, 2.0 equivalent) were sequentially added to a dry sealed tube, followed by three nitrogen purging cycles. Toluene (5 mL) was added under nitrogen protection, and the mixture was stirred in a 100°C oil bath. After reacting for 12 hours, it was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / ethyl acetate = 30:1) to obtain product 6-NH as a pale green foamy solid of 604 mg (yield 73%). This was then used directly in the next reaction.

[0092] Synthesis of ligand L6: Equipped with a magnetic stirring rod, 6-NH (604 mg, 0.73 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (238 mg, 1.46 mmol, 2.0 equivalents) were sequentially added to a dry sealed tube, followed by three nitrogen purgings. Under nitrogen protection, triethyl orthoformate (10 mL) was added, and the mixture was placed in an oil bath at 80°C and stirred. After reacting for 10 hours, the mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The resulting crude product was separated and purified by silica gel chromatography (eluent: dichloromethane) to obtain product L6 as a pale green foamy solid of 538 mg (yield 75%). 1H NMR (500 MHz, DMSO-d6): δ 1.09 (d, J = 6.5 Hz, 6H), 1.18 (d, J = 7.0 Hz, 6H), 1.30 (s, 9H), 1.36 (s, 9H), 2.35-2.40 (m, 2H), 7.23 (dd, J = 8.5, 6.0 Hz, 1H), 7.31- 7.37 (m, 2H), 7.44-7.49 (m, 3H), 7.52 (t, J = 2.0 Hz, 1H), 7.53 (d, J = 2.5 Hz, 1H), 7.61 (d, J = 8.0 Hz, 1H), 7.66 - 7.79 (m, 7H), 7.89 (s, 2H), 7.96 (dd, J = 8.0, 6.5 Hz, 1H), 8.24 (dd, J = 7.5, 7.0 Hz, 1H), 8.33 (d, J = 8.5 Hz, 1H), 8.58 (d, J = 5.5 Hz, 1H), 10.64 (s, 1H).

[0093] Synthesis of Pt6: Equipped with a magnetic stirring rod, L6 (538 mg, 0.55 mmol, 1.0 equivalent), (1,5-cyclooctadiene)platinum dichloride (206 mg, 0.55 mmol, 1.0 equivalent), and sodium acetate (223 mg, 1.64 mmol, 3.0 equivalents) were sequentially added to a dry sealed tube, followed by three nitrogen purgings. Under nitrogen protection, 30 mL of diethylene glycol dimethyl ether was added, and the mixture was bubbling with nitrogen gas for 30 minutes. The mixture was then wrapped in tin foil to prevent light from entering, placed in an oil bath at 120°C, stirred, and reacted for 3 days. After cooling to room temperature, deionized water was added and stirred for 5-10 minutes to quench, dichloromethane was added for extraction, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The crude product obtained was separated and purified by silica gel chromatography (eluent: petroleum ether / dichloromethane = 2:1) to obtain product Pt6 as a yellow solid of 463 mg (yield 82%). 1H NMR (500 MHz, DMSO-d6): δ 0.96-1.3 (m, 21H), 1.47 (s, 9H), 3.9-4.20 (m, 2H), 6.34 (dd, J =6.5, 6.0 Hz, 1H), 7.04 (d, J = 2.0 Hz, 1H), 7.11 (d, J = 8.5 Hz, 1H), 7.24 (d, J = 8.5 Hz, 1H), 7.28 - 7.33 (m, 1H), 7.36 (t, J = 7.5 Hz, 1H), 7.43 (t, J = 7.5 Hz, 1H), 7.47 (t, J =7.5 Hz, 1H), 7.58 (t, J =8.0 Hz, 1H), 7.68 - 7.88 (m, 8H), 8.10 (d, J = 8.0 Hz, 1H), 8.34 (d, J = 8.5 Hz, 1H), 8.53 (d, J = 6.5 Hz, 1H).

[0094] Spectral test experiments were conducted on the prepared platinum complexes Pt1, Pt4-Pt6. Figure 1 shows the room-temperature emission spectra of the prepared platinum complexes Pt1, Pt4-Pt6 in dichloromethane solution. As can be seen from Figure 1, Pt1, Pt4-Pt6 all emit a deep blue light and have high color purity. The maximum emission peak of Pt1 is 454 nm, it emits a deep blue light, and its full width at half maximum is 19 nm. This invention improves the charge distribution in the excited state by introducing fluorine atoms at appropriate positions in the ligand, thereby increasing the excited state of the material and enabling more charge transfer states from metal to pyridocarbene ( 3 It provides MLCT (Multiple Cellular Coherence Tolerance), which is beneficial for improving emissivity and extending device life. It offers an effective route for designing platinum(II) complexes for high-quality blue phosphorescent materials.

[0095] (Example 7: Synthesis of Pt225) The synthesis route for the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt225 is as follows:

[0096] [ka]

[0097] Pt225 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference. The target product 225-NH was obtained as a pale green foamy solid (804 mg) in 77% yield. The target product L225 was obtained as a pale green foamy solid (705 mg) in 63% yield. Molecular weight [M] + :721.6. The target product, Pt225, was obtained as a yellow solid (606 mg) in 82% yield. Molecular weight [M+H] + :767.7.

[0098] (Example 8: Synthesis of Pt16) The synthesis route for the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt16 is as follows:

[0099] [ka]

[0100] Pt16 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference. The target product 16-NH was obtained as a pale green foamy solid (804 mg) in 77% yield. The target product L16 was obtained as a pale green foamy solid (705 mg) in 63% yield. Molecular weight [M] + :876.4. The target product, Pt16, was obtained as a yellow solid (606 mg) in 82% yield. Molecular weight [M+H] + :1068.4.

[0101] (Example 9: Synthesis of Pt19) The synthesis route for the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt19 is as follows:

[0102] [ka]

[0103] Pt19 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference. The target product 19-NH was obtained as a pale green foamy solid (906 mg) in 79% yield. The target product L19 was obtained as a pale green foamy solid (509 mg) in 59% yield. Molecular weight [M] + :888.5. The target product Pt19 was obtained as a yellow solid (203 mg) in 48% yield. Molecular weight [M+H] + :1080.2.

[0104] (Example 10: Synthesis of Pt21) The synthesis route for the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt21 is as follows:

[0105] [ka]

[0106] Pt21 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference. The target product 21-NH was obtained as a pale green foamy solid (1.56 g) in 61% yield. The target product L21 was obtained as a pale green foamy solid (705 mg) in 70% yield. Molecular weight [M] + :942.4. The target product Pt21 was obtained as a yellow solid (432 mg) in 55% yield. Molecular weight [M+H] + :1134.5.

[0107] (Example 11: Synthesis of Pt24) The synthesis route for the tetradentate cyclometalated platinum(II) complex phosphorescent material Pt24 is as follows:

[0108] [ka]

[0109] Pt24 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference. The target product 24-NH was obtained as a pale green foamy solid (1.02 g) in 75% yield. The target product L24 was obtained as a pale green foamy solid (708 mg) in 63% yield. Molecular weight [M]+ :756.4. The target product, Pt24, was obtained as a yellow solid (201 mg) in 50% yield. Molecular weight [M+H] + :948.3.

[0110] (Example 12: Synthesis of Pt37) Pt37 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference, and the target product was obtained as a yellow solid (562 mg) in 70% yield. Molecular weight [M+H] + :1065.1.

[0111] (Example 13: Synthesis of Pt39) Pt39 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference, and the target product was obtained as a yellow solid (624 mg) in a yield of 56%. Molecular weight [M+H] + :1067.1.

[0112] (Example 14: Synthesis of Pt65) Pt65 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference, and the target product was obtained as a yellow solid (661 mg) in 82% yield. Molecular weight [M+H] + :996.1.

[0113] (Example 15: Synthesis of Pt81) Pt81 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference, and the target product was obtained as a yellow solid (484 mg) in a yield of 67%. Molecular weight [M+H] + :939.0.

[0114] (Example 16: Synthesis of Pt82) Pt82 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference, and the target product was obtained as a yellow solid (455 mg) in 60% yield. Molecular weight [M+H] + :981.0.

[0115] (Example 17: Synthesis of Pt86) Pt86 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference, and the target product was obtained as a yellow solid (410 mg) in a yield of 66%. Molecular weight [M+H]+ :1019.1.

[0116] (Example 18: Synthesis of Pt111) Pt111 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference, and the target product was obtained as a yellow solid (369 mg) in a yield of 58%. Molecular weight [M+H] + :1080.2.

[0117] (Example 19: Synthesis of Pt112) Pt112 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference, and the target product was obtained as a yellow solid (492 mg) in 82% yield. Molecular weight [M+H] + :1096.2.

[0118] (Example 20: Synthesis of Pt210) Pt210 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference, and the target product was obtained as a yellow solid (471 mg) in 80% yield. Molecular weight [M+H] + :1089.2.

[0119] (Example 21: Synthesis of Pt233) Pt233 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference, and the target product was obtained as a yellow solid (596 mg) in 74% yield. Molecular weight [M+H] + :835.9.

[0120] (Example 22: Synthesis of Pt311) Pt311 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference, and the target product was obtained as a yellow solid (615 mg) in a yield of 68%. Molecular weight [M+H] + :931.9.

[0121] (Example 23: Synthesis of Pt318) Pt318 was synthesized using the synthesis steps and reaction conditions of compound Pt1 as a reference, and the target product was obtained as a yellow solid (582 mg) in a yield of 66%. Molecular weight [M+H] + :881.8.

[0122] (Explanation of theoretical calculations) The geometric structure of the ground state (S0) molecule was optimized using density functional theory (DFT). The DFT was calculated using the B3LYP functional, with the 6-31G(d) basis set used for C, H, O, and N atoms, and the LANL2DZ basis set used for Pt atoms.

[0123] [Table 1-1] [Table 1-2]

[0124] The calculation data shown in Table 1 indicates that all compound materials provided by the present invention have a large energy gap (>3.20 eV) and can meet the needs of blue light materials. Furthermore, it can be seen that the energy levels (HOMO and LUMO) of the frontier orbitals of platinum(II) complexes can be adjusted by controlling the ligand structure. The majority of the LUMO of pyridocarbene platinum(II) complexes is located in the pyridocarbene portion. The present invention improves the charge distribution of the excited states by introducing fluorine atoms to appropriate positions in the ligand, thereby increasing the excited states of the material to more charge transfer states from metal to pyridocarbene. 3 The MLCT component can be incorporated, and because both coordinate bonds and feedback π bonds exist between the carbene and platinum(II), its stability is higher than that of the coordinate bond between pyridine and platinum(II). The results described above contribute to increased emissivity, thereby extending the device's lifespan.

[0125] Manufacturing of OLED devices As a reference manufacturing method for an example of the device, the present invention involves depositing a p-type doping material onto the surface or anode of an ITO glass having a 2 mm × 2 mm light-emitting area, or co-depositing a p-type doping material with a hole injection material at a concentration of 1% to 50%, to form a 5 to 100 nm hole injection layer (HIL) and a 5 to 200 nm hole transport layer (HTL). Subsequently, a 10 to 100 nm light-emitting layer (EML) (which may contain the compound of the present invention) is formed on the hole transport layer, and an electron transport layer (ETL) of 20 to 200 nm and a cathode of 50 to 200 nm are formed. If necessary, an electron blocking layer (EBL) is added between the HTL and EML layers, and an electron injection layer (EIL) is added between the ETL and the cathode to manufacture an OLED device. The OLED is tested using a standard method. Unless otherwise specified, the device material according to the present invention can be obtained by known synthesis methods.

[0126] In a preferred embodiment, the structure of 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) (mass ratio of Pt-1:HTH-85:ETH-45 is 10:60:30) / ETH-5 (5 nm) / ET-14 (40 nm) / LiQ (1 nm) / Al (100 nm).

[0127] Device Examples 2 to 22 and Comparative Example 1 were prepared using a structure similar to Device Example 1, with the only difference being that Pt-2, Pt-3, Pt-4, Pt-5, Pt-225, Pt-16, Pt-19, Pt-21, Pt-24, Pt-37, Pt-39, Pt-65, Pt-81, Pt-82, Pt-86, Pt-111, Pt-112, Pt-210, Pt-233, Pt-311, Pt-318, and R1 replaced Pt-1 in Device Example 1. Table 2 shows the data obtained by testing the luminescence characteristics of the comparative example and each device example prepared above using the standard method. The structural formulas of the devices involved are as follows, where P-4 is HATCN and ET-14 is BPyTP.

[0128] [ka]

[0129] [Table 2]

[0130] As can be seen from Table 2, compared to Comparative Example 1, Device Examples 1 to 22 prepared in this application exhibit superior device performance in terms of drive voltage, current efficiency, and device life. The improvement in the performance of each device example is based on the superior electron transport capability of the specific compound material of the present invention. When this is manufactured into an electronic device as an emissive layer material, it can be seen that the drive voltage can be reduced while current efficiency and device life can be improved. The compounds provided by the present invention have a certain commercial application value.

[0131] In a preferred embodiment, the structure of device example 23 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) (mass ratio of Pt1:BN1-8:HTH-85:ETH-45 is 10:1:59:30) / ETH-5 (5 nm) / ET-14 (40 nm) / LiQ (1 nm) / Al (100 nm).

[0132] Device Examples 24 to 30 were fabricated using structures similar to Device Example 23, with the only difference being that the platinum(II) complex and boron-containing compound in Device Example 23 were replaced with the compounds listed in Table 3. The device structure and luminescence properties are shown in Table 3.

[0133] [Table 3]

[0134] As can be seen from Table 3, when the compounds of the present invention are applied to devices as sensitizers and the boron-containing compounds as light-emitting materials, the performance of each device is significantly improved, demonstrating that the compounds provided by the present invention have a certain commercial application value.

[0135] Furthermore, the devices prepared according to the present invention are uniformly deep blue light devices, and their CIEy values ​​are uniformly less than 0.20. By further sensitizing the device structure after adding a boron-containing compound, the CIEy value can be further reduced, thereby further improving the purity of the device's emission color.

[0136] The applicant declares that what is described above is only one of the preferred embodiments of the present invention and is not limited to the scope of protection of the present invention, and it will be apparent to those skilled in the art that any changes or substitutions that can be easily conceived within the technical scope disclosed herein by anyone familiar with the art fall within the scope of protection and disclosure of the present invention.

[0137] (Note) (Note 1) A fluorine-containing tetradentate cyclometalated platinum(II) complex, wherein the complex has a structure represented by formula (I) or formula (II). A fluorine-containing tetradentate cyclometalated platinum(II) complex characterized by the following features. [ka] [In formula (I) or formula (II), F n This indicates that there is one or more F substitutions on the benzene ring where it is located, and n is a positive integer from 1 to 5. R a This represents a mono, dya, tia, quaternary substitution or no substitution, and R a is selected from H or C1-C30 alkyl groups. R1, R2, and R3 are each independently selected from the group consisting of hydrogen, F, N, O, S, CN, C1-C30 alkyl groups, C1-C30 cycloalkyl groups, C1-C30 cycloheteroalkyl groups, C1-C30 haloalkyl groups, C6-C60 aryl groups, and C6-C60 heteroaryl groups.

[0138] (Note 2) At least one of the hydrogen atoms R1, R2, and R3 may be replaced with deuterium or F. The fluorine-containing tetradentate cyclometalated platinum(II) complex described in Appendix 1, characterized by the above.

[0139] (Note 3) R1 and R3 are each independently selected from hydrogen or C1-C30 alkyl groups. The fluorine-containing tetradentate cyclometalated platinum(II) complex described in Appendix 1, characterized by the above.

[0140] (Note 4) Each of the R2s is independently selected from hydrogen, deuterium, CN, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 heteroalkyl group, a substituted or unsubstituted C1-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 cycloheteroalkyl group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C6-C60 heteroaryl group, wherein the heteroatoms on the heteroalkyl group, cycloheteroalkyl group, or heteroaryl group are selected from one or more of O, S, and / or N. The fluorine-containing tetradentate cyclometalated platinum(II) complex described in Appendix 1, characterized by the above.

[0141] (Note 5) Choose one of the following chemical structural formulas, where "D" represents deuterium. The fluorine-containing tetradentate cyclometalated platinum(II) complex described in Appendix 1, characterized by the above. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0142] (Note 6) Applications of fluorine-containing tetradentate cyclometalated platinum(II) complexes described in any one of appendices 1 to 5 in electronic devices.

[0143] (Note 7) Examples of the aforementioned electronic devices include organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic photodetectors, organic photoreceptors, organic electric field quenching elements, light-emitting electrochemical cells, and organic laser diodes. The application described in Appendix 6, characterized by the features described therein.

[0144] (Note 8) An organic electroluminescent device comprising a cathode, an anode, and an organic functional layer interposed between the anode and the cathode, wherein the organic functional layer contains a fluorine-containing cyclometalated platinum(II) complex described in any one of Appendices 1 to 5. An organic electroluminescent device characterized by the above.

[0145] (Appendix 9) An organic electroluminescent device, wherein the organic functional layer includes a light-emitting layer, and the light-emitting layer contains a fluorine-containing cyclometalated platinum(II) complex described in any one of Appendices 1 to 5. An organic electroluminescent device characterized by the above.

[0146] (Appendix 10) The light-emitting layer also contains a fluorescent doping material selected from any one or more of the compounds represented by Formula (BN1) to Formula (BN5). The organic electroluminescent device according to Appendix 9, characterized by the above. [In the formula, X is O, S, Se or NR where X 300 is X 1 X 2 X 3 X 4 are each independently represented by O, S, Se or N, R b ~R e each independently represents mono-, di-, tri-, tetra-substituted or unsubstituted. R b ~R e each independently is selected from the group consisting of hydrogen, deuterium, N, a C1-C30 alkyl group, and a C6-C60 aryl group, and R4 to R 11 each independently represents the group consisting of hydrogen, deuterium, N, a C1-C30 alkyl group, and a C6-C60 aryl group.]

[0147] (Appendix 11) R4-R6 and R9 are each independently selected from substituted or unsubstituted diphenylamines and substituted or unsubstituted carbazolyl groups, and the substitution may be multiple substitutions. If a substituent is present, the substituent is selected from deuterium, C1-C30 alkyl groups and C6-C30 aryl groups. The organic electroluminescent device described in Appendix 10, characterized by the features described herein.

[0148] (Note 12) Above R7~R8, R 10 ~R 11 Each of these is independently selected from the group consisting of hydrogen, C1-C30 alkyl groups, and C6-C60 aryl groups. The organic electroluminescent device described in Appendix 10, characterized by the features described herein.

[0149] (Note 13) The aforementioned fluorescent doping material is selected from one of the following chemical structural formulas, where Ph represents a phenyl group and D4 and D5 are substituted with 4 and 5 deuterium atoms, respectively. The organic electroluminescent device described in Appendix 10, characterized by the features described herein. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0150] (Supplementary Note 14) An organic optoelectronic device comprising a substrate layer, a first electrode on the substrate, an organic light-emitting functional layer on the first electrode, and a second electrode on the organic light-emitting functional layer, wherein the organic light-emitting functional layer contains a fluorine-containing tetradentate cyclometalated platinum(II) complex described in any one of Supplementary Notes 1 to 5. An organic optoelectronic device characterized by the above.

[0151] (Supplementary Note 15) The organic light-emitting functional layer also contains a fluorescent doping material selected from any one or more of the compounds represented by Formula (BN1) to Formula (BN5). The organic optoelectronic device according to Supplementary Note 14, characterized by the above. [Chemical formula] [In the formula, X is O, S, Se or NR 300 and X 1 X 2 X 3 X 4 are each independently represented by O, S, Se or N, R b ~R e each independently represents mono-, di-, tri-, tetra-substituted or unsubstituted. R b ~R e each independently is selected from the group consisting of hydrogen, deuterium, N, a C1-C30 alkyl group, and a C6-C60 aryl group, and the above R4~R 11 each independently represents a group consisting of hydrogen, deuterium, N, a C1-C30 alkyl group, and a C6-C60 aryl group.]

[0152] (Supplementary Note 16) A composition containing a fluorine-containing tetradentate platinum(II) complex described in any one of Supplementary Notes 1 to 5. A composition characterized by the above.

[0153] (Note 17) A pharmaceutical preparation containing a fluorine-containing tetra-tooth platinum(II) complex described in any one of the appendices 1 to 5, A formulation characterized by the following features.

[0154] (Note 18) A display or lighting device comprising one or more organic electroluminescent devices described in any one of the appendices 10 to 13, A display or lighting device characterized by the following features.

Claims

1. A fluorine-containing tetradentate cyclometalated platinum(II) complex, wherein the complex has a structure represented by formula (I) or formula (II). A fluorine-containing tetradentate cyclometalated platinum(II) complex characterized by the following features. 【Chemistry 1】 [In formula (I) or formula (II), F ｎ This indicates that there is one or more F substitutions on the benzene ring where it is located, and n is a positive integer from 1 to 5. R ａ This represents a mono, dya, tia, or quaternary substitution or no substitution, and R ａ is selected from H or C1-C30 alkyl groups. R １ , R ２ , R ３ Each of these is independently selected from the group consisting of hydrogen, F, N, O, S, CN, C1-C30 alkyl groups, C1-C30 cycloalkyl groups, C1-C30 cycloheteralkyl groups, C1-C30 haloalkyl groups, C6-C60 aryl groups, and C6-C60 heteroaryl groups.

2. R １ 、 R ２ 、 R ３ At least one hydrogen of which may be replaced by deuterium or F The fluorine-containing tetradentate cyclometalated platinum(II) complex according to feature 1.

3. The aforementioned R １ , R ３ Each is independently selected from hydrogen or C1-C30 alkyl groups. The fluorine-containing tetradentate cyclometalated platinum(II) complex according to feature 1.

4. The aforementioned R ２ Each is independently selected from hydrogen, deuterium, CN, substituted or unsubstituted C1-C30 alkyl groups, substituted or unsubstituted C1-C30 heteroalkyl groups, substituted or unsubstituted C1-C30 cycloalkyl groups, substituted or unsubstituted C1-C30 cycloheteralkyl groups, substituted or unsubstituted C1-C30 haloalkyl groups, substituted or unsubstituted C6-C60 aryl groups, and substituted or unsubstituted C6-C60 heteroaryl groups, wherein the heteroatoms on the heteroalkyl groups, cycloheteralkyl groups, or heteroaryl groups are selected from one or more of O, S, and / or N. The fluorine-containing tetradentate cyclometalated platinum(II) complex according to feature 1.

5. Select one of the following chemical structural formulas, where "D" represents deuterium. The fluorine-containing tetradentate cyclometalated platinum(II) complex according to feature 1. 【Chemistry 2-1】 【Chemistry 2-2】 [Chemistry 2-3] [Chemistry 2-4] 【Chemistry 2-5】 【Chemistry 2-6】 【Chemistry 2-7】 【Chemistry 2-8】 【Chemistry 2-9】 【Chemistry 2-10】 【Chemistry 2-11】 【Chemistry 2-12】 【Chemistry 2-13】

6. An electronic device comprising a fluorine-containing tetradentate cyclometalated platinum(II) complex according to any one of claims 1 to 5.

7. Examples of the aforementioned electronic devices include organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic photodetectors, organic photoreceptors, organic electric field quenching elements, light-emitting electrochemical cells, and organic laser diodes. The electronic device described in Feature 6.

8. An organic electroluminescent device comprising a cathode, an anode, and an organic functional layer interposed between the anode and the cathode, wherein the organic functional layer contains a fluorine-containing tetradentate cyclometalated platinum(II) complex as described in any one of claims 1 to 5. An organic electroluminescent device characterized by the following features.

9. An organic electroluminescent device, wherein the organic functional layer includes a light-emitting layer, and the light-emitting layer contains a fluorine-containing tetradentate cyclometalated platinum(II) complex according to any one of claims 1 to 5. An organic electroluminescent device characterized by the following features.

10. The light-emitting layer also contains a fluorescent doping material selected from one or more compounds represented by formulas (BN1) to (BN5). The organic electroluminescent device according to feature 9. 【Transformation 3】 [In the formula, X is O, S, or Se, X １ , X ２ , X ３ , X ４ These are represented independently by O, S, or Se, R ｂ ~R ｅ These independently represent mono, bis, tertiary, tetrapermutations or no substitutions, respectively. ｂ ~R ｅ Each is independently selected from the group consisting of hydrogen, deuterium, N, C1-C30 alkyl groups, and C6-C60 aryl groups, R ４ ~R ６ , R ９ Each of these independently represents a group consisting of hydrogen, deuterium, nitrogen, C1-C30 alkyl groups, and C6-C60 aryl groups.

11. The aforementioned R ４ ~R ６ , R ９ Each is independently selected from substituted or unsubstituted diphenylamines and substituted or unsubstituted carbazolyl groups, wherein the substitution may be multiple substitutions, and if substituents are present, the substituents are selected from deuterium, C1-C30 alkyl groups and C6-C30 aryl groups. The organic electroluminescent device according to feature 10.

12. The aforementioned R ９ This is selected from the group consisting of hydrogen, C1-C30 alkyl groups, and C6-C60 aryl groups. The organic electroluminescent device according to feature 10.

13. An organic optoelectronic device comprising a substrate layer, a first electrode on the substrate, an organic light-emitting functional layer on the first electrode, and a second electrode on the organic light-emitting functional layer, wherein the organic light-emitting functional layer contains a fluorine-containing tetradentate cyclometalated platinum(II) complex as described in any one of claims 1 to 5. An organic optoelectronic device characterized by the following features.

14. The organic light-emitting functional layer also contains a fluorescent doping material selected from one or more compounds represented by formulas (BN1) to (BN5). The organic optoelectronic device according to feature 13. 【Chemistry 4】 [In the formula, X is O, S, or Se, X １ , X ２ , X ３ , X ４ These are represented independently by O, S, or Se, R ｂ ~R ｅ These independently represent mono, bis, tertiary, tetrapermutations or no substitutions, respectively. ｂ ~R ｅ Each is independently selected from the group consisting of hydrogen, deuterium, N, C1-C30 alkyl groups, and C6-C60 aryl groups, and the R ４ ~R ６ , R ９ Each of these independently represents a group consisting of hydrogen, deuterium, nitrogen, C1-C30 alkyl groups, and C6-C60 aryl groups.

15. A composition containing a fluorine-containing tetradentate cyclometalated platinum(II) complex according to any one of claims 1 to 5, A composition characterized by the following features.

16. A pharmaceutical preparation containing a fluorine-containing tetradentate cyclometalated platinum(II) complex according to any one of claims 1 to 5, A formulation characterized by the following features.

17. A display or lighting device comprising one or more of the organic electroluminescent devices described in claim 10, A display or lighting device characterized by the following features.

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