Tetradentate cyclometallized platinum (II) complex, electronic device, and applications thereof

Abstract

To provide a tetradentate cyclometallized platinum (II) complex, an electronic device, and applications thereof.SOLUTION: The present invention belongs to a technical field of organic electroluminescence, and particularly relates to a tetradentate cyclometallized platinum (II) complex, an electronic device, and applications thereof. In the present invention, by introducing a 2,6-di(phenyl)tert-butylphenyl at an appropriate position of a ligand, a dihedral angle between pyridine units is increased, and the stacking between molecules is reduced. At the same time, the charge distribution of an excited state is improved, the excited state of a material is made to have a charge transfer state from more metals to the pyridocarbene so as to prolong a device lifetime, and it is easy to produce an evaporated OLED device having excellent chemical and thermal stability. After being combined with a fluorescent doping material, the transport of holes and electrons is balanced, and an energy transfer between a host and a guest is made to be more efficient. When used as an organic electroluminescent device, the current efficiency and the lifetime are significantly improved, and a turn-on voltage is significantly reduced. It is expected to be widely applied to the fields of OLED display and lighting.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to the technical field of organic electroluminescence, and in particular to tetradentate cyclometallated platinum(II) complexes, electronic devices and their applications. [Background technology]

[0002] Organic light-emitting diode (OLED) is a new generation full-color display and lighting technology. Compared with liquid crystal displays, which have the disadvantages of slow response speed, narrow viewing angle, need for backlight, and high power consumption, OLED is a self-emitting device that does not require backlight and is energy-saving, has low driving voltage, fast response speed, high resolution and contrast, wide viewing angle, and excellent low temperature characteristics. OLED devices can be made thinner and more flexible. They also have the advantages of low manufacturing cost, simple manufacturing process, and large area production. Therefore, OLED has a wide and huge application potential in the high-end electronic products and aerospace fields. With the gradual increase in investment, deeper research and development, and upgrade and improvement of manufacturing equipment, OLEDs will have a very wide range of application scenarios and development prospects in the future.

[0003] The core of the development of OLED is the design and development of emitting materials. Most of the emitting layers in currently applied OLED devices use the host-guest emitting mechanism in which a guest emitting material is doped into a host material. The energy gap of the host material is generally larger than that of the guest emitting material, and energy is transferred from the host material to the guest material, which is excited to emit light. Commonly used organic phosphorescent guest materials are generally heavy metal atoms such as iridium (III), platinum (II), and Pd (II). The 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 level, and when used as an organic material, they can efficiently transfer triplet energy from the organic emitting material to the guest phosphorescent emitting material. However, mCBP has the property that holes are easily transported but electrons are difficult to flow, and 2,6-mCPy has poor hole transport, which causes the charge balance of the emissive layer to be lost and the current efficiency of the emissive layer to be reduced. In addition, the number of heavy metal phosphorescent organic complex molecules, cyclometalated iridium(III) complex molecules, currently in use is limited. The abundance of metallic platinum element in the earth's crust and the annual production in the world as a whole are about 10 times that of metallic iridium element, and the price of IrCl3·H2O used to prepare iridium(III) complex phosphorescent materials is also much higher than the price of PtCl2 used to prepare platinum(II) complex phosphorescent materials. In addition, the preparation of iridium(III) complex phosphorescent materials involves four-step reactions, including iridium(III)-containing dimers, ligand exchange of iridium(III) intermediates, synthesis of mer-iridium(III) complexes, and conversion of mer- to fac-iridium(III) complex isomers, which significantly reduces the total yield and the utilization rate of the raw material IrCl3·H2O, thus increasing the preparation cost of iridium(III) complex phosphorescent materials. In contrast, the preparation of platinum(II) complex phosphorescent materials only requires the final reaction of ligand metallization and design platinum salt, which has a high utilization rate of platinum element, and can further reduce the preparation cost of platinum(II) complex phosphorescent materials.In short, the preparation cost of platinum (II) complex phosphorescent materials is much 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 how to improve the efficiency and life of devices has become an important research topic. Therefore, there is an urgent need to develop new phosphorescent metal platinum (II) complexes. Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention has been made in view of the above circumstances, and aims to provide a tetradentate cyclometallated platinum(II) complex, an electronic device, and their applications. The tetradentate cyclometallated platinum(II) complex of the present invention can provide excellent performance to the device as a guest phosphorescent material in the light-emitting layer. Furthermore, when the tetradentate cyclometallated platinum(II) complex is combined with a specific host material, it can not only improve the current efficiency of electronic devices, particularly organic electroluminescent devices, and extend the device life, but also reduce the operating voltage of the components. [Means for solving the problem]

[0005] The present invention provides a tetradentate cyclometallated platinum(II) complex selected from any one of the following structural formulas: where "D" represents deuterium and "Ph" represents a phenyl group.

[0006] [ka] [ka]

[0007] The present invention also provides applications of tetradentate cyclometallated platinum(II) complexes having structures represented by the above formulas Pt1 to Pt45 in electronic devices.

[0008] Examples of the electronic device 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 quenchers (O-FQDs), light emitting electrochemical cells (LECs), and organic laser diodes (O-lasers).

[0009] In another aspect, the present invention also provides organic electroluminescent devices comprising tetradentate cyclometallated platinum(II) complexes having the structures shown in the formulas Pt1-Pt45 above.

[0010] The organic electroluminescent device also includes a cathode, an anode, and an organic functional layer interposed between the anode and the cathode, and the organic functional layer contains a tetradentate cyclometallated platinum(II) complex having a structure represented by formula (I) or formula (II) as described above.

[0011] Preferably, the organic functional layer includes a light-emitting layer, and the light-emitting layer contains tetradentate cyclometallated platinum(II) complexes having the structures represented by the above formulas Pt1 to Pt45.

[0012] The light-emitting layer also contains a fluorescent doping material, and the fluorescent doping material is selected from any one or more of the compounds represented by formulae (BN1) to (BN5).

[0013] [ka] [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 eR each independently represents mono-, di-, tri-, tetra- or no substitution. 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, 11 each independently represents the group consisting of hydrogen, deuterium, N, a C1-C30 alkyl group, and a C6-C60 aryl group.

[0014] Preferably, R4, R5, R6, and R9 are each independently selected from a substituted or unsubstituted diphenylamine, a substituted or unsubstituted carbazolyl group, and the substitution may be multiple times. When the substituent is present, the substituent is selected from a deuterium atom, a C1-C30 alkyl group, and a C6-C30 aryl group.

[0015] Preferably, R7 to R8 and R 10 ~R 11 are each independently selected from the group consisting of hydrogen, a C1-C30 alkyl group, and a C6-C60 aryl group.

[0016] More preferably, R4 to R 11 At least one hydrogen atom may be replaced with deuterium.

[0017] In addition, the fluorescent doping material is selected from any one of the chemical structural formulas shown below, in which Ph represents a phenyl group, and D4 and D5 represent substitutions with 4 and 5 deuterium atoms, respectively.

[0018] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0019] In another aspect, 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, the organic light-emitting functional layer containing a tetradentate cyclometallated platinum(II) complex having a structure represented by any one of the formulas Pt1 to Pt45 above. For example, the platinum(II) complex may be included in the organic light-emitting functional layer as a light-emitting material.

[0020] The organic light-emitting functional layer also contains a fluorescent doping material having at least one of the compounds represented by the above formulas (BN1) to (BN5).

[0021] The present invention also provides a composition containing a tetradentate cyclometallated platinum(II) complex having the structure represented by the above formulas Pt1 to Pt45. Preferably, the composition also contains a fluorescent doping material having one or more of the compounds represented by the above formulas (BN1) to (BN5).

[0022] The present invention also provides a formulation containing a tetradentate cyclometallated platinum(II) complex having a structure represented by the above formulas Pt1 to Pt45 or the above composition and at least one solvent. The solvent is not particularly limited, and those well known to those skilled in the art can be used, such as 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.

[0023] Preferably, the composition also contains a fluorescent doping material having at least one of the compounds represented by the above formulas (BN1) to (BN5).

[0024] The present invention also provides a display or lighting device comprising one or more of the above organic optoelectronic devices. Effect of the Invention

[0025] Compared with the prior art, the advantages of the present invention include: The present invention provides a phosphorescent material of tetradentate cyclometalated platinum(II) complex. By introducing 2,6-di(phenyl)tert-butylphenyl into the appropriate position of the ligand, the dihedral angle between pyridine units is increased and the stacking between molecules is reduced. At the same time, it improves the charge distribution in the excited state, and the excited state of the material has more metal-to-pyridocarbene charge transfer states (3MLCT), which is beneficial for improving the emissivity and extending the device life. The material according to the present invention has good chemical and thermal stability, and is easy to fabricate deposition-type OLED devices. After being combined with a fluorescent doping material, the transport of holes and electrons is balanced, and the energy transfer between the host and the guest is more efficient. The organic electroluminescent device fabricated using the compound of the present invention as the light-emitting layer has obvious improvements in terms of current efficiency and life, and the lighting voltage is greatly reduced. Especially when combined with a phosphorescence-sensitized boron-containing compound, it can improve the color purity of the light of the device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] 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 such an embodiment or specific example.

[0027] As used herein, the term "substituted" includes all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include cyclic and acyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more and can be the same or different for appropriate organic compounds. For purposes of this invention, heteroatoms (e.g., nitrogen) can have hydrogen substituents and / or any permissible substituents of organic compounds described herein that satisfy the valences of the heteroatoms. This invention is not intended to be limited in any manner with respect to the permissible substituents of organic compounds. Similarly, the terms "substituted" or "substituted with" have the implication that such substitution is in accordance with the permissible valences of the atom and the substituent being substituted, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously transform, e.g., rearrange, cyclize, or eliminate). Moreover, in certain embodiments, it is contemplated that individual substituents may be optionally further substituted (i.e., may or may not be further substituted), unless clearly indicated to the contrary.

[0028] In the definitions of various terms, "R1" to "R 11 " is used herein as a generic symbol to represent various specific substituents. These symbols may be any substituent and are not limited to the substituents disclosed herein, and when defined as a certain substituent in one instance, it may be defined as a different substituent in another instance.

[0029] As used herein, "R1", "R2", "R3" ... "R n " (where n is an integer) may independently contain one or more of the groups listed above. For example, R 1When is a straight chain alkyl group, one of the hydrogen atoms of the alkyl group may be optionally replaced by a hydroxyl group, an alkoxy group, an alkyl group, a halogen, etc. Depending on the group selected, the first group may be incorporated into the second group, or the first group may be pendant (i.e., attached) to the second group. For example, in the phrase "an alkyl group that includes an amino group," the amino group may be attached within the backbone of the alkyl group. Optionally, the amino group may be attached to the backbone of the alkyl group. The nature of the group selected will determine whether the first group is incorporated into or attached to the second group.

[0030] 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, tetracosyl, and the like. 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, as described herein.

[0031] As used herein, the term "aryl" refers to a group of 5 to 60 carbon atoms containing any carbon-based aromatic group, including but not limited to benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, anthryl, phenanthrenyl, and the like. The term "aryl" also includes "heteroaryl", which is defined as a group containing an aromatic group with one heteroatom incorporated within 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" 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. Aryl groups may be optionally substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, halogen, hydroxy, carbonyl, azido, nitro, silyl, sulfo-oxo, or mercapto, as described herein.

[0032] As used herein, the term "amine" or "amino" refers to a group of the formula -NR 1 R 2 wherein R 1 and R 2 may be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl groups.

[0033] The compounds of the present invention may contain "optionally substituted" moieties. In general, the term "substituted", whether preceded by the term "optionally" or not, means that one or more hydrogens of the specified moiety are replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when one or more positions of any given structure are substitutable with one or more substituents selected from a specified group, the substituents may be the same or different at all positions. Combinations of substituents envisioned by the present invention are preferably those combinations that result in the formation of stable or chemically feasible compounds. Furthermore, in certain embodiments, it is contemplated that individual substituents may be optionally further substituted (i.e., may be further substituted or unsubstituted), unless clearly indicated to the contrary.

[0034] The structure of the compound may be represented by the following formula:

[0035] [ka]

[0036] This formula is understood to be the same as the formula:

[0037] [ka] [wherein n is usually an integer. That is, R n is a group consisting of five independent substituents R a(1) , R a(2) , R a(3) , R a(4) , R a(5) By "independent substituents" it is meant that each R substituent may be defined independently. For example, in one example, R n(a) is a halogen, R a(m) does not necessarily have to be a halogen in the examples.

[0038] The compounds disclosed herein can exhibit desirable properties and have emission and / or absorption spectra that can be tailored by selection of appropriate ligands. Additionally, the present invention can exclude any one or more compounds, structures, or portions thereof specifically described herein.

[0039] The compounds of the present invention can be prepared in a variety of ways, including but not limited to, those methods described in the examples provided herein.

[0040] It should be noted that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention.

[0041] The present application may be understood more readily by reference to the following specific embodiments and examples included therein.

[0042] Before the present compounds, devices and / or methods are disclosed and described, it is to be understood that unless otherwise specified, the present invention is not limited to a particular synthetic method (shown separately) or to a particular reagent (shown separately), which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, exemplary methods and materials are described herein. All raw materials and solvents in the synthetic examples were commercially available unless otherwise specified, and solvents were used as is without further treatment.

[0043] The substrate of the present invention can be any substrate used in typical organic optoelectronic devices, and can be a glass or transparent plastic substrate, a substrate made of opaque materials such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness, and waterproof properties, and the direction of use varies according to the nature of the substrate. As the materials for the hole injection layer, hole transport layer, and electron injection layer, any material can be selected from known materials used in OLED devices, and the present invention is not particularly limited thereto.

[0044] [Synthesis Example] The following examples of compound synthesis, composition, device, or method are only intended to provide a general approach to the industry and are not intended to limit the scope of patent protection. Data (amounts, temperatures, etc.) given in the patents are as accurate as possible, but may have some errors. Unless otherwise indicated, measurements are taken separately, temperatures are in °C or at ambient temperature, and pressures are close to ambient pressure.

[0045] In the following examples, the preparation method of the novel compound is provided, but the preparation of such compound is not limited to this method. The compound sought to be protected in the present invention is easy to modify and prepare in this technical field, so it can be prepared by the methods listed below or other methods. The following examples are merely examples and are not intended to limit the scope of protection of this patent. The temperature, catalyst, concentration, reactants, and reaction process can be changed, and different conditions can be selected for different reactants to prepare the compound.

[0046] 1 H NMR (500 MHz), 1 H NMR (400 MHz), 13 C NMR (126 MHz) spectra were measured on an ANANCE III (500M) nuclear magnetic resonance spectrometer. Unless otherwise stated, the nuclear magnetic resonance spectra were uniformly measured using DMSO-d or CDCl containing 0.1% TMS as the solvent. 1For H NMR spectra, TMS (δ=0.00 ppm) is used as the internal standard when CDCl3 is used as the solvent. When DMSO-d6 is used as the solvent, TMS (δ=0.00 ppm) or the residual DMSO peak (δ=2.50 ppm) or the residual water peak (δ=3.33 ppm) is used as the internal standard. 13 In the C NMR spectra, CDCl3 (δ = 77.00 ppm) or DMSO-d6 (δ = 39.52 ppm) was used as an internal standard. HPLC-MS was measured on an Agilent 6210 TOF LC / MS mass spectrometer, and HRMS spectra were measured on an Agilent 6210 TOF LC / MS liquid chromatograph time-of-flight mass spectrometer. 1 H NMR spectral data: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad.

[0047] (Example 1: Synthesis route of intermediate (dPh-tBuNH2)) [ka]

[0048] Synthesis of intermediate (dBr-tBuNH2): p-tert-Butylaniline (15.0 g, 100 mmol, 1.0 equiv.) was added to the reaction flask and dissolved in dichloromethane (150 mL), followed by addition of N-bromosuccinimide (37.7 g, 210 mmol, 2.1 equiv.) and reaction at room temperature for 48 h before quenching. The organic phase was separated, concentrated, and subjected to silica gel column chromatography to give 25.6 g of a red liquid in 84% yield. No structural characterization was performed and the product was used directly in the next step.

[0049] Synthesis of intermediate (dBr-tBuNO2): dBr-tBuNH2 (5 g, 16.3 mmol, 1.0 equiv) was added to the reaction flask and dissolved in N-methylpyrrolidone (50 mL), followed by sodium hydride (1.96 g, 49 mmol, 3.0 equiv), o-fluoronitrobenzene (3.45 g, 24.5 mmol, 1.5 equiv) and reaction was stopped at room temperature for 48 h. The organic phase was separated, concentrated and subjected to silica gel column chromatography to give 5.08 g of a yellow solid in 73% yield. No structural characterization was performed and the product was used directly in the next step.

[0050] Synthesis of intermediate (dBr-tBu2NH2): dBr-tBuNO2 (4.8 g, 11.2 mmol, 1.0 equiv), stannous chloride (10.1 g, 44.8 mmol, 4.0 equiv) were added to the reaction flask, followed by ethyl acetate (50 mL) and ethanol (50 mL). After 24 h in oil at 78 °C, the reaction was quenched, cooled to room temperature, and the organic phase was separated, concentrated, and subjected to silica gel column chromatography to give 3.43 g of a white solid in 82% yield. No structural characterization was performed and the product was used directly in the next step.

[0051] Synthesis of intermediate (dPh-tBuNH2): dBr-tBu2NH2 (3.2 g, 8 mmol, 1.0 equiv), phenylboronic acid (2.93 g, 24 mmol, 3.0 equiv), tetrakistriphenylphosphine 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) were added to the reaction flask. After 24 hours at 90°C, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated and subjected to silica gel column chromatography to obtain 2.66 g of a white solid in 84% yield. 1H 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).

[0052] (Example 2: Synthesis route of Pt1) [ka]

[0053] Synthesis of intermediate (M1-OMe): 4-(tert-butyl)-2-chloropyridine (20.6 g, 121.2 mmol, 1.2 equiv), 2-methoxycarbazole (20 g, 101 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (925 mg, 1.01 mmol, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (904 mg, 3.03 mmol, 3 mol%) and sodium tert-butoxide (19.41 g, 202 mmol, 2.0 equiv) were added to a reaction flask and toluene (200 mL) was added. After 48 h at 110 °C, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated and subjected to silica gel column chromatography to give 32.71 g of a white solid in 98% yield. No structural characterization was performed and the product was used directly in the next step.

[0054] Synthesis of intermediate (M1-OH): M1-OMe and hydrogen bromide (80.91 g, 990 mmol, 10.0 equiv.) were added to the reaction flask. After 24 h at 120° C., the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated, and subjected to silica gel column chromatography to give 30.6 g of a white solid in 97% yield. No structural characterization was performed and the product was used directly in the next step.

[0055] Synthesis of intermediate (M1-Cl): M1-OH (5 g, 15.8 mmol, 1.0 equiv), 3-chloro-5-bromo-tert-butylbenzene (4.3 g, 17.4 mmol, 1.1 equiv), 2-picolinic acid (390 mg, 3.16 mmol, 20 mmol%), copper iodide (301 mg, 1.58 mmol, 10 mmol%) and potassium phosphate (522 mg, 2.46 mmol, 2.0 equiv) were added to a reaction flask and dimethylsulfoxide (50 mL) was added. After 12 hours at 100°C, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated and subjected to silica gel column chromatography to give 6.94 g of a white solid in 91% yield.

[0056] [ka]

[0057] Synthesis of intermediate (LNH-Pt1): dPh-tBuNH2 (400 mg, 1.02 mmol, 1.0 equiv) was added to the reaction flask, followed by M1-Cl (492 mg, 1.02 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (28 mg, 0.03 mmol, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (19 mg, 0.06 mmol, 6 mol%) and sodium tert-butoxide (167 mg, 1.74 mmol, 2.0 equiv), followed by toluene (5 mL). After 17 h at 100 °C, the reaction was stopped, cooled to room temperature and the organic phase was separated, concentrated and subjected to silica gel column chromatography to give 760 mg of a white solid in 89% yield. No structural characterization was performed and the product was used directly in the next step.

[0058] Synthesis of ligand (L-Pt1): LNH-Pt1 (730 mg, 0.87 mmol, 1.0 equiv.) was added to the reaction flask, followed by ammonium hexafluorophosphate (284 mg, 1.74 mmol, 2.0 equiv.) and triethyl orthoformate (5 mL). After 8 hours at 80°C, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated, and subjected to silica gel column chromatography to obtain 320 mg of a white solid in 39% yield. 1 H NMR (500 MHz, CDCl3) δ 1.27 (s, 9H), 1.29 (s, 9H), 1.43 (s, 9H), 6.81 (t, J = 2.0 Hz, 1H), 6.95 (t, J = 1.5 Hz, 1H), 7.08 - 8211; (m, 6H), 7.13 - 7.16 (m, 5H), 7.34 - 7.35 (m, 1H), 7.45 -7.49 (m, 5H), 7.51 - 7.57 (m, 2H), 7.65 - 7.69 (m, 2H), 7.72 (s, 2H), 7.76 (d, J = 7.5 Hz, 1H), 8.27 (d, J = 7.5 Hz, 1H), 8.35 (d, J = 8.5 Hz, 1H), 8.58 (d, J = 6.0 Hz, 1H), 10.24 (s, 1H).

[0059] Synthesis of Pt1: L-Pt1 (200 mg, 0.2 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (79 mg, 0.21 mmol, 1.05 equiv.) and sodium acetate (50 mg, 0.60 mmol, 3.0 equiv.) were added to the reaction flask, and diethylene glycol dimethyl ether (10 mL) was added. After reacting at 120°C for 72 hours, the reaction was stopped, cooled to room temperature, concentrated, and subjected to silica gel column chromatography to obtain 172 mg of a yellow solid in 83% yield. 1H NMR (500 MHz, DMSO) δ 1.22 (s, 9H), 1.41 (s, 9H), 1.42 (s, 9H), 6.51 - 6.68 (m, 3H), 6.85 - 7.23 (m, 9H), 7.31 - 7.69 (m, 9H), 7.82 (d, J = 8.0 Hz, 1H), 7.91 (d, J = 2.0 Hz, 1H), 8.04 (d, J = 8.0 Hz, 1H), 8.12 (d, J = 8.5 Hz, 1H), 8.19 (d, J = 3.5 Hz, 1H), 8.93 (d, J = 6.5Hz, 1H).

[0060] (Example 3: Synthesis route of Pt2) [ka]

[0061] Synthesis of intermediate (M2-Cl): M1-OH (8.0 g, 25.3 mmol, 1.0 equiv), m-chlorobromobenzene (5.34 g, 27.8 mmol, 1.1 equiv), 2-picolinic acid (623 mg, 5.06 mmol, 20 mmol%), copper iodide (481 mg, 2.53 mmol, 10 mmol%) and potassium phosphate (10.74 g, 50.6 mmol, 2.0 equiv) were added to a reaction flask and dimethylsulfoxide (80 mL) was added. After 12 h at 100 °C, the reaction was quenched, cooled to room temperature, concentrated and subjected to silica gel column chromatography to give 6.94 g of a white solid in 93% yield. Structural characterization was not performed and the product was used directly in the next step.

[0062] [ka]

[0063] Synthesis of intermediate (LNH-Pt2): dPh-tBuNH2 (5 g, 12.7 mmol, 1.0 equiv) was added to the reaction flask, followed by M2-Cl (5.43 mg, 12.7 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (349 mg, 0.38 mmol, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (230 mg, 0.76 mmol, 6 mol%) and sodium tert-butoxide (2.44 g, 25.4 mmol, 2.0 equiv), followed by toluene (50 mL). After 9 h at 100 °C, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated and subjected to silica gel column chromatography to give 8.85 g of a white solid in 87% yield. No structural characterization was performed and the product was used directly in the next step.

[0064] Synthesis of ligand (L-Pt2): LNH-Pt2 (4.19 g, 5.4 mmol, 1.0 equiv.) was added to the reaction flask, followed by ammonium hexafluorophosphate (1.76 g, 10.8 mmol, 2.0 equiv.) and triethyl orthoformate (20 mL). After 7 hours at 80°C, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated, and subjected to silica gel column chromatography to obtain 3.67 g of a white solid in 72% yield. 1 H NMR (500 MHz, DMSO) δ 1.30 (s, 9H), 1.45 (s, 9H), 6.98 (t, J = 2.5 Hz, 1H), 7.11 - 7.19 (m, 12H), 7.36 - 7.42 (m, 2H), 7.47 - 7.59 (m, 6H), 7.69 - 7.79 (m, 6H), 8.29 (d, J = 7.5 Hz, 1H), 8.37 (d, J = 8.5 Hz, 1H), 8.60 (d, J = 5.0 Hz, 1H), 10.27 (s, 1H).

[0065] Synthesis of Pt2: L-Pt2 (500 mg, 0.53 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (194 mg, 0.56 mmol, 1.05 equiv.) and sodium acetate (130 mg, 1.59 mmol, 3.0 equiv.) were added to the reaction flask, and diethylene glycol dimethyl ether (10 mL) was added. After reacting at 120°C for 72 hours, the reaction was stopped, cooled to room temperature, concentrated, and subjected to silica gel column chromatography to obtain 173 mg of a pale yellow solid in 33% yield. 1 H NMR (500 MHz, CDCl3) δ 1.20 (s, 9H), 1.41 (s, 9H), 6.29 (d, J = 8.5 Hz, 1H), 6.35 - 7.19 (m, 11H), 7.21 - 7.25 (m, 2H), 7.31 (d, J = 8.5Hz, 2H), 7.39 - 7.65 (m, 6H), 7.80 (d, J = 8.5 Hz, 1H), 7.89 - 7.92 (m, 2H), 7.99 (d, J = 8.0 Hz, 1H), 8.12 (d, J = 7.0 Hz, 1H), 9.09 (d, J = 6.0 Hz, 1H).

[0066] Example 4: Synthesis route of Pt3 [ka]

[0067] Synthesis of intermediate (M3-OH): 4-(tert-Butyl)-2-bromopyridine (20.6 g, 46.7 mmol, 1.1 equiv), 2-bromocarbazole (10.43 g, 42.4 mmol, 1.0 equiv), copper iodide (807 mg, 4.24 mmol, 10 mol%), N-methylimidazole (696 mg, 8.48 mmol, 20 mol%) and lithium tert-butoxide (6.78 g, 84.8 mmol, 2.0 equiv) were added to a reaction flask and toluene (80 mL) was added. After 48 h at 120 °C, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated and subjected to silica gel column chromatography to give 14.5 g of a white solid in 90% yield. No structural characterization was performed and the product was used directly in the next step.

[0068] [ka]

[0069] Synthesis of intermediate (A3): A1 (20 g, 82.9 mmol, 1.0 equiv), A2 (24.7 g, 133 mmol, 1.6 equiv), n-butyllithium (40 mL, 99.48 mmol, 1.2 equiv), N-methylimidazole (696 mg, 8.48 mmol, 20 mol%) and lithium tert-butoxide (6.78 g, 84.8 mmol, 2.0 equiv) were added to a reaction flask and tetrahydrofuran (200 mL) was added. After 24 h at room temperature, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated and subjected to silica gel column chromatography to give A3 as a white solid 13.4 g (75% yield). Structural characterization was not performed and it was used directly in the next step.

[0070] Synthesis of intermediate (diPr-Cl-OMe): A3 (7.81 g, 27.1 mmol, 1.2 equiv) was added to the reaction flask, followed by A4 (5.0 g, 22.6 mmol, 1.0 equiv), 1,1-bis(diphenylphosphino)ferrocene]dichloropalladium (330 mg, 0.45 mmol, 2 mol%), sodium hydroxide (1.81 g, 45.2 mmol, 2.0 equiv), dioxane (50 mL) and water (10 mL). After 24 h at 100 °C, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated and subjected to silica gel column chromatography to give diPr-Cl-OMe as a white solid 4.79 g (70% yield). No structural characterization was performed and the product was used directly in the next step.

[0071] Synthesis of intermediate (diPr-Cl-OH): diPr-Cl-OMe (6.93 g, 22.9 mmol, 1.0 equiv) was added to the reaction flask, followed by boron tribromide (11.48 g, 45.8 mmol, 2.0 equiv) and dichloromethane (10 mL). After 8 h at room temperature, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated, and subjected to silica gel column chromatography to give diPr-Cl-OH as a white solid, 4.5 g (81% yield). No structural characterization was performed and the product was used directly in the next step.

[0072] Synthesis of intermediate (M3-Cl): diPr-Cl-OH (4.5 g, 15.6 mmol, 1.5 equiv), M3-Br (3.94 g, 10.4 mmol, 1.0 equiv), 2-picolinic acid (256 mg, 2.08 mmol, 20 mmol%), copper iodide (198 mg, 1.04 mmol, 10 mmol%) and potassium phosphate (4.42 g, 20.8 mmol, 2.0 equiv) were added to a reaction flask and dimethylsulfoxide (50 mL) was added. After 12 h at 110 °C, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated and subjected to silica gel column chromatography to give M3-C as a white solid 4.45 g (73% yield). Structural characterization was not performed and the product was used directly in the next step.

[0073] [ka]

[0074] Synthesis of intermediate (LNH-Pt3): dPh-tBuNH2 (5.5 g, 1.4 mmol, 1.0 equiv) was added to the reaction flask, followed by M3-Cl (8.22 g, 14 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (384 mg, 0.42 mmol, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (250 mg, 0.84 mmol, 6 mol%) and sodium tert-butoxide (2.7 g, 28 mmol, 2.0 equiv), followed by toluene (100 mL). After 12 h at 100 °C, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated and subjected to silica gel column chromatography to give 9.24 g of a white solid in 70% yield. No structural characterization was performed and the product was used directly in the next step.

[0075] Synthesis of the ligand (L-Pt3): LNH-Pt3 (13.6 g, 14.4 mmol, 1.0 equiv.) was added to the reaction flask, followed by ammonium hexafluorophosphate (4.7 g, 28.8 mmol, 2.0 equiv.), followed by triethyl orthoformate (50 mL). After 10 h at 80°C, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated, and subjected to silica gel column chromatography to give 8.42 g of a white solid in 61% yield. 1H NMR (500 MHz, DMSO) δ 0.87 (d, J = 6.9 Hz, 6H), 1.06 (d, J = 6.9 Hz, 6H), 1.28 (s, 9H), 1.44 (s, 9H), 2.39 - 2.45 (m, 2H), 7.02 (dd, J = 2.5, 1.5 Hz, 1H), 7.04 - 7.07 (m, 2H), 7.10 - 7.14 (m, 4H), 7.18 - 7.23 (m, 8H), 7.32 - 7.36 (m, 2H), 7.42 (t, J = 2.0 Hz, 1H), 7.43 - 7.46 (m,2H), 7.48 - 7.50 (m, 2H), 7.53 - 7.57 (m, 1H), 7.59 - 7.62 (m, 1H), 7.69 (d, J = 2.5 Hz, 1H), 7.73 - 7.76 (m, 4H), 8.25 (d, J = 7.5 Hz, 1H), 8.34 (d, J = 8.5 Hz, 1H), 8.55 (d, J = 5.5 Hz, 1H), 10.28 (s, 1H).

[0076] Synthesis of Pt3: L-Pt3 (5.0 g, 4.5 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (1.64 g, 4.72 mmol, 1.05 equiv.) and sodium acetate (1.11 g, 13.5 mmol, 3.0 equiv.) were added to the reaction flask, and diethylene glycol dimethyl ether (50 mL) was added. After 72 hours at 120°C, the reaction was stopped, cooled to room temperature, concentrated, and subjected to silica gel column chromatography to obtain Pt3 as a pale yellow solid, 3.61 g (70% yield). NMR confirmed the product.

[0077] Example 5: Synthesis route of Pt4 [ka]

[0078] Synthesis of intermediate (LNH-Pt4): dPh-CN-NH2 (500 mg, 1.38 mmol, 1.2 equiv) was added to the reaction flask, followed by M1-Br (861 mg, 1.38 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (37 mg, 0.04 mmol, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (33 mg, 0.08 mmol, 6 mol%) and sodium tert-butoxide (265 mg, 2.76 mmol, 2.0 equiv) and toluene (5 mL). After 12 h at 110 °C, the reaction was stopped, cooled to room temperature and the organic phase was separated, concentrated and subjected to silica gel column chromatography to give 726 mg of a white solid in 65% yield. No structural characterization was performed and the product was used directly in the next step.

[0079] Synthesis of ligand (L-Pt4): LNH-Pt4 (726 mg, 0.90 mmol, 1.0 equiv) was added to the reaction flask, followed by ammonium hexafluorophosphate (293 mg, 1.80 mmol, 2.0 equiv), followed by triethyl orthoformate (5 mL). After 11 hours at 80°C, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated, and subjected to silica gel column chromatography to give 342 mg of a white solid in 56% yield. 1 H NMR (500 MHz, DMSO) δ 1.28 (s, 9H), 1.30 (s, 9H), 6.85 (t, J = 2.0 Hz, 1H), 6.93 (t, J = 2.0 Hz, 1H), 7.14 - 7.19 (m, 11H), 7.36 (t, J = 8.0 Hz, 1H), 7.46 - 7.49 (m, 4H), 7.54 - 7.58 (m, 3H), 7.66 - 7.70 (m, 2H), 7.75 (d, J = 9.0 Hz, 1H), 8.27 (d, J = 8.0 Hz, 1H), 8.34 - 8.36 (m, 3H), 8.58 (d, J = 6.0 Hz, 1H), 10.31 (s, 1H).

[0080] Synthesis of Pt4: L-Pt4 (150 mg, 0.16 mmol, 1.0 equiv), dichloro(1,5-cyclooctadiene)platinum(II) (59 mg, 0.17 mmol, 1.05 equiv) and sodium acetate (40 mg, 0.48 mmol, 3.0 equiv) were added to the reaction flask, followed by diethylene glycol dimethyl ether (10 mL). After reacting at 120 °C for 72 h, the reaction was stopped, cooled to room temperature, concentrated and subjected to silica gel column chromatography to obtain 96 mg of a pale yellow solid in 60% yield. 1 H NMR (500 MHz, DMSO) δ 1.34 (s, 9H), 1.42 (s, 9H), 5.99 - 6.83 (m, 6H), 6.87 - 7.70 (m, 14H), 7.80 (d, J = 8.2 Hz, 1H), 8.08 (d, J = 2.0 Hz, 1H), 8.12 - 8.34 (m, 3H), 8.40 (d, J = 8.0 Hz, 1H), 8.80 (d, J = 6.0 Hz, 1H).

[0081] (Example 6: Synthesis route of Pt5) [ka]

[0082] Synthesis of intermediate (LNH-Pt5): dPh-tBuNH2 (5.0 g, 12.7 mmol, 1.2 equiv) was added to the reaction flask, followed by M2-Br (6.0 g, 12.7 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (349 mg, 0.40 mmol, 3 mol%), 2-(di-tert-butylphosphine)biphenyl (230 mg, 0.80 mmol, 6 mol%) and sodium tert-butoxide (2.44 mg, 25.4 mmol, 2.0 equiv) and toluene (5 mL). After 11 h at 110 °C, the reaction was stopped, cooled to room temperature and the organic phase was separated, concentrated and subjected to silica gel column chromatography to give 5.97 g of a white solid in 60% yield. No structural characterization was performed and the product was used directly in the next step.

[0083] Synthesis of the ligand (L-Pt5): LNH-Pt5 (7.84 g, 10.0 mmol, 1.0 equiv) was added to the reaction flask, followed by ammonium hexafluorophosphate (3.26 mg, 20.0 mmol, 2.0 equiv), followed by triethyl orthoformate (20 mL). After 5 h at 75°C, the reaction was stopped, cooled to room temperature, and the organic phase was separated, concentrated, and subjected to silica gel column chromatography to give 3.08 mg of a white solid in 52% yield. 1 H NMR (500 MHz, DMSO) δ 1.30 (s, 9H), 1.45 (s, 9H), 6.97 (t, J = 2.0 Hz, 1H), 7.10 - 7.19 (m, 13H), 7.41 (dd, J = 8.5, 3.5Hz, 1H), 7.46 - 7.51 (m, 3H), 7.52 - 7.59 (m, 2H), 7.67 - 7.71 (m, 2H), 7.72 - 7.74 (m, 3H), 8.37 (d, J = 8.5 Hz, 1H), 8.59 (d, J = 4.5Hz, 1H), 10.26 (s, 1H).

[0084] Synthesis of Pt5: L-Pt5 (5.64 g, 6.0 mmol, 1.0 equiv.), dichloro(1,5-cyclooctadiene)platinum(II) (1.96 g, 6.3 mmol, 1.05 equiv.) and sodium acetate (1.48 mg, 18 mmol, 3.0 equiv.) were added to the reaction flask, and diethylene glycol dimethyl ether (10 mL) was added. After reacting at 120°C for 72 hours, the reaction was stopped, cooled to room temperature, concentrated, and subjected to silica gel column chromatography to obtain 1.30 g of a pale yellow solid in 34% yield. 1H NMR (500 MHz, CDCl3) δ 1.20 (s, 9H), 1.41 (s, 9H), 6.19 - 7.18 (m, 15H), 7.22 - 7.24 (m, 2H), 7.31 (d, J = 8.5 Hz, 1H), 7.48 (d, J = 8.5Hz, 2H), 7.80 (d, J = 8.0 Hz, 1H), 7.92 (d, J = 2.0 Hz, 1H), 7.99 (d, J = 8.5 Hz, 1H), 9.09 (d, J = 6.0 Hz, 1H).

[0085] Example 7: Synthesis of Pt6 Pt6 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (562 mg) in a yield of 75%. Molecular weight [M+H] + :994.1.

[0086] Example 8: Synthesis of Pt7 Pt7 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (624 mg) in a yield of 58%. Molecular weight [M+H] + :1212.5.

[0087] Example 9: Synthesis of Pt8 Pt8 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (661 mg) in a yield of 72%. Molecular weight [M+H] + :1216.5.

[0088] Example 10: Synthesis of Pt9 Pt9 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (484 mg) in a yield of 66%. Molecular weight [M+H] + :1218.5.

[0089] Example 11: Synthesis of Pt10 Pt10 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (455 mg) in a yield of 69%. Molecular weight [M+H] + :1219.5.

[0090] (Example 12: Synthesis of Pt11) Pt11 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (410 mg) in a yield of 67%. Molecular weight [M+H] + :1045.2.

[0091] Example 13: Synthesis of Pt12 Pt12 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (369 mg) in a yield of 58%. Molecular weight [M+H] + :989.1.

[0092] (Example 14: Synthesis of Pt13) Pt13 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (492 mg) in a yield of 82%. Molecular weight [M+H] + :1149.4.

[0093] (Example 15: Synthesis of Pt14) Pt14 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (471 mg) in a yield of 80%. Molecular weight [M+H] + :1006.1.

[0094] Example 16: Synthesis of Pt15 Pt15 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (596 mg) in a yield of 74%. Molecular weight [M+H] + :993.1.

[0095] Example 17: Synthesis of Pt16 Pt16 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (615 mg) in a yield of 68%. Molecular weight [M+H] + :995.1.

[0096] (Example 18: Synthesis of Pt17) Pt17 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (582 mg) in a yield of 66%. Molecular weight [M+H] + :1213.5.

[0097] (Example 19: Synthesis of Pt18) Pt18 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (471 mg) in a yield of 76%. Molecular weight [M+H] + :1217.6.

[0098] (Example 20: Synthesis of Pt19) Pt19 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (596 mg) in a yield of 78%. Molecular weight [M+H] + :1218.6.

[0099] (Example 21: Synthesis of Pt20) Pt20 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (597 mg) in a yield of 72%. Molecular weight [M+H] + :1275.7.

[0100] (Example 22: Synthesis of Pt21) Pt21 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (576 mg) in a yield of 74%. Molecular weight [M+H] + :1010.1.

[0101] (Example 23: Synthesis of Pt22) Pt22 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (615 mg) in a yield of 68%. Molecular weight [M+H] + :1228.6.

[0102] (Example 24: Synthesis of Pt23) Pt23 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (592 mg) in a yield of 66%. Molecular weight [M+H] + :1232.6.

[0103] (Example 25: Synthesis of Pt24) Pt24 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (571 mg) in a yield of 76%. Molecular weight [M+H] + :1234.6.

[0104] (Example 26: Synthesis of Pt25) Pt25 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (596 mg) in a yield of 78%. Molecular weight [M+H] + :1235.6.

[0105] (Example 27: Synthesis of Pt26) Pt26 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (597 mg) in a yield of 72%. Molecular weight [M+H] + :1003.1.

[0106] (Example 28: Synthesis of Pt27) Pt27 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (696 mg) in a yield of 74%. Molecular weight [M+H] + :1005.1.

[0107] (Example 29: Synthesis of Pt28) Pt28 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (615 mg) in a yield of 68%. Molecular weight [M+H] + :1061.3.

[0108] (Example 30: Synthesis of Pt34) Pt34 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (582 mg) in a yield of 66%. Molecular weight [M+H] + :1025.4.

[0109] Example 31: Synthesis of Pt39 Pt39 was synthesized by referring to the synthesis process and reaction conditions of compound Pt1, and the target product was obtained as a yellow solid (471 mg) in a yield of 76%. Molecular weight [M+H] + :1235.6.

[0110] [Table 1]

[0111] As can be seen from Table 1, the metal complexes provided by the present invention are all in the blue and deep blue emission ranges, have narrow half-widths, and are good blue phosphorescent materials.

[0112] OLED device manufacturing As a reference method for the device embodiment, the present invention involves evaporating a p-type doping material or co-evaporating a p-type doping material with a hole injection material at a concentration of 1% to 50% on the surface or anode of an ITO glass having a light-emitting area of ​​2 mm x 2 mm to form a hole injection layer (HIL) of 5 to 100 nm and a hole transport layer (HTL) of 5 to 200 nm, and then forming an emissive layer (EML) of 10 to 100 nm (which may contain a compound of the present invention) on the hole transport layer, and forming an electron transport layer (ETL) of 20 to 200 nm and a cathode of 50 to 200 nm. 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 produce an OLED device. The OLED is tested by standard methods. The device materials according to the present invention can be obtained by known synthesis methods unless otherwise specified.

[0113] In a preferred 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) (mass ratio of Pt1:HTH-85:ETH-45 is 10:60:30) / ETH-5 (5 nm) / ET-14 (40 nm) / LiQ (1 nm) / Al (100 nm).

[0114] Device examples 2 to 30 and comparative example 1 were prepared using structures similar to device example 1, with the only difference being that Pt2, Pt3, Pt4, Pt5, Pt-6, Pt7, Pt8, Pt9, Pt10, Pt11, Pt12, Pt13, Pt14, Pt15, Pt16, Pt17, Pt18, Pt19, Pt20, Pt21, Pt22, Pt23, Pt24, Pt25, Pt26, Pt27, Pt28, Pt34, Pt39, and R1 were substituted for Pt1 in device example 1. The luminescence properties of the comparative example and each device example prepared above by standard methods were tested and the data are shown in Table 2. The structural formulas of the devices involved are as follows, where P-4 is HATCN and ET-14 is BPyTP.

[0115] [ka]

[0116] [Table 2]

[0117] As can be seen from Table 2, compared with Comparative Example 1, Device Example 1 to Device Example 30 prepared in the present application show good device performance in terms of driving voltage, current efficiency and device life. The improvement in performance of each device example is based on the better electron transport ability of the specific compound material of the present invention. It can be seen that when this is used as a light-emitting layer material to manufacture an electronic device, it is possible to reduce the driving voltage and improve the current efficiency and device life. In addition, all of the devices manufactured by the present invention are deep blue light devices, and the CIEy value is evenly less than 0.20. This shows that the compounds provided by the present invention have a certain commercial application value.

[0118] In a preferred embodiment, the structure of device example 31 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).

[0119] Device Examples 32 to 38 were each fabricated using a structure similar to Device Example 31, 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 structures and luminescence property data are shown in Table 3.

[0120] [Table 3]

[0121] As can be seen from Table 3, when the compound of the present invention is used as a sensitizing material and the boron-containing compound is used as an emitting material in a device, the performance of each device is greatly improved, which shows that the compound provided by the present invention has a certain commercial application value. In addition, if the device structure is sensitized after adding the boron-containing compound, the CIEy value can be further reduced, and the purity of the emission color of the device can be further improved.

[0122] The applicant declares that the above is only any preferred embodiment of the present invention, and does not limit the protection scope of the present invention. Any changes or replacements that can be easily thought of within the technical scope disclosed in the present invention by anyone familiar with the art will be obvious to those skilled in the art and fall within the protection scope and disclosure scope of the present invention.

[0123] (Additional Note) (Appendix 1) A tetradentate cyclometallated platinum(II) complex, characterized in that the tetradentate cyclometallated platinum(II) complex is selected from any one of the chemical structural formulas shown below, in which "D" represents deuterium and "Ph" represents a phenyl group. [ka] [ka]

[0124] (Appendix 2) Application of the tetradentate cyclometallated platinum(II) complexes described in Appendix 1 in electronic devices.

[0125] (Appendix 3) The application of claim 2, wherein the electronic device includes 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 quencher, a light-emitting electrochemical cell, and an organic laser diode.

[0126] (Appendix 4) 1. An organic electroluminescent device comprising a cathode, an anode, and an organic functional layer interposed between the anode and the cathode, the organic functional layer comprising the tetradentate cyclometallated platinum(II) complex described in Appendix 1.

[0127] (Appendix 5) An organic electroluminescent device, characterized in that the organic functional layer includes an emitting layer, and the emitting layer contains the tetradentate cyclometallated platinum(II) complex described in Appendix 1.

[0128] (Appendix 6) The organic electroluminescence device according to claim 5, further comprising a fluorescent doping material in the light-emitting layer, the fluorescent doping material being selected from any one or more of the compounds represented by formulae (BN1) to (BN5). [ka] [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 R each independently represents mono-, di-, tri-, tetra- or no substitution. 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, 11 each independently represents the group consisting of hydrogen, deuterium, N, a C1-C30 alkyl group, and a C6-C60 aryl group.

[0129] (Appendix 7) The organic electroluminescent device described in Appendix 6, wherein R4, R5, R6, and R9 are each independently selected from a substituted or unsubstituted diphenylamine, a substituted or unsubstituted carbazolyl group, and the substitution may be multiple times, and when the substituent is included, the substituent is selected from deuterium, a C1-C30 alkyl group, and a C6-C30 aryl group.

[0130] (Appendix 8) Above R7~R8, R 10 ~R 11 and each independently is selected from the group consisting of hydrogen, a C1-C30 alkyl group, and a C6-C60 aryl group.

[0131] (Appendix 9) The organic electroluminescent device described in Appendix 6, characterized in that the fluorescent doping material is selected from any one of the following chemical structural formulas, in which Ph represents a phenyl group, and D4 and D5 represent substitutions with 4 and 5 deuterium atoms, respectively. [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0132] (Appendix 10) 1. 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, the organic light-emitting functional layer comprising a tetradentate cyclometallated platinum(II) complex as described in Appendix 1.

[0133] (Appendix 11) The organic optoelectronic device according to claim 10, characterized in that the organic light-emitting functional layer also contains a fluorescent doping material having one or more of the compounds represented by formulas (BN1) to (BN5). [ka] [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 R each independently represents mono-, di-, tri-, tetra- or no substitution. 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, 11 each independently represents the group consisting of hydrogen, deuterium, N, a C1-C30 alkyl group, and a C6-C60 aryl group.

[0134] (Appendix 12) A composition comprising a tetradentate cyclometallated platinum(II) complex as described in Appendix 1.

[0135] (Appendix 13) 10. A formulation comprising a tetradentate cyclometallated platinum(II) complex as described in Appendix 1.

[0136] (Appendix 14) A display or lighting device, comprising at least one of the organic electroluminescence devices according to any one of claims 4 to 9.

Claims

1. A tetradentate cyclometallated platinum(II) complex, characterized in that the tetradentate cyclometallated platinum(II) complex is selected from any one of the chemical structural formulas shown below, wherein "D" represents deuterium and "Ph" represents a phenyl group. 【Chemistry 1-1】 【Chemistry 1-2】

2. Application of the tetradentate cyclometallated platinum(II) complexes according to claim 1 in electronic devices.

3. 3. The application of claim 2, characterized in that the 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 field quenchers, light emitting electrochemical cells and organic laser diodes.

4. 1. An organic electroluminescent device comprising a cathode, an anode and an organic functional layer interposed between the anode and the cathode, the organic functional layer comprising the tetradentate cyclometallated platinum(II) complex according to claim 1.

5. 13. An organic electroluminescence device, comprising: the organic functional layer including an emitting layer, the emitting layer containing the tetradentate cyclometallated platinum(II) complex according to claim 1.

6. The organic electroluminescence device according to claim 5, further comprising a fluorescent doping material in the light-emitting layer, the fluorescent doping material being selected from any one or more of the compounds represented by formulas (BN1) to (BN5). 【Chemistry 2】 [Wherein, 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 R each independently represents mono-, di-, tri-, tetra- or no substitution. 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; ４ ~R １１ each independently represents the group consisting of hydrogen, deuterium, N, a C1-C30 alkyl group, and a C6-C60 aryl group.

7. The R ４ , R ５ , R ６ , R ９ are each independently selected from a substituted or unsubstituted diphenylamine, a substituted or unsubstituted carbazolyl group, the substitution may be multiple times, and when the compound contains a substituent, the substituent is selected from deuterium, a C1-C30 alkyl group, and a C6-C30 aryl group. The organic electroluminescent device according to claim 6,

8. The R ７ ~R ８ , R １０ ~R １１ and each independently is selected from the group consisting of hydrogen, a C1-C30 alkyl group, and a C6-C60 aryl group.

9. The organic electroluminescent device according to claim 6, characterized in that the fluorescent doping material is selected from any one of the following chemical structural formulas, in which Ph represents a phenyl group, and D4 and D5 respectively mean that they are substituted with 4 and 5 deuterium atoms. 【Chemistry 3-1】 【Chemistry 3-2】 【Chemistry 3-3】 【Chemistry 3-4】 【Chemistry 3-5】 【Chemistry 3-6】 【Chemistry 3-7】

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, the organic light-emitting functional layer comprising the tetradentate cyclometallated platinum(II) complex of claim 1.

11. The organic optoelectronic device according to claim 10, characterized in that the organic light-emitting functional layer also contains a fluorescent doping material having any one or more of the compounds represented by formula (BN1) to formula (BN5). 【Chemistry 4】 [Wherein, 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 R each independently represents mono-, di-, tri-, tetra- or no substitution. 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; ４ ~R １１ each independently represents the group consisting of hydrogen, deuterium, N, a C1-C30 alkyl group, and a C6-C60 aryl group.

12. A composition comprising the tetradentate cyclometallated platinum(II) complex of claim 1.

13. A formulation comprising the tetradentate cyclometallated platinum(II) complex of claim 1.

14. A display or lighting device, characterized in that it comprises one or more organic electroluminescent devices according to any one of claims 4 to 9.

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