Organic electroluminescent device, organic optoelectronic device, and display and lighting device including said organic electroluminescent device

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 belongs 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 diodes (OLEDs) are a new generation of full-color display and lighting technology. Compared to LCDs, which have drawbacks such as slow response times, narrow viewing angles, the need for backlighting, and high power consumption, OLEDs are self-emitting devices that do not require backlighting and are energy-efficient. They also have low driving voltages, fast response times, high resolution and contrast, a wide viewing angle, and excellent low-temperature properties. OLED devices can be made thinner and more flexible. They also have the advantages of low manufacturing costs, simple manufacturing processes, and the ability to be fabricated on large areas. Therefore, OLEDs have enormous potential for a wide range of applications in high-end electronics and aerospace. With gradual increases in investment, deeper research and development, and upgrades and improvements to manufacturing facilities, OLEDs will have a very wide range of application scenarios and development prospects in the future.

[0003] The design and development of emissive materials is at the heart of OLED development. Most currently used emissive layers in OLED devices utilize a host-guest emissive system, in which a guest emissive material is doped into a host material. The host material typically has a larger energy gap than the guest emissive material, transferring energy from the host to the guest material, which is then excited and emits light. Commonly used organic phosphorescent guest materials are heavy metal atoms such as iridium(III), platinum(II), and palladium(II). Commonly used phosphorescent organic materials, mCBP (3,3'-bis(9-carbazolyl)-biphenyl) and 2,6-mCPy (2,6-bis(9-carbazolyl)-pyridine), have high efficiency and high triplet energy levels. When used as organic materials, they can efficiently transfer triplet energy from the organic emissive material to the guest phosphorescent material. However, mCBP has the property of easily transporting holes but poorly transporting electrons, and 2,6-mCPy has poor hole transport properties, resulting in an imbalance of charge in the emissive layer and reduced current efficiency. Furthermore, the number of cyclometallated iridium(III) complex molecules, a heavy metal phosphorescent organic complex molecule, currently in use is limited. The abundance of metallic platinum in the Earth's crust and the global annual production are approximately 10 times that of metallic iridium. The price of IrCl3·H2O, used to prepare iridium(III) complex phosphorescent materials, is also much higher than that of PtCl2, used to prepare platinum(II) complex phosphorescent materials. Furthermore, the preparation of iridium(III) complex phosphorescent materials involves four steps: iridium(III)-containing dimerization, ligand exchange of the iridium(III) intermediate, synthesis of mer-iridium(III) complex, and conversion of mer- to fac-iridium(III) complex isomers. This significantly reduces the overall yield and utilization rate of the raw material IrCl3·H2O, increasing the preparation cost of iridium(III) complex phosphorescent materials. In contrast, the preparation of platinum(II) complex phosphorescent materials requires only the final step of ligand metallization and platinum salt synthesis, which increases the utilization rate of platinum element and further reduces 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 lifespan 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 applications thereof. The tetradentate cyclometallated platinum(II) complex of the present invention can be used as a guest phosphorescent material in an emissive layer to provide excellent device performance. 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 lifetime, 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: wherein "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 formulae 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-quenched devices (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 to 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 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 one or more of the compounds represented by formulae (BN1) to (BN5).

[0013] [ka] 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 eR each independently represents mono-, di-, tri-, tetra- or unsubstituted. 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 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 R4, R5, R6, and R9 contain a substituent, the substituent is selected from a deuterium atom, a C1-C30 alkyl group, and a C6-C30 aryl group.

[0015] Preferably, the 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, the R4 to R 11 At least one hydrogen atom in the formula (I) may be substituted with deuterium.

[0017] The fluorescent doping material is selected from any one of the following chemical structural formulas, where Ph represents a phenyl group, and D4 and D5 represent substitutions with four and five 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, wherein the organic light-emitting functional layer contains a tetradentate cyclometallated platinum(II) complex having a structure represented by any of the above formulas Pt1 to Pt45. For example, the platinum(II) complex may be contained 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 a 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 any of the above formulae Pt1 to Pt45 or the above composition and at least one solvent. The solvent is not particularly limited, and examples thereof include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butylbenzene, and tert-butylbenzene; halogenated saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, and bromocyclohexane; halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene; ether solvents such as tetrahydrofuran and tetrahydropyran; and ester solvents such as alkyl benzoates.

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

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

[0025] Compared with the prior art, the advantageous effects of the present invention are: The present invention provides a phosphorescent material based on a tetradentate cyclometallated platinum(II) complex. The introduction of 2,6-di(phenyl)tert-butylphenyl at the appropriate position of the ligand increases the dihedral angle between pyridine units and reduces intermolecular stacking. At the same time, the charge distribution in the excited state is improved, allowing the material to have more metal-to-pyridocarbene charge transfer states (3MLCT), which is beneficial for improving emissivity and extending device lifetime. The material of the present invention has good chemical and thermal stability, making it easy to fabricate vapor-deposited OLED devices. When combined with a fluorescent doping material, the transport of holes and electrons is balanced, resulting in more efficient energy transfer between the host and guest. Organic electroluminescent devices fabricated using the compound of the present invention as the emissive layer exhibit significant improvements in current efficiency and lifetime, and significantly reduced lighting voltage. In particular, when combined with a phosphorescent-sensitized boron-containing compound, the color purity of the device light can be improved. DETAILED DESCRIPTION OF THE INVENTION

[0026] The present invention will be described in detail below. The following description of the components may be based on typical embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.

[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" connote that such substitution is subject to the permissible valences of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not undergo spontaneous transformation, such as rearrangement, cyclization, or elimination). Furthermore, in certain embodiments, it is contemplated that individual substituents may optionally be 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 general 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 groups listed above. For example, R 1When is a straight-chain alkyl group, one of the hydrogen atoms of the alkyl group may optionally be replaced by a hydroxyl group, an alkoxy group, an alkyl group, a halogen, or the like. 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 comprising 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, including, for example, 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 can be cyclic or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can 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, and phenanthrenyl. 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 included within the term "aryl" and is defined as a group containing an aromatic group that does not contain a heteroatom. Aryl groups can 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 where 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," means that one or more hydrogen atoms of the specified moiety have been replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted" group can have a suitable substituent at each substitutable position of the group, and when one or more positions in 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 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., further substituted or unsubstituted) unless clearly indicated to the contrary.

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

[0035] [ka]

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

[0037] [ka] [wherein n is typically an integer, i.e., 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) "Independent substituents" means that each R substituent can be defined independently. For example, in one example, R n(a) is a halogen, R a(m) is not necessarily a halogen in that example.

[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 specific synthetic methods (shown separately) or to particular reagents (shown separately), as such 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, including glass or transparent plastic substrates, opaque substrates such as silicon or stainless steel, or flexible PI films. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and waterproof properties, and their use varies depending on the properties of the substrate. Materials for the hole injection layer, hole transport layer, and electron injection layer 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 syntheses, compositions, devices, or methods are intended only 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 contain some errors. Unless otherwise stated, measurements are taken separately, temperatures are in °C or near ambient, and pressures are near ambient.

[0045] The following examples provide methods for preparing novel compounds, but the preparation of such compounds is not limited to these methods. The compounds sought to be protected in the present invention are easy to modify and prepare in this technical field, and 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. Temperature, catalyst, concentration, reactants, and reaction process can be changed, and different conditions can be selected for different reactants to prepare the compounds.

[0046] 1 H NMR (500 MHz), 1 H NMR (400 MHz), 13 C NMR (126 MHz) spectra were measured on a ANANCE III (500 M) nuclear magnetic resonance spectrometer. Unless otherwise specified, nuclear magnetic resonance spectra were measured uniformly using DMSO-d or CDCl containing 0.1% TMS as the solvent. 1For H NMR spectra, TMS (δ = 0.00 ppm) was used as the internal standard when CDCl3 was used as the solvent. When DMSO-d6 was used 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) was used as the internal standard. 13 For C NMR spectra, CDCl (δ = 77.00 ppm) or DMSO-d (δ = 39.52 ppm) was used as the internal standard. HPLC-MS 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: Synthetic 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 a reaction flask and dissolved in dichloromethane (150 mL). N-bromosuccinimide (37.7 g, 210 mmol, 2.1 equiv.) was added and the reaction was continued at room temperature for 48 hours 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-tBuNH (5 g, 16.3 mmol, 1.0 equiv.) was added to the reaction flask and dissolved in N-methylpyrrolidone (50 mL). Sodium hydride (1.96 g, 49 mmol, 3.0 equiv.) and o-fluoronitrobenzene (3.45 g, 24.5 mmol, 1.5 equiv.) were added and the reaction was continued at room temperature for 48 h before quenching. 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. Structural characterization was not performed and the product was used directly in the next step.

[0050] Synthesis of intermediate (dBr-tBu2NH2): dBr-tBuNO (4.8 g, 11.2 mmol, 1.0 equiv.), stannous chloride (10.1 g, 44.8 mmol, 4.0 equiv.) were added to a reaction flask, followed by ethyl acetate (50 mL) and ethanol (50 mL). After 24 h in oil at 78 °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 3.43 g of a white solid in 82% yield. Structural characterization was not performed and the product was used directly in the next step.

[0051] Synthesis of intermediate (dPh-tBuNH2): To a reaction flask was added dBr-tBuNH (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). After 24 h at 90 °C, the reaction was stopped and cooled to room temperature. The organic phase was separated, concentrated, and subjected to silica gel column chromatography to give 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 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. Structural characterization was not 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 and cooled to room temperature. 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 solid 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 dimethyl sulfoxide (50 mL) was added. After 12 h at 100 °C, the reaction was stopped and cooled to room temperature. The organic phase was separated, concentrated, and subjected to silica gel column chromatography to obtain 6.94 g of a white solid in 91% yield.

[0056] [ka]

[0057] Synthesis of intermediate (LNH-Pt1): dPh-tBuNH (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). Toluene (5 mL) was added. 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. Structural characterization was not performed and the product was used directly in the next step.

[0058] Synthesis of the 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 and cooled to room temperature. The organic phase was separated, concentrated, and purified by 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 a reaction flask, and diethylene glycol dimethyl ether (10 mL) was added. 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 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 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 dimethyl sulfoxide (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). Toluene (50 mL) was added. 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. Structural characterization was not performed and the product was used directly in the next step.

[0064] Synthesis of the 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 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 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-Pt (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 a reaction flask, and diethylene glycol dimethyl ether (10 mL) was added. After 72 h at 120 °C, 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 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. Structural characterization was not 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 the product 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 a 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). Structural characterization was not 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). Structural characterization was not 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 dimethyl sulfoxide (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 a 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). Toluene (100 mL) was added. 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. Structural characterization was not 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.), and then 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 obtain 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 a reaction flask, and diethylene glycol dimethyl ether (50 mL) was added. After 72 h 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 identity of the product.

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

[0078] Synthesis of intermediate (LNH-Pt4): dPh-CN-NH (500 mg, 1.38 mmol, 1.2 equiv) was added to a 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). Toluene (5 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 726 mg of a white solid in 65% yield. Structural characterization was not performed and the product was used directly in the next step.

[0079] Synthesis of the 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), and then triethyl orthoformate (5 mL). After 11 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 obtain 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-Pt (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 a reaction flask, followed by diethylene glycol dimethyl ether (10 mL). After 72 h at 120 °C, 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 of Pt5 [ka]

[0082] Synthesis of intermediate (LNH-Pt5): dPh-tBuNH2 (5.0 g, 12.7 mmol, 1.2 equiv) was added to a 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). Toluene (5 mL) was added. 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. Structural characterization was not 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), and then 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 obtain 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 a reaction flask, and diethylene glycol dimethyl ether (10 mL) was added. 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 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 75% yield. 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 82% yield. 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 80% yield. 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 68% yield. 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 72% yield. 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 74% yield. 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 68% yield. 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 region, have narrow half-widths, and are excellent blue phosphorescent materials.

[0112] OLED device manufacturing As a reference method for device examples, the present invention involves vapor deposition of a p-type doping material or co-evaporation of 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 substrate having a 2 mm x 2 mm light-emitting area to form a 5-100 nm hole injection layer (HIL) and a 5-200 nm hole transport layer (HTL). A 10-100 nm emissive layer (EML) (which may contain a compound of the present invention) is then formed on the hole transport layer, followed by a 20-200 nm electron transport layer (ETL) and a 50-200 nm cathode. An electron blocking layer (EBL) is optionally added between the HTL and EML layers, and an electron injection layer (EIL) is added between the ETL and the cathode to fabricate an OLED device. The OLED is then tested using standard methods. Unless otherwise specified, the device materials of the present invention can be obtained by known synthetic methods.

[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) (the 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 each prepared using a structure 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 used to replace Pt1 in Device Example 1. The luminescence characteristics of the comparative example and each device example prepared above were tested using standard methods, 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 to Comparative Example 1, Device Examples 1 to 30 prepared in the present invention exhibit better device performance in terms of driving voltage, current efficiency, and device life. The improved performance of each device example is based on the superior electron transport ability of the specific compound material of the present invention. When this compound is used as a light-emitting layer material in an electronic device, it is possible to reduce the driving voltage while improving the current efficiency and device life. Furthermore, all of the devices prepared according to the present invention are deep blue light-emitting devices, and all have CIEy values ​​less than 0.20. This indicates that the compounds provided by the present invention have certain commercial application value.

[0118] In a preferred embodiment, the structure of Example 31 of the device 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) (the 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 compounds of the present invention are used as sensitizers and boron-containing compounds as luminescent materials in devices, the performance of each device is significantly improved, demonstrating that the compounds provided by the present invention have certain commercial application value. Furthermore, adding boron-containing compounds to sensitize the device structure can further reduce the CIEy value, thereby further improving the purity of the emitted color of the device.

[0122] The applicant declares that the above-described are only any preferred embodiments of the present invention, and do not limit the protection scope of the present invention. It will be obvious to those skilled in the art that any changes or substitutions that can be easily thought of within the technical scope disclosed in the present invention by anyone familiar with the art will fall within the protection scope and disclosure scope of the present invention.

[0123] (Addendum) (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, wherein "D" represents deuterium and "Ph" represents a phenyl group. [ka] [ka]

[0124] (Appendix 2) Applications 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, wherein the organic functional layer contains the tetradentate cyclometallated platinum(II) complex described in Appendix 1.

[0127] (Appendix 5) An organic electroluminescent device, wherein 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 electroluminescent device according to Appendix 5, characterized in that 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 formulas (BN1) to (BN5). [ka] 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 unsubstituted. 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 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 and a substituted or unsubstituted carbazolyl group, and the substitution may be multiple times. When the organic electroluminescent device contains a substituent, the substituent is selected from a deuterium atom, a C1-C30 alkyl group, and a C6-C30 aryl group.

[0130] (Appendix 8) Above R7~R8, R 10 ~R 11 and each independently are 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 mean that they are substituted 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, wherein the organic light-emitting functional layer contains a tetradentate cyclometallated platinum(II) complex as described in Appendix 1.

[0133] (Appendix 11) The organic optoelectronic device described in Appendix 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] 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 unsubstituted. 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 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, characterized in that it comprises one or more organic electroluminescent devices according to any one of appendices 4 to 9.

Claims

1. 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 comprises a light-emitting layer, and the light-emitting layer contains a tetradentate cyclometallated platinum(II) complex having a structure selected from any of the chemical structural formulas shown below, wherein "D" represents deuterium and "Ph" represents a phenyl group: 【Chemistry 1-1】 【Chemistry 1-2】 an organic electroluminescence device, wherein 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 formulas (BN1) to (BN5). 【Chemistry 2】 wherein X is O, S or Se; X 1 is O, S, Se or NR 10 ; X 2 is O, S, Se or NR 8 ; X 3 is O, S, Se or NR 7 ; X 4 is represented by O, S, Se or NR 11 ; R ｂ ~R ｅ R each independently represents mono-, di-, tri-, tetra- or unsubstituted. 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 are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted carbazolyl group, a C1-C30 alkyl group, and a C6-C60 aryl group.

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

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

4. 2. The organic electroluminescent device according to claim 1, wherein 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 four and five deuterium atoms, respectively. 【Chemistry 3-1】 【Chemistry 3-2】 【Chemistry 3-3】 [Chemistry 3-4] [Transformation 3-5] [Chemistry 3-6] 【Chemistry 3-7】

5. 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, wherein the organic light-emitting functional layer contains a tetradentate cyclometallated platinum(II) complex having a structure selected from the chemical structural formulas shown below, wherein "D" represents deuterium and "Ph" represents a phenyl group: 【Chemistry 4-1】 【Chemistry 4-2】 An organic optoelectronic device, characterized in that the organic light-emitting functional layer also contains a fluorescent doping material having one or more compounds represented by the following formulas (BN1) to (BN5): 【Transformation 5】 wherein X is O, S or Se; X 1 is O, S, Se or NR 10 ; X 2 is O, S, Se or NR 8 ; X 3 is O, S, Se or NR 7 ; X 4 is represented by O, S, Se or NR 11 ; R ｂ ~R ｅ R each independently represents mono-, di-, tri-, tetra- or unsubstituted. 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 are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted carbazolyl group, a C1-C30 alkyl group, and a C6-C60 aryl group.

6. A display or lighting device, characterized in that it comprises one or more organic electroluminescent devices according to any one of claims 1 to 4.

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