Tetradentate cyclometalated platinum (II) complex having n-heterocyclic carbene structure, electronic device, apparatus, and use thereof

Abstract

The present invention relates to the technical field of the preparation of organic electroluminescent materials, and specifically relates to a tetradentate cyclometalated platinum (II) complex having an N-heterocyclic carbene structure, an electronic device, an apparatus, and the use thereof. By introducing an alkyl or an aryl at the 4-, 3'- and 5'-positions of 1,1'-biphenyl to increase steric hindrance, the red shift or the luminescence quenching caused by molecular aggregation is avoided; and peripheral deuteration of a cyclometalating ligand can improve the material stability, thereby endowing a phosphorescent material with excellent chemical and thermal stability, and making it easy to prepare an evaporation-type OLED device. An organic electroluminescent device made by using a complex as a luminescent layer material results in a significant improvement in both current efficiency and service life, and has great application prospects in the field of OLED display and illumination.

Description

A tetradentate ring platinum(II) complex with a nitrogen-hexane carbene structure, electronic devices, apparatuses and their applications Technical Field

[0001] This invention belongs to the field of organic electroluminescent material preparation technology, specifically relating to a tetradentate ring platinum(II) complex with a nitrogen-hexane carbene structure, electronic devices, apparatuses and their applications. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are a new generation of full-color display and lighting technology. Compared to liquid crystal displays (LCDs), which suffer from slow response times, narrow viewing angles, the need for backlighting, and high energy consumption, OLEDs, as self-emissive devices, do not require backlighting, thus saving energy. Furthermore, they offer low driving voltage, fast response times, high resolution and contrast, wide viewing angles, and excellent low-temperature performance. OLED devices can be made thinner and can be fabricated into flexible structures. In addition, they have advantages such as low production costs, simple manufacturing processes, and the ability to be mass-produced. Therefore, OLEDs have broad and enormous application prospects in high-end electronic products and aerospace. With increasing investment, further research and development, and upgrades to production equipment, OLEDs have a very wide range of application scenarios and development prospects in the future.

[0003] The core of OLED development lies in the design and development of luminescent materials. Early OLED devices primarily used small organic molecule fluorescent materials as their luminescent agents. However, spin statistical quantum mechanics shows that under electroluminescence, the generated singlet and triplet excitons account for only 25% and 75%, respectively. Since traditional fluorescent materials can only utilize excitons in the singlet state, their maximum theoretical internal quantum efficiency is only 25%, with the remaining 75% of triplet excitons lost through non-radiative transitions. In 1998, Professor Forrest of Princeton University and Professor Thompson of the University of Southern California discovered the phosphorescence electroluminescence phenomenon of heavy metal organic complex molecules at room temperature. Due to the strong spin-orbit coupling of heavy metal atoms, excitons can more easily undergo intersystem crossing (ISC) from the singlet to the triplet state. This allows OLED devices to fully utilize all singlet and triplet excitons generated by electro-excitation, enabling the theoretical internal quantum efficiency of the luminescent material to reach 100% (Nature, 1998, 395, 151).

[0004] Currently, almost all OLED devices utilize a host-guest emission mechanism in their emitting layers. This involves doping a host material with a guest emitting material. The host material typically has a higher energy level than the guest material, transferring energy from the host material to the guest material, thus exciting it to emit light. Commonly used organic phosphorescent guest materials are heavy metal atoms such as iridium(III), platinum(II), and Pd(II). Currently, the number of heavy metal phosphorescent organic complex molecules, specifically iridium(III) cyclic complexes, is limited. The abundance of platinum in the Earth's crust and its annual global production are approximately ten times that of iridium. The price of IrCl3·H2O (1100 RMB / gram), used to prepare iridium(III) complex phosphorescent materials, is also significantly higher than that of PtCl2 (210 RMB / gram), used to prepare platinum(II) complex phosphorescent materials. Furthermore, the preparation of iridium(III) complex phosphorescent materials involves four steps: iridium(III) dimer formation, iridium(III) intermediate ligand exchange, mer-iridium(III) complex synthesis, and mer-to-fac-iridium(III) complex isomer conversion. This significantly reduces the overall yield, greatly decreasing the utilization rate of the raw material IrCl3·H2O and increasing the preparation cost of iridium(III) complex phosphorescent materials. In contrast, the preparation of platinum(II) complex phosphorescent materials only involves the final step of ligand metallization design of platinum salts, resulting in high platinum utilization and further reducing the preparation cost. In summary, the preparation cost of platinum(II) complex phosphorescent materials is much lower than that of iridium(III) complex phosphorescent materials.

[0005] However, the development of platinum complex materials and devices still faces some technical challenges. How to improve the chemical and thermal stability of materials, avoid redshift or luminescence quenching caused by molecular aggregation, and thus improve device lifespan? This problem is particularly important for blue and deep blue luminescent materials, as it significantly impacts the efficiency and energy utilization of commercially available top-emitting devices. Therefore, there is an urgent need to develop novel phosphorescent platinum(II) complexes. Summary of the Invention

[0006] The purpose of this invention is to provide a tetradentate cyclic platinum(II) complex with a nitrogen-hexane carbene structure, electronic devices, apparatuses, and their applications. The provided tetradentate cyclic platinum(II) complex has a 4,3',5'-substituted [1,1'-biphenyl]-2-azacarbene structure. By introducing alkyl or aryl groups at the 4,3',5' positions, steric hindrance is increased, avoiding redshift or luminescence quenching caused by molecular aggregation. Deuteration around the cyclic metal ligand improves material stability, exhibiting excellent chemical and thermal stability, and facilitating the fabrication of vapor-deposited OLED devices. Organic electroluminescent devices fabricated using the complex of this invention as the emitting layer show significant improvements in current efficiency and lifetime, demonstrating great application potential in OLED displays and lighting.

[0007] The objective of this invention is achieved through the following technical solutions;

[0008] In many embodiments, the present invention provides a tetradentate ring platinum(II) complex having the structure shown in formula (I):

[0009] In equation (I), R 1 R 2 and R 3 The same or different, each independently represented as a C1–C30 alkyl, a C1–C30 deuterated alkyl, a C1–C30 haloalkyl, a C3–C30 cycloalkyl, a substituted or unsubstituted C6–C60 aryl, or a substituted or unsubstituted C5–C60 heteroaryl; R a R b R c R d R e R f R g Each can be independently represented as monosubstituted, disubstituted, trisubstituted, or tetrasubstituted; R a -R g Each is independently represented as hydrogen, deuterium, or a C1–C30 alkyl group; when substituted, the substituent may be selected from one or more of deuterium, C1–C14 alkyl, or C6–C60 aryl.

[0010] Preferably, in the tetradentate cyclic platinum(II) complex having the structure shown in formula (I), the hydrogen atoms can be partially or completely replaced by deuterium. More preferably, the R... a R b R c R d R e R f R g At least one hydrogen atom is replaced by deuterium.

[0011] In many implementations, R 1 R 2 and R 3 Each of the following is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodel, sec-decyl, tert-decyl, adamantyl, C1–C6 alkyl-substituted or unsubstituted phenyl, C1–C6 alkyl-substituted or unsubstituted pyridyl, or a combination thereof.

[0012] Furthermore, the R a It may be selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isonyl, sec-nonyl, tert-nonyl, n-decyl, isodel, sec-decyl, tert-decyl, adamantyl, one or a combination thereof.

[0013] Preferably, the R b R c R d R e R f R g They are independently represented as hydrogen and deuterium.

[0014] In many embodiments, the tetradentate cyclic platinum(II) complex is selected from any of the following chemical structures: where “D” represents deuterium:

[0015] In many embodiments, the present invention also provides the use of tetradentate ring platinum (II) complexes having the structure shown in formula (I) above in the fabrication of electronic devices.

[0016] Furthermore, the electronic device includes one or more of the following: organic electroluminescent device, organic optoelectronic device, organic integrated circuit, organic field-effect transistor, organic thin-film transistor, organic light-emitting transistor, organic solar cell, organic optical detector, organic photoreceptor, organic field quenching device, luminescent electrochemical cell, or organic laser diode.

[0017] In many embodiments, the present invention provides an organic electroluminescent device comprising: a cathode, an anode, and an organic functional layer therebetween, the organic functional layer comprising a tetradentate ring platinum (II) complex having the structure shown in formula (I) above.

[0018] Preferably, the organic functional layer includes a light-emitting layer, which includes a tetradentate cyclic platinum (II) complex having the structure shown in formula (I) above.

[0019] More preferably, the light-emitting layer further comprises a fluorescent dopant material; the fluorescent dopant material is preferably a boron-containing organic luminescent material, and more preferably a boron-containing compound.

[0020] In many embodiments, 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 comprises a tetradentate ring platinum(II) complex having the structure shown in formula (I) above. For example, the platinum(II) complex can be included as a light-emitting material in the organic light-emitting functional layer.

[0021] Furthermore, the organic light-emitting functional layer also contains any one or more fluorescent doping materials, wherein the fluorescent doping material is preferably a boron-containing organic luminescent material, and more preferably a phosphorus-sensitive boron-containing compound.

[0022] In this invention, organic optoelectronic devices can be fabricated by depositing metals or conductive oxides and their alloys onto a substrate using methods such as sputtering, electron beam evaporation, and vacuum deposition to form the anode. A hole injection layer, hole transport layer, light-emitting layer, air-blocking layer, and electron transport layer are then sequentially deposited onto the surface of the anode, followed by the deposition of the cathode. Alternatively, organic electroluminescent devices can be fabricated by depositing the cathode, organic functional layer, and anode onto a substrate in that order. The organic functional layer can include a multilayer structure comprising a hole injection layer, a hole transport layer, a light-emitting layer, a hole-blocking layer, and an electron transport layer. In this invention, the organic functional layer is prepared using polymer materials via solvent engineering (spin-coating, tape-casting, doctor-blading, screen-printing, inkjet printing, or thermal imaging, etc.) instead of evaporation methods, which can reduce the number of device layers.

[0023] The present invention also provides a composition comprising a tetradentate cyclic platinum(II) complex having the structure shown in formula (I) above. Preferably, the composition further comprises a fluorescent dopant material, which is preferably a boron-containing organic luminescent material, and more preferably a phosphorescently sensitizable boron-containing compound.

[0024] The present invention also provides a formulation comprising a tetradentate cyclic platinum(II) complex having the structure shown in formula (I) as described above and at least one solvent. The solvent is not particularly limited and may be any solvent well known to those skilled in the art, such as unsaturated hydrocarbon solvents, halogenated saturated hydrocarbon solvents, halogenated unsaturated hydrocarbon solvents, ether solvents, or ester solvents; wherein the unsaturated hydrocarbon solvent is toluene, xylene, mesitylene, tetrahydronaphthalene, n-butylbenzene, sec-butylbenzene, or tert-butylbenzene; the halogenated saturated hydrocarbon solvent is carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, or bromocyclohexane; the halogenated unsaturated hydrocarbon solvent is chlorobenzene, dichlorobenzene, or trichlorobenzene; the ether solvent is tetrahydrofuran or tetrahydropyran; and the ester solvent is an alkyl benzoate ester.

[0025] The present invention also provides a display or lighting device comprising one or more of the organic electroluminescent devices or organic optoelectronic devices as described above.

[0026] Preferably, the organic electroluminescent device of the present invention is any one of organic photovoltaic devices, organic light-emitting devices (OLEDs), organic solar cells (OSCs), electronic paper (e-paper), organic photosensitive materials (OPCs), organic thin-film transistors (OTFTs), organic memory elements, lighting and display devices.

[0027] The materials used in the organic electroluminescent devices according to the present invention can be classified as top-emitting, low-emitting, or bifacial-emitting.

[0028] The compounds of the organic electroluminescent devices according to embodiments of the present invention can be applied to electroluminescent devices such as organic solar cells, OLEDs for lighting, flexible OLEDs, organic photosensitive materials, and organic thin-film transistors, based on similar principles to those of organic light-emitting devices.

[0029] Compared with the prior art, the beneficial effects of this invention are as follows: This invention provides a tetradentate cyclic platinum(II) metal complex with a 4,3',5'-substituted [1,1'-biphenyl]-2-azacarbene structure. Firstly, by introducing sterically hindered alkyl or aryl groups at the 4,3',5' positions, steric hindrance is increased, widening the intermolecular distance and preventing redshift or luminescence quenching caused by molecular aggregation. Secondly, deuteration around the cyclic metal ligand improves CH bond stability, thereby giving the phosphorescent material of this invention excellent chemical and thermal stability, facilitating the fabrication of vapor-deposited OLED devices. Thirdly, organic electroluminescent devices fabricated using the compound of this invention as the emitting layer exhibit more efficient energy transfer between the host and guest, with significant improvements in current efficiency and lifetime. Further use of phosphorus-sensitized boron-containing compound systems can improve the color purity of the device. Detailed Implementation

[0030] As used in this invention, the terms "optional" or "optionally" mean that the event or situation described below may or may not occur, and the description includes both the case where the event or situation occurs and the case where it does not occur.

[0031] The term "substituted" as used in this invention is intended to encompass all permissible substituents of organic compounds. In a broad sense, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and non-aromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. For a suitable organic compound, permissible substituents may be one or more, the same or different. For the purposes of this invention, heteroatoms (e.g., nitrogen) can have hydrogen substituents and / or any permissible substituent of the organic compound described herein, satisfying the valence bond of that heteroatom. This disclosure is not intended to limit in any way to permissible substituents of organic compounds. Similarly, the terms "substituted" or "substituted with" imply that such substitution conforms to the permissible valence bond of the substituted atom and the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformations (e.g., by rearrangement, cyclization, elimination, etc.)). It is also expected that, in some respects, unless explicitly stated otherwise, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted).

[0032] When defining various terms, R 1 R 2 R 3 R a -R g In this invention, the general symbols are used to denote various specific substituents. These symbols can be any substituent, not limited to those disclosed in this invention, and while they may be defined as certain substituents in one case, they may be defined as other substituents in other cases.

[0033] As used in this invention, the term "alkyl" refers to a branched or unbranched saturated hydrocarbon group with 1 to 30 carbon atoms. Preferred alkyl groups are alkyl groups containing 1 to 24 carbon atoms, more preferably 1 to 9 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, semi-alkyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group may be cyclic or acyclic. It may be branched or unbranched. It may also be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups, including but not limited to the optionally substituted alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxyl, nitro, silyl, sulfoxo, or mercapto groups described in this invention.

[0034] Throughout this specification, "alkyl" is generally used to refer to both unsubstituted and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to in this invention by identifying the specific substituents on the alkyl group. For example, the terms "halogenated alkyl" or "halogenated alkyl" specifically refer to an alkyl group substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "deuterated alkyl" specifically refers to an alkyl group substituted with one or more deuterium atoms. The alkyl term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, as described below, etc. When "alkyl" is used in one context and a specific term such as "alkyl alcohol" is used in another context, it does not imply that the term "alkyl" does not simultaneously refer to the specific term such as "alkyl alcohol," etc.

[0035] This practice is also applied to other groups described in this invention. That is, when a term such as "cycloalkyl" refers to both an unsubstituted and a substituted cycloalkyl portion, the substituted portion may be specifically identified separately in this invention; for example, a specifically substituted cycloalkyl may be referred to as, for example, "alkylcycloalkyl". Similarly, a substituted alkoxy may be specifically referred to as, for example, "halogenated alkoxy", and a specifically substituted alkenyl may be, for example, "enol", etc. Likewise, the practice of using the general term such as "cycloalkyl" and the specific term such as "alkylcycloalkyl" is not intended to imply that the general term does not simultaneously include the specific term.

[0036] As used in this invention, the term "cycloalkyl" refers to a non-aromatic carbon-based ring consisting of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, adamantyl, etc. The term "heterocyclic alkyl" is a class of cycloalkyl groups as defined above and is included in the meaning of the term "cycloalkyl," wherein at least one ring carbon atom is substituted by a heteroatom, such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl and heterocyclic alkyl groups may be substituted or unsubstituted. The cycloalkyl and heterocyclic alkyl groups may be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxyl, nitro, silyl, sulfo-oxo, or mercapto groups as described in this invention.

[0037] As used in this invention, the term "aryl" refers to any carbon-based aromatic group containing 6 to 60 carbon atoms, preferably aryl groups containing 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms. The carbon-based aromatic groups include, but are not limited to, phenyl, naphthyl, phenyl, biphenyl, phenoxyphenyl, anthracene, phenanthrene, etc. The term "aryl" also includes "heteroaryl," which is defined as a group containing an aromatic group having at least one heteroatom introduced into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Aryl groups may be substituted or unsubstituted. Aryl groups may be substituted with one or more groups, including, but not limited to, the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azide, nitro, silyl, sulfo-oxo, or mercapto groups described in this invention. The term "biaryl" refers to a specific type of aryl group and is included in the definition of "aryl". A biaryl group is two aryl groups that are bonded together by a fused ring structure, as in naphthalene, or two aryl groups that are linked by one or more carbon-carbon bonds, as in biphenyl.

[0038] This document discloses compounds or complexes containing platinum. The terms "compound" and "complex" are used interchangeably in this invention. Additionally, the compounds disclosed herein have a neutral charge.

[0039] The compounds disclosed herein are applicable to a wide variety of optical and electro-optic devices, including but not limited to light-absorbing devices such as solar and photosensitive devices, organic light-emitting diodes, light-emitting devices or devices capable of both light absorption and emission, and as markers for biological applications.

[0040] As stated above, the disclosed compounds are platinum complexes. Furthermore, the compounds disclosed herein can be used as host materials for OLED applications, such as full-color displays.

[0041] The compounds disclosed herein can be used in a variety of applications. As luminescent materials, these compounds can be used in organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting devices.

[0042] In addition, compared with traditional materials, the compounds in this invention can improve luminous efficiency and device operating time when used in light-emitting devices (such as OLEDs).

[0043] The compounds of the present invention can be prepared using a variety of methods, including but not limited to those described in the examples provided herein.

[0044] The compounds disclosed in the embodiments of the present invention are applicable to a wide variety of optical and electro-optic devices, including but not limited to light-absorbing devices such as solar cells and photosensors, organic light-emitting diodes (OLEDs), light-emitting devices or devices that have both light absorption and light emission capabilities, and markers for use in biological applications.

[0045] The compounds provided by embodiments of the present invention can be used in a light-emitting device such as an OLED, the device comprising at least one cathode, at least one anode, and at least one light-emitting layer, wherein at least one of the light-emitting layers comprises a tetradentate ring platinum(II) complex of formula (I). Specifically, the light-emitting device may comprise an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode, which are sequentially deposited. The hole transport layer, the light-emitting layer, and the electron transport layer are all organic layers, and the anode and cathode are electrically connected.

[0046] It should be noted that the general instructions above and the detailed instructions below are merely illustrative and explanatory, and are not restrictive.

[0047] This disclosure can be more readily understood by referring to the following detailed description and the embodiments contained therein.

[0048] Before disclosing and describing the compounds, devices, and / or methods of the present invention, it should be understood that they are not limited to specific synthetic methods (otherwise indicated) or specific reagents (otherwise indicated), as these are, of course, subject to variation. It should also be understood that the terminology used in this invention is for descriptive purposes only and is not intended to be limiting. While any methods and materials similar to or equivalent to those described in this invention may be used in this practice or experiment, exemplary methods and materials are described below.

[0049] Synthesis Examples

[0050] The examples of compound synthesis, composition, devices, or methods below are intended to provide a general approach to the industry and are not intended to limit the scope of this patent. While we strive for accuracy in the data (quantities, temperatures, etc.) mentioned in the patent, some errors may still exist. Unless otherwise specified, weighings are performed separately, temperatures are in °C or room temperature, and pressures are close to atmospheric pressure.

[0051] The examples below provide methods for preparing novel compounds, but the preparation of such compounds is not limited to these methods. In this field of expertise, since the compounds protected in this patent are easily modified and prepared, their preparation can be carried out using the methods listed below or other methods. The examples below are merely illustrative and are not intended to limit the scope of protection of this patent. Temperature, catalyst, concentration, reactants, and reaction process can all be varied to select different conditions for preparing the compounds with different reactants.

[0052] HPLC-MS was performed on an Agilent 6210 TOF LC / MS mass spectrometer; HRMS spectra were performed on an Agilent 6210 TOF LC / MS liquid chromatography-time-of-flight mass spectrometer.

[0053] Synthetic route

[0054] Example 1: Tetradentate ring platinum(II) complex Pt1

[0055] The synthesis route is as follows:

[0056] Synthesis of the intermediate chiral 1-OMe: Cl (1.2 equivalents), Cz-OMe (1.0 equivalent), Pd2(dba)3 (3 mol%), SPhos (12 mol%), and sodium tert-butoxide (2.0 equivalents) were added sequentially to a reaction flask. Nitrogen gas was purged three times, and toluene (25 mL) was added. The reaction mixture was stirred at 110 °C for 42 hours, and the solvent was removed by vacuum distillation. The mixture was purified by silica gel column chromatography with petroleum ether / ethyl acetate as eluent (50-10:1) to give 930 mg of 1-OMe as a yellow solid (90% yield).

[0057] Synthesis of the intermediate chiral 1-OH: 1-OMe (1.0 equivalent), hydrobromic acid (48%) (9 mL), and acetic acid (6 mL) were added sequentially to a reaction flask. The mixture was stirred at 120 °C for 16 hours and then cooled to room temperature. The solution was neutralized with aqueous NaHCO3, extracted with dichloromethane, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The product 1-OH was obtained by slurrying with petroleum ether / ethyl acetate, yielding 800 mg of a white solid (90% yield).

[0058] Synthesis of the intermediate chiral 1-Cl: 1-OH (1.0 equivalent), 1-bromo-3-tert-butyl-5-chlorobenzene (1.2 equivalent), cuprous iodide (10 mol%), 2-pyridinecarboxylic acid (20 mol%), and potassium phosphate (2.0 equivalent) were added sequentially to a reaction flask. The mixture was purged with nitrogen three times, and then dimethyl sulfoxide (40 mL) was added. The reaction mixture was stirred at 100 °C for 26 hours. The mixture was diluted with water, extracted three times with ethyl acetate, washed once with brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by vacuum distillation. The solution was purified by silica gel column chromatography with an eluent ratio of petroleum ether / ethyl acetate of 20:1–10:1, yielding 549 mg of a white solid (81% yield). MS: m / z 428.16 (M+H) + .

[0059] Synthesis of intermediate (1-1): tBu-Cl-Br (1.0 equivalent), NH2-NO2 (1.2 equivalent), tris(dibenzylacetone)palladium (0.03 equivalent), 2-(dicyclohexylphosphine)-3,6-dimethoxy-2'-4'-6'-tris-1-propyl-11'-biphenyl (BrettPhos) (0.06 equivalent), and cesium carbonate (2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was then purged with nitrogen three times, and toluene (60 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 110 °C for 24 hours, then cooled to room temperature. The mixture was extracted with ethyl acetate, washed with water, dried over sodium sulfate, and the solvent was removed by vacuum distillation. The crude product was separated and filtered using a silica gel column chromatography. The eluent was petroleum ether / ethyl acetate = 30:1, yielding 1.50 g of a yellow solid, 83% yield. MS: m / z 304.10 (M+H) + .

[0060] Synthesis of intermediates (1-2): 1-1 (1.0 equivalent), DtBu-Bpin (1.1 equivalent), tetraphenylphosphine palladium (0.02 equivalent), and potassium carbonate (2.5 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was then purged with nitrogen three times. Under nitrogen protection, 1,4-dioxane (80 mL) and water (20 mL) were added. The reaction was carried out in an oil bath at 90 °C for 18 hours, then cooled to room temperature. Extraction was performed with ethyl acetate, followed by washing with water and drying with sodium sulfate. The solvent was removed by vacuum distillation, and the crude product was separated and filtered using a silica gel column chromatography. Petroleum ether / ethyl acetate ratio of 30:1 yielded 2.1 g of a red solid, 96% yield. MS: m / z 458.29 (M+H) + .

[0061] Synthesis of intermediates (1-3): 1-2 (1.0 equivalent) and stannous chloride (4.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. Nitrogen was then purged three times. Ethanol (30 mL) and water (30 mL) were added under nitrogen protection, followed by another three purgings. The reaction was carried out in an oil bath at 78°C under nitrogen atmosphere for 12 hours, then cooled to room temperature. Extraction was performed with ethyl acetate, followed by washing with water and drying with sodium sulfate. The solvent was removed by vacuum distillation, and the crude product was separated and filtered using a silica gel column chromatography. Petroleum ether / ethyl acetate ratio of 50:1 yielded 1.8 g of a pale yellow solid, 90% yield. MS: m / z 428.32 (M+H) + .

[0062] Synthesis of intermediates (1-4): 1-3 (1.0 equivalent), 1-Cl (1.0 equivalent), tris(dibenzylacetone)palladium (0.03 equivalent), 2-(di-tert-butylphosphine)biphenyl (JohnPhos) (0.06 equivalent), and sodium tert-butoxide (2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. Nitrogen was purged three times, and toluene (50 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 100 °C for 18 hours, then cooled to room temperature. The mixture was filtered, and the solvent was removed by vacuum distillation. The crude product was separated by silica gel column chromatography with petroleum ether / ethyl acetate as eluent (25:1) to give 2.6 g of a gray solid, yield 84%. MS: m / z 819.50 (M+H) + .

[0063] Synthesis of ligand L1: 1-4 (1.0 equivalent) ammonium hexafluorophosphate (2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was purged with nitrogen three times. Triethyl orthoformate (10 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 70°C for 2 hours, then cooled to room temperature. The solvent was removed by vacuum distillation. Separation was performed by silica gel column chromatography with dichloromethane / methanol as the eluent (100:1-50:1), yielding 2.7 g of a purple-red solid (91% yield). MS: m / z 975.45 (M+H) + .

[0064] Synthesis of Pt1: L1 (1.0 equivalent), (1,5-cyclooctadiene)diplatinum chloride (1.05 equivalent), and sodium acetate (3.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was purged with nitrogen three times. Diethylene glycol dimethyl ether (100 mL) was added under nitrogen protection, and the mixture was bubbled with nitrogen for 30 min to remove oxygen. The reaction was carried out in an oil bath at 150 °C for 24 hours. After cooling to room temperature, the solvent was removed by vacuum distillation. The crude product was separated by silica gel column chromatography with petroleum ether / dichloromethane as eluent (3:1-1:1), yielding 630 mg of a yellow solid (31% yield). MS: m / z 1023.44 (M+H) + .

[0065] Example 2: Tetradentate ring platinum(II) complex Pt14

[0066] The synthesis route is as follows:

[0067] Synthesis of intermediate (2-1): iPr-Cl-Br (1.0 equivalent), NH2-NO2 (1.2 equivalent), tris(dibenzylacetone)palladium (0.03 equivalent), 2-(dicyclohexylphosphine)-3,6-dimethoxy-2'-4'-6'-tris-1-propyl-11'-biphenyl (BrettPhos) (0.06 equivalent), and cesium carbonate (2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was then purged with nitrogen three times. Toluene (100 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 110 °C for 18 hours, then cooled to room temperature. The mixture was extracted with ethyl acetate, washed with water, dried over sodium sulfate, and the solvent was removed by vacuum distillation. The crude product was separated and filtered using a silica gel column chromatography. The eluent was petroleum ether / ethyl acetate = 30:1, yielding 1.73 g of a yellow solid, 89% yield. MS: m / z 290.08 (M+H) + .

[0068] Synthesis of intermediate (2-2): 2-1 (1.0 equivalent), tBu-Bpin (1.1 equivalent), tetraphenylphosphine palladium (0.02 equivalent), and potassium carbonate (2.5 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was then purged with nitrogen three times. Under nitrogen protection, 1,4-dioxane (80 mL) and water (20 mL) were added. The reaction was carried out in an oil bath at 90 °C for 12 hours, then cooled to room temperature. Extraction was performed with ethyl acetate, followed by washing with water and drying with sodium sulfate. The solvent was removed by vacuum distillation, and the crude product was separated and filtered using a silica gel column chromatography. Petroleum ether / ethyl acetate ratio of 30:1 yielded 2.8 g of a red solid, 94% yield. MS: m / z 464.25 (M+H) + .

[0069] Synthesis of intermediate (2-3): 2-2 (1.0 equivalent) and stannous chloride (4.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. Nitrogen was then purged three times. Ethanol (50 mL) and water (50 mL) were added under nitrogen protection, followed by another three purgings. The reaction was carried out in an oil bath at 78°C under nitrogen atmosphere for 12 hours, then cooled to room temperature. Extraction was performed with ethyl acetate, followed by washing with water and drying with sodium sulfate. The solvent was removed by vacuum distillation, and the crude product was separated and filtered using a silica gel column chromatography. Petroleum ether / ethyl acetate ratio of 50:1 yielded 2.3 g of a yellow solid, 92% yield. MS: m / z 434.27 (M+H) + .

[0070] Synthesis of intermediates (2-4): 2-3 (1.0 equivalent), 1-Cl (1.0 equivalent), tris(dibenzylacetone)palladium (0.03 equivalent), 2-(di-tert-butylphosphine)biphenyl (JohnPhos) (0.06 equivalent), and sodium tert-butoxide (2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. Nitrogen was purged three times, and toluene (75 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 100 °C for 24 hours, then cooled to room temperature. The mixture was filtered, and the solvent was removed by vacuum distillation. The crude product was separated by silica gel column chromatography with petroleum ether / ethyl acetate as eluent (25:1) to give 2.6 g of a gray solid, yield 84%. MS: m / z 825.45 (M+H) + .

[0071] Synthesis of ligand L2: 2-4 (1.0 equivalent) and ammonium hexafluorophosphate (2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was purged with nitrogen three times. Triethyl orthoformate (10 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 70°C for 2 hours, then cooled to room temperature. The solvent was removed by vacuum distillation. Separation was performed by silica gel column chromatography with dichloromethane / methanol as the eluent (100:1-50:1), yielding 3.5 g of a green solid (85% yield). MS: m / z 981.41 (M+H) + .

[0072] Synthesis of Pt14: L2 (1.0 equivalent), (1,5-cyclooctadiene)diplatinum chloride (1.05 equivalent), and sodium acetate (3.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was purged with nitrogen three times. Diethylene glycol dimethyl ether (100 mL) was added under nitrogen protection, and the mixture was bubbled with nitrogen for 30 min to remove oxygen. The reaction was carried out in an oil bath at 150 °C for 24 hours. After cooling to room temperature, the solvent was removed by vacuum distillation. The crude product was separated by silica gel column chromatography with petroleum ether / dichloromethane as eluent (3:1-1:1) to give 850 mg of a yellow solid, yield 28%. MS: m / z 1029.39 (M+H) + .

[0073] Example 3: Tetradentate ring platinum(II) complex Pt135

[0074] The synthesis route is as follows:

[0075] Synthesis of intermediate (3-1): tBu-Cl-Br (1.0 equivalent), NH2-NO2 (1.2 equivalent), tris(dibenzylacetone)palladium (0.03 equivalent), 2-(dicyclohexylphosphine)-3,6-dimethoxy-2'-4'-6'-tris-1-propyl-11'-biphenyl (BrettPhos) (0.06 equivalent), and cesium carbonate (2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was then purged with nitrogen three times, and toluene (60 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 110 °C for 24 hours, then cooled to room temperature. The mixture was extracted with ethyl acetate, washed with water, dried over sodium sulfate, and the solvent was removed by vacuum distillation. The crude product was separated and filtered using a silica gel column chromatography. The eluent was petroleum ether / ethyl acetate = 30:1, yielding 1.50 g of a yellow solid, 83% yield. MS: m / z 304.10 (M+H) + .

[0076] Synthesis of intermediate (3-2): 3-1 (1.0 equivalent), tBu-Bpin (1.1 equivalent), tetraphenylphosphine palladium (0.02 equivalent), and potassium carbonate (2.5 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was then purged with nitrogen three times. Under nitrogen protection, 1,4-dioxane (80 mL) and water (20 mL) were added. The reaction was carried out in an oil bath at 90 °C for 18 hours, then cooled to room temperature. Extraction was performed with ethyl acetate, followed by washing with water and drying with sodium sulfate. The solvent was removed by vacuum distillation, and the crude product was separated and filtered using a silica gel column chromatography. Petroleum ether / ethyl acetate ratio of 30:1 yielded 2.0 g of a red solid, 93% yield. MS: m / z 535.32 (M+H) + .

[0077] Synthesis of intermediate (3-3): 3-2 (1.0 equivalent) and stannous chloride (4.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. Nitrogen was then purged three times. Ethanol (30 mL) and water (30 mL) were added under nitrogen protection, followed by another three purgings. The reaction was carried out in an oil bath at 78°C under nitrogen atmosphere for 12 hours, then cooled to room temperature. Extraction was performed with ethyl acetate, followed by washing with water and drying with sodium sulfate. The solvent was removed by vacuum distillation, and the crude product was separated and filtered using a silica gel column chromatography. Petroleum ether / ethyl acetate ratio of 50:1 yielded 1.6 g of a pale yellow solid, 90% yield. MS: m / z 505.35 (M+H) + .

[0078] Synthesis of intermediates (3-4): 3-3 (1.0 equivalent), 1-Cl (1.0 equivalent), tris(dibenzylacetone)palladium (0.03 equivalent), 2-(di-tert-butylphosphine)biphenyl (JohnPhos) (0.06 equivalent), and sodium tert-butoxide (2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was purged with nitrogen three times, and toluene (50 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 100 °C for 16 hours, then cooled to room temperature. The mixture was filtered, and the solvent was removed by vacuum distillation. The crude product was separated by silica gel column chromatography with petroleum ether / ethyl acetate as eluent (25:1) to give 2.4 g of a gray solid, yield 84%. MS: m / z 896.53 (M+H) + .

[0079] Synthesis of ligand L3: 3-4 (1.0 equivalent) and ammonium hexafluorophosphate (2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. Nitrogen was purged three times. Under nitrogen protection, triethyl orthoformate (10 mL) was added. The reaction was carried out in an oil bath at 70°C for 1 hour, then cooled to room temperature. The solvent was removed by vacuum distillation. Separation was performed by silica gel column chromatography with dichloromethane / methanol as the eluent (100:1-50:1), yielding 2.5 g of a purple solid (91% yield). MS: m / z 1052.48 (M+H) + .

[0080] Synthesis of Pt135: L3 (1.0 equivalent), (1,5-cyclooctadiene)diplatinum chloride (1.05 equivalent), and sodium acetate (3.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was purged with nitrogen three times. Diethylene glycol dimethyl ether (100 mL) was added under nitrogen protection, and the mixture was bubbled with nitrogen for 30 min to remove oxygen. The reaction was carried out in an oil bath at 150 °C for 24 hours. After cooling to room temperature, the solvent was removed by vacuum distillation. The crude product was separated by silica gel column chromatography with petroleum ether / dichloromethane as eluent (3:1-1:1) to give 730 mg of a yellow solid, yield 31%. MS: m / z 1100.47 (M+H) + .

[0081] Example 4: Pt2, a tetradentate ring platinum(II) complex

[0082] Complex Pt2 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final result was 138 mg of a yellow solid, with a yield of 38%. MS: m / z 1026.46 (M+H) + .

[0083] Example 5: Tetradentate ring platinum(II) complex Pt4

[0084] Complex Pt4 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final result was 120 mg of a yellow solid, with a yield of 41%. MS: m / z 1025.45 (M+H) + .

[0085] Example 6: Tetradentate ring platinum(II) complex Pt5

[0086] Complex Pt5 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final result was 93 mg of a yellow solid, with a yield of 32%. MS: m / z 1026.46 (M+H) + .

[0087] Example 7: Tetradentate ring platinum(II) complex Pt6

[0088] Complex Pt6 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final result was 98 mg of a yellow solid, with a yield of 40%. MS: m / z 1025.45 (M+H) + .

[0089] Example 8: Tetradentate ring platinum(II) complex Pt9

[0090] Complex Pt9 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final result was 128 mg of a yellow solid, with a yield of 36%. MS: m / z 1025.45 (M+H) + .

[0091] Example 9: Tetradentate ring platinum(II) complex Pt11

[0092] Complex Pt11 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 124 mg of a yellow solid, with a yield of 42%. MS: m / z 1027.47 (M+H) + .

[0093] Example 10: Tetradentate ring platinum(II) complex Pt12

[0094] Complex Pt12 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 105 mg of a yellow solid, with a yield of 38%. MS: m / z 1026.46 (M+H) + .

[0095] Example 11: Tetradentate ring platinum(II) complex Pt16

[0096] Complex Pt16 was synthesized using the same method as in Example 1, except that the ligand precursor for the corresponding fragment was replaced. The final yield was 135 mg of a yellow solid, with a yield of 39%. MS: m / z 981.39 (M+H) + .

[0097] Example 12: Tetradentate ring platinum(II) complex Pt25

[0098] Complex Pt25 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 137 mg of a yellow solid, with a yield of 43%. MS: m / z 1045.42 (M+H) + .

[0099] Example 13: Tetradentate ring platinum(II) complex Pt27

[0100] Complex Pt27 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final yield was 128 mg of a yellow solid, with a yield of 40%. MS: m / z 1045.42 (M+H) + .

[0101] Example 14: Tetradentate ring platinum(II) complex Pt30

[0102] Complex Pt30 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 125 mg of a yellow solid, with a yield of 36%. MS: m / z 1046.43 (M+H) + .

[0103] Example 15: Tetradentate ring platinum(II) complex Pt31

[0104] Complex Pt31 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 136 mg of a yellow solid, with a yield of 42%. MS: m / z 1046.43 (M+H) + .

[0105] Example 16: Tetradentate ring platinum(II) complex Pt32

[0106] Complex Pt32 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 132 mg of a yellow solid, with a yield of 41%. MS: m / z 1015.46 (M+H) + .

[0107] Example 17: Tetradentate ring platinum(II) complex Pt36

[0108] Complex Pt36 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 127 mg of a yellow solid, with a yield of 36%. MS: m / z 1015.46 (M+H) + .

[0109] Example 18: Tetradentate ring platinum(II) complex Pt41

[0110] Complex Pt41 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 145 mg of a yellow solid, with a yield of 42%. MS: m / z 984.41 (M+H) + .

[0111] Example 19: Tetradentate ring platinum(II) complex Pt42

[0112] Complex Pt42 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 153 mg of a yellow solid, with a yield of 40%. MS: m / z 986.42 (M+H) + .

[0113] Example 20: Tetradentate ring platinum(II) complex Pt51

[0114] Complex Pt51 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 142 mg of a yellow solid, with a yield of 29%. MS: m / z 1079.40 (M+H) + .

[0115] Example 21: Tetradentate ring platinum(II) complex Pt59

[0116] Complex Pt59 was synthesized using the same method as complex Pt1 in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final product was a yellow solid, 106 mg, with a yield of 46%. MS: m / z 1069.41 (M+H) +.

[0117] Example 22: Tetradentate ring platinum(II) complex Pt60

[0118] Complex Pt60 was prepared using the same synthetic method as complex Pt1 in Example 1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 126 mg of a yellow solid, with a yield of 39%. MS: m / z 1069.41 (M+H) + .

[0119] Example 23: Tetradentate ring platinum(II) complex Pt71

[0120] Complex Pt71 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final result was 122 mg of a yellow solid, with a yield of 41%. MS: m / z 1135.55 (M+H) + .

[0121] Example 24: Tetradentate ring platinum(II) complex Pt77

[0122] Complex Pt77 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final result was 118 mg of a yellow solid, with a yield of 30%. MS: m / z 1155.53 (M+H) + .

[0123] Example 25: Tetradentate ring platinum(II) complex Pt78

[0124] Complex Pt78 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 102 mg of a yellow solid, with a yield of 29%. MS: m / z 1158.55 (M+H) + .

[0125] Example 26: Tetradentate ring platinum(II) complex Pt81

[0126] Complex Pt81 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 138 mg of a yellow solid, with a yield of 47%. MS: m / z 1158.55 (M+H) + .

[0127] Example 27: Tetradentate ring platinum(II) complex Pt83

[0128] Complex Pt83 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 107 mg of a yellow solid, with a yield of 31%. MS: m / z 1158.55 (M+H) + .

[0129] Example 28: Tetradentate ring platinum(II) complex Pt90

[0130] Complex Pt90 was prepared using the same synthetic method as complex Pt1 in Example 1, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final yield was 115 mg of a yellow solid, with a yield of 33%. MS: m / z 1161.57 (M+H) + .

[0131] Example 29: Tetradentate ring platinum(II) complex Pt91

[0132] Complex Pt91 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 122 mg of a yellow solid, with a yield of 37%. MS: m / z 1102.49 (M+H) + .

[0133] Example 30: Tetradentate ring platinum(II) complex Pt93

[0134] Complex Pt93 was prepared using the same synthetic method as complex Pt1 in Example 1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 133 mg of a yellow solid, with a yield of 45%. MS: m / z 1104.50 (M+H) + .

[0135] Example 31: Tetradentate ring platinum(II) complex Pt96

[0136] Complex Pt96 was synthesized using the same method as in Example 1 for complex Pt1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 122 mg of a yellow solid, with a yield of 44%. MS: m / z 947.40 (M+H) + .

[0137] Example 32: Tetradentate ring platinum(II) complex Pt100

[0138] Complex Pt100 was prepared using the same synthetic method as complex Pt1 in Example 1, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final result was 120 mg of a yellow solid, with a yield of 31%. MS: m / z 948.40 (M+H)+ .

[0139] Example 33: Tetradentate ring platinum(II) complex Pt101

[0140] Complex Pt101 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 123 mg of a yellow solid, with a yield of 37%. MS: m / z 1108.53 (M+H) + .

[0141] Example 34: Tetradentate ring platinum(II) complex Pt104

[0142] Complex Pt104 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 134 mg of a yellow solid, with a yield of 40%. MS: m / z 1108.53 (M+H) + .

[0143] Example 35: Tetradentate ring platinum(II) complex Pt105

[0144] Complex Pt105 was prepared using the same synthetic method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 123 mg of a yellow solid, with a yield of 35%. MS: m / z 1104.51 (M+H) + .

[0145] Example 36: Tetradentate ring platinum(II) complex Pt109

[0146] Complex Pt109 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final product was a yellow solid, 101 mg, with a yield of 41%. MS: m / z 1182.55 (M+H) + .

[0147] Example 37: Tetradentate ring platinum(II) complex Pt111

[0148] Complex Pt111 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final product was a yellow solid, 104 mg, with a yield of 41%. MS: m / z 1181.54 (M+H) + .

[0149] Example 38: Tetradentate ring platinum(II) complex Pt112

[0150] Complex Pt112 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 101 mg of a yellow solid, with a yield of 31%. MS: m / z 1182.55 (M+H) + .

[0151] Example 39: Tetradentate ring platinum(II) complex Pt114

[0152] Complex Pt114 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 108 mg of a yellow solid, with a yield of 31%. MS: m / z 1182.55 (M+H) + .

[0153] Example 40: Tetradentate ring platinum(II) complex Pt115

[0154] Complex Pt115 was prepared using the same synthetic method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 141 mg of a yellow solid, with a yield of 37%. MS: m / z 1200.59 (M+H) + .

[0155] Example 41: Tetradentate ring platinum(II) complex Pt116

[0156] Complex Pt116 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 101 mg of a yellow solid, with a yield of 41%. MS: m / z 1185.57 (M+H) + .

[0157] Example 42: Tetradentate ring platinum(II) complex Pt117

[0158] Complex Pt117 was prepared using the same synthetic method as complex Pt1 in Example 1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 116 mg of a yellow solid, with a yield of 43%. MS: m / z 1182.55 (M+H) + .

[0159] Example 43: Tetradentate ring platinum(II) complex Pt125

[0160] Complex Pt125 was prepared using the same synthetic method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 121 mg of a yellow solid, with a yield of 35%. MS: m / z 1184.56 (M+H) + .

[0161] Example 44: Tetradentate ring platinum(II) complex Pt128

[0162] Complex Pt128 was prepared using the same synthetic method as complex Pt1 in Example 1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 113 mg of a yellow solid, with a yield of 33%. MS: m / z 982.39 (M+H) + .

[0163] Example 45: Tetradentate ring platinum(II) complex Pt137

[0164] Complex Pt137 was prepared using the same synthetic method as in Example 1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 124 mg of a yellow solid, with a yield of 31%. MS: m / z 1103.48 (M+H) + .

[0165] Example 46: Tetradentate ring platinum(II) complex Pt142

[0166] Complex Pt142 was synthesized using the same method as in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 135 mg of a yellow solid, with a yield of 34%. MS: m / z 1087.46 (M+H) + .

[0167] Photophysical properties:

[0168] Table 1 shows the photophysical properties of some of the platinum(II) complexes of this invention in toluene solution at room temperature. The data in Table 1 show that the emission wavelength of the platinum metal complex phosphorescent materials is in the blue light emission region around 460 nm; the full width at half maximum (FWHM) is small, all at or below 35 nm, indicating high color purity; their quantum efficiency in polymethyl methacrylate (PMMA) is high, mostly above 80%, and even reaching 95% or higher; deuteration of the ligand periphery ensures improved material stability while having almost no impact on the emission wavelength and FWHM; furthermore, through the analysis of R… 1 R 2 and R 3 By using substituents for modulation, precise adjustment of the emission wavelength can be achieved.

[0169] Table 1. Photophysical properties of some platinum(II) complexes of the present invention in toluene solution at room temperature.

[0170] Fabrication of OLED devices:

[0171] An OLED device is fabricated by depositing p-doped material onto the surface or anode of an ITO glass with a light-emitting area of ​​2 mm × 2 mm, or by co-evaporating p-doped material with hole injection material at a concentration of 1% to 50% to form a 5-100 nm hole injection layer (HIL) and a 5-200 nm hole transport layer (HTL). Subsequently, a 10-100 nm light-emitting layer (EML) (which may contain the compound described in this invention) is formed on the hole transport layer, followed by a 20-200 nm electron transport layer (ETL) and a 50-200 nm cathode. 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. The OLED is then tested using standard methods. Unless otherwise specified, the device materials involved in this invention can be obtained using known synthesis methods.

[0172] In a preferred embodiment, the structure of the device Example 1 provided by the present invention is: ITO / P-4 (10nm) / HT1 (60nm) / HTH-85 (5nm) / platinum (II) complex:HTH-85:ETH-45 (25nm) (Pt1:HTH-85:ETH-45 mass ratio is 10:60:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0173] Device Examples 2-25 and Comparative Example 1 were fabricated using structures similar to those in Device Example 1, the only difference being that Pt1 in Device Example 1 was replaced with platinum(II) complexes as shown in Table 2. The luminescence properties of the comparative examples and each device example prepared above were tested using standard methods and are shown in Table 2. The device structural formulas involved are as follows: where P-4 is HATCN and ET-14 is BPyTP.

[0174] Table 2. Light-emitting characteristic data of some compound devices of the present invention

[0175] As shown in Table 2, compared with Comparative Example 1, Device Examples 1-25 prepared in this application exhibit excellent device performance in terms of driving voltage, current efficiency, and device lifetime. The performance improvement of each device example is based on the high chemical stability and better electron transport capability of the specific compound material of this invention. It is evident that using this as a light-emitting layer material to prepare electronic devices results in higher current efficiency, device lifetime, and color purity while reducing the driving voltage. This indicates that the complex provided by this invention has certain commercial application value. Furthermore, all devices prepared in this invention are deep blue light devices with CIEy values ​​less than 0.2.

[0176] In a preferred embodiment, the structure of device example 26 provided by the present invention is as follows: ITO / P-4 (10nm) / HT1 (60nm) / HTH-85 (5nm) / platinum (II) complex: boron-containing compound: HTH-85:ETH-45 (25nm) (Pt1:BN1-8:HTH-85:ETH-45 mass ratio is 10:1:59:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0177] Devices 27-38 were fabricated using structures similar to those in Device Example 26, the only difference being that the platinum(II) complex and boron-containing compound in Device Example 26 were replaced with platinum(II) complexes, boron-containing compounds, and other compounds listed in Table 3. The device structural formulas are as follows, and the device structure and luminescence characteristic data are shown in Table 3.

[0178] Table 3. Data on the structure and luminescence properties of some devices

[0179] As shown in Table 3, when the complexes of this invention are used as sensitizing materials, together with boron-containing compounds as luminescent materials in devices, the performance of each device is significantly improved. This further demonstrates that the compounds provided by this invention have certain commercial application value. Adding boron-containing compounds to sensitize the device structure can further reduce the CIEy value, thereby improving the purity of the device's luminescent color.

[0180] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A tetradentate cyclic platinum(II) complex, characterized in that, The complex has the structure shown in formula (I): In equation (I), R 1 R 2 and R 3 The same or different, each independently represented as a C1–C30 alkyl, a C1–C30 deuterated alkyl, a C1–C30 haloalkyl, a C3–C30 cycloalkyl, a substituted or unsubstituted C6–C60 aryl, or a substituted or unsubstituted C5–C60 heteroaryl; R a R b R c R d R e R f R g Each can be independently represented as monosubstituted, disubstituted, trisubstituted, or tetrasubstituted; R a -R g Each is independently represented as hydrogen, deuterium, or a C1–C30 alkyl group; when substituted, the substituent may be selected from one or more of deuterium, C1–C14 alkyl, or C6–C60 aryl.

2. The tetradentate ring platinum(II) complex according to claim 1, characterized in that, R 1 R 2 and R 3 Each of the following is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodel, sec-decyl, tert-decyl, adamantyl, C1–C6 alkyl-substituted or unsubstituted phenyl, C1–C6 alkyl-substituted or unsubstituted pyridyl, or a combination thereof.

3. The tetradentate ring platinum(II) complex according to claim 1, characterized in that, In formula (I), hydrogen atoms can be partially or completely replaced by deuterium.

4. The tetradentate ring platinum(II) complex according to claim 1, characterized in that, R a It may be selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isonyl, sec-nonyl, tert-nonyl, n-decyl, isodel, sec-decyl, tert-decyl, adamantyl, one or a combination thereof.

5. The tetradentate ring platinum(II) complex according to claim 1, characterized in that, The complex is selected from any of the chemical structures shown below, where "D" represents deuterium:

6. The use of the tetradentate ring platinum(II) complex according to any one of claims 1-5 in the preparation of electronic devices.

7. The application according to claim 6, characterized in that, The electronic devices include one or more of the following: organic electroluminescent devices, organic optoelectronic devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photosensors, organic field quenching devices, luminescent electrochemical cells, or organic laser diodes.

8. An organic electroluminescent device, characterized in that, The organic electroluminescent device comprises a cathode, an anode, and an organic functional layer between them; the organic functional layer contains the tetradentate ring platinum(II) complex as described in any one of claims 1-5.

9. The organic electroluminescent device according to claim 8, characterized in that, The organic functional layer further comprises a light-emitting layer, wherein the light-emitting layer contains the tetradentate cyclic platinum(II) complex according to any one of claims 1-5.

10. The organic electroluminescent device according to claim 8, characterized in that, The organic functional layer further includes a light-emitting layer, which contains the tetradentate cyclic platinum(II) complex according to any one of claims 1-5; the light-emitting layer further includes a fluorescent dopant material, which is a boron-containing compound.

11. An organic optoelectronic device, characterized in that, The organic optoelectronic device comprises: 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 comprises the tetradentate cyclic platinum(II) complex according to any one of claims 1-5.

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

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

14. A display or lighting device, characterized in that, The device comprises one or more of the organic electroluminescent device of claim 8 or the organic optoelectronic device of claim 11.

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