Tetradentate cyclometalated platinum (II) complex guest phosphorescent material based on 2,3',5'-substituted 1,1'-biphenyl structure, and use thereof

Abstract

The present invention belongs to the field of organic electroluminescence, and specifically relates to a tetradentate cyclometalated platinum (II) complex guest phosphorescent material based on a 2,3',5'-substituted 1,1'-biphenyl structure and the use thereof. In the present invention, by introducing alkyl or aryl to the positions 2, 3' and 5' of 1,1'-biphenyl to increase the steric hindrance, red shift or luminescence quenching caused by molecular aggregation can be avoided. Deuteration at the periphery of a cyclometalating ligand can improve the stability of the material, so that the phosphorescent material provided by the present invention has good chemical stability and thermal stability and can be easily used for manufacturing evaporation-type OLED devices. Organic electroluminescent devices manufactured by using the complex of the present invention as a light-emitting layer material have significant improvement in both current efficiency and service lifetime, thereby achieving great application prospects in the fields of OLED display and illumination.

Description

Guest phosphorescent materials based on tetradentate cyclic platinum(II) complexes with 2,3′,5′ substituted 1,1′ biphenyl structures and their applications Technical Field

[0001] This invention belongs to the field of organic electroluminescent material preparation, specifically relating to a tetradentate cyclic platinum(II) complex guest phosphorescent material based on a 2,3',5'-substituted 1,1' biphenyl structure and its application. 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, making them energy-efficient. They also feature 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. Furthermore, they offer 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 electronics 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 used OLED devices almost entirely employ 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 iridium(III) complex molecules used in heavy metal phosphorescent organic complexes is limited. The abundance of platinum in the Earth's crust and its global annual production are approximately ten times that of iridium. IrCl3, used to prepare iridium(III) complex phosphorescent materials, is a suitable candidate. . The price of H2O is also much higher than that of PtCl2 used in the preparation of platinum(II) complex phosphorescent materials; in addition, the preparation of iridium(III) complex phosphorescent materials involves four steps: iridium(III) dimer, iridium(III) intermediate ligand exchange, synthesis of mer-iridium(III) complex, and isomer conversion from mer- to fac-iridium(III) complex, which greatly reduces the overall yield and significantly lowers the cost of the raw material IrCl3. . The increased utilization of H₂O raises the preparation cost of iridium(III) complex phosphorescent materials. In contrast, the preparation of platinum(II) complex phosphorescent materials involves only the final step of ligand metallization design of platinum salts, resulting in high platinum utilization and further reducing the preparation cost. Therefore, the preparation cost of platinum(II) complex phosphorescent materials is significantly 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 guest phosphorescent material based on a tetradentate cyclic platinum(II) metal complex with a 2,3',5'-substituted 1,1'-biphenyl structure and its applications. This invention increases steric hindrance by introducing alkyl or aryl groups at the 2,3',5' positions, thus avoiding redshift or luminescence quenching caused by molecular aggregation. Deuteration around the cyclic metal ligand improves material stability, giving the phosphorescent material of this invention excellent chemical and thermal stability, making it easy to fabricate 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, and have great application prospects in the fields of 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 guest phosphorescent material having the general structure shown in formula (I):

[0009] In equation (I), R 1 R 2 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 of the following can be independently represented as hydrogen, deuterium, C1–C30 alkyl, C1–C30 deuterated alkyl, C3–C30 cycloalkyl, substituted or unsubstituted C6–C60 aryl; when substituted, the substituent can be monosubstituted or polysubstituted, and each substituent can be independently selected from one or more of deuterium, C1–C14 alkyl, and C6–C60 aryl.

[0010] Preferably, in the tetradentate ring platinum(II) complex guest phosphorescent material of 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 one or a combination of 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, phenyl, and pyridyl.

[0012] In many implementations, R a R b R c R e R f and R g Each can be independently represented as hydrogen or deuterium; R d It is independently selected from one or a combination of 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, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodel, sec-decyl, tert-decyl, adamantyl, C1-C10 alkyl-substituted or unsubstituted phenyl groups.

[0013] In many embodiments, the present invention provides a tetradentate cyclic platinum(II) complex guest phosphorescent material, said tetradentate cyclic platinum(II) complex guest phosphorescent material being selected from any of the following chemical structures: where “D” represents deuterium:

[0014] In many embodiments, the present invention also provides the application of tetradentate ring platinum(II) complex guest phosphorescent materials having the general structure shown in formula (I) above in the fabrication of electronic devices.

[0015] 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.

[0016] 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 guest phosphorescent material having the general structure shown in Formula (I) above.

[0017] Preferably, the organic functional layer includes a light-emitting layer, which contains a tetradentate ring platinum(II) complex guest phosphorescent material having the general structure shown in formula (I) above.

[0018] 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.

[0019] 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 cyclic platinum(II) complex guest phosphorescent material having the general structure shown in formula (I) above. For example, the tetradentate cyclic platinum(II) complex can be included as a light-emitting material in the organic light-emitting functional layer.

[0020] 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.

[0021] 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.

[0022] The present invention also provides a composition comprising a tetradentate cyclic platinum(II) complex guest phosphorescent material having the general structure shown in formula (I) as described 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.

[0023] The present invention also provides a formulation comprising a tetradentate cyclic platinum(II) complex guest phosphorescent material having the general 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.

[0024] 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.

[0025] 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.

[0026] The materials used in the organic electroluminescent devices according to the present invention can be classified as top-emitting, low-emitting, or bifacial-emitting.

[0027] 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.

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0029] (1) By introducing sterically hindered alkyl or aryl groups at the 2, 3', and 5' positions, the steric hindrance is increased, the distance between molecules is expanded, and the red shift or luminescence quenching caused by molecular aggregation is avoided.

[0030] (2) Deuteration around the cyclic metal ligand can improve the stability of CH bonds, thereby giving the phosphorescent material provided by the present invention excellent chemical and thermal stability, and making it easy to prepare vapor-deposited OLED devices.

[0031] (3) When the complex of the present invention is used as the light-emitting layer to make an organic electroluminescent device, the energy transfer between the host and the guest is more efficient, and the current efficiency and lifetime are significantly improved; and the use of phosphorus photosensitization boron-containing compound system can further improve the light color purity of the device. Attached Figure Description

[0032] Figure 1 shows the room temperature emission spectra of the platinum(II) complex Pt1 in toluene and dichloro solutions. Detailed Implementation

[0033] 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.

[0034] 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).

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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).

[0046] 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.

[0047] 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.

[0048] 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 platinum(II) complex guest phosphorescent material with the structure shown in formula (I). Specifically, the light-emitting device may include 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.

[0049] It should be noted that the general instructions above and the detailed instructions below are merely illustrative and explanatory, and are not restrictive.

[0050] This disclosure can be more readily understood by referring to the following detailed description and the embodiments contained therein.

[0051] 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.

[0052] Synthesis Examples

[0053] 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.

[0054] 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.

[0055] HPLC-MS was performed on an Agilent 6210TOF LC / MS mass spectrometer; HRMS spectra were performed on an Agilent 6210TOF LC / MS liquid chromatography-time-of-flight mass spectrometer.

[0056] Synthetic route

[0057] Example 1: Tetradentate ring platinum(II) complex Pt1

[0058] The synthesis route is as follows:

[0059] Synthesis of intermediate (1-1): Br-OH (20.00 g, 87.29 mmol, 1.1 equivalents), NO2-NH2 (10.96 g, 79.36 mmol, 1.0 equivalents), tris(dibenzylacetone)palladium (2.18 g, 2.38 mmol, 3 mol%), 2-(dicyclohexylphosphine)-3,6-dimethoxy-2'-4'-6'-tris-1-propyl-11'-biphenyl (BrettPhos) (2.56 g, 4.76 mmol, 6 mol%), and cesium carbonate (51.71 g, 158.72 mmol, 2.0 equivalents) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was purged with nitrogen three times, and toluene (300 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 90°C for 28 hours, then cooled to room temperature, filtered, and the solvent was removed by vacuum distillation. The crude product was then separated by silica gel column chromatography with petroleum ether / ethyl acetate as the eluent at a ratio of 10:1, yielding 20.25 g of a deep red solid, with a yield of 89%. MS: m / z 286.13 (M+H) + .

[0060] Synthesis of intermediates (1-2): 1-1 (18.00 g, 62.86 mmol, 1.0 equivalent) and dipyridine (14.92 g, 188.59 mmol, 3.0 equivalent) and chloromethane (230 mL) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was cooled to 15 °C in an ice bath with ethanol, and then trifluoromethanesulfonic anhydride (24.83 g, 88.01 mmol, 1.4 equivalent) was slowly added dropwise. The mixture was then allowed to return to room temperature, and the reaction was stirred for 28 hours. The reaction solution 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 the eluent at a ratio of 120:1 to 60:1, yielding 21.50 g of an orange-red solid, in 81.70% yield. MS: m / z 418.08 (M+H) + .

[0061] Synthesis of intermediates (1-3): 1-2 (18.50 g, 44.22 mmol, 1.0 equivalent), DtBu-Bpin (15.48 g, 57.48 mmol, 1.3 equivalent), tetraphenylphosphine palladium (1.53 g, 1.33 mmol, 3 mol%), and potassium carbonate (12.22 g, 88.44 mmol, 2.0 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, ethylene glycol dimethyl ether (160 mL) and water (140 mL) were added. The reaction was carried out in a 90°C oil bath for 39 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. Eluent: petroleum ether / ethyl acetate = 100:1, yielding 15.00 g of a red solid, 75% yield. MS: m / z 458.29 (M+H) + .

[0062] Synthesis of intermediates (1-4): 1-3 (7.20 g, 16.35 mmol, 1.0 equivalent) and palladium on carbon (1.16 g, 0.49 mmol, 3 mol%) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was then purged with nitrogen three times. Ethanol (100 mL) and ethyl acetate (100 mL) were added under nitrogen protection, followed by purging with hydrogen three times. The reaction was carried out in an oil bath at 45 °C for 51 hours under a hydrogen atmosphere. After cooling to room temperature, the solvent was removed by vacuum distillation, yielding 6.00 g of a gray solid, 86% yield. MS: m / z 428.32 (M+H) + .

[0063] Synthesis of intermediates (1-5): 1-4 (5.00 g, 11.66 mmol, 1.0 equivalent), 1-Cl (4.98 g, 11.66 mmol, 1.0 equivalent), tris(dibenzylacetone)palladium (214 mg, 0.23 mmol, 2 mol%), 2-(di-tert-butylphosphine)biphenyl (John Phos) (139 mg, 0.49 mmol, 4 mol%), and sodium tert-butoxide (2.24 g, 23.32 mmol, 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 (80 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 85 °C for 27 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 the eluent at a ratio of 10:1, yielding 9.60 g of a gray solid (99% yield). MS: m / z 818.49 (M+H) + .

[0064] Synthesis of ligand L1: 1-5 (9.60 g, 11.72 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (3.82 g, 23.44 mmol, 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 (20 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 75 °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 dichloro / ethyl acetate as the eluent (10:1), yielding 9.3 g of a gray solid (81% yield). MS: m / z 829.47 (M+H) + .

[0065] Synthesis of Pt1: L1 (6.00 g, 6.16 mmol, 1.0 equivalent), (1,5-cyclooctadiene)diplatinum chloride (2.30 g, 6.16 mmol, 1.0 equivalent), and sodium acetate (1.52 g, 18.48 mmol, 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 (240 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 120 °C for 48 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 at a ratio of 2:1 to 1:1, yielding 1.81 g of a yellow solid (29% yield). MS: m / z 1021.44 (M+H) + .

[0066] Example 2: Tetradentate ring platinum(II) complex Pt2

[0067] The synthesis route is as follows:

[0068] 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).

[0069] 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).

[0070] Synthesis of the intermediate chiral D-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) + .

[0071] Synthesis of intermediates (2-5): 1-4 (1.0 equivalent), D-Cl (1.0 equivalent), tris(dibenzylacetone)palladium (2 mol%), 2-(di-tert-butylphosphine)biphenyl (JohnPhos) (4 mol%), 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 (8 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 85°C for 20 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 the eluent at a ratio of 10:1, yielding 450 mg of a gray solid in 60% yield. MS: m / z 819.50 (M+H) + .

[0072] Synthesis of ligand L2: 2-5 (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 (3 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 75°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 dichloroethyl / ethyl acetate as the eluent (10:1), yielding 300 mg of a gray solid (56% yield). MS: m / z 830.49 (M+H) + .

[0073] Synthesis of Pt2: L2 (1.0 equivalent), (1,5-cyclooctadiene)diplatinum chloride (1.0 equivalent), and sodium acetate (3.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. Nitrogen was purged three times. Diethylene glycol dimethyl ether (2 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 120 °C for 48 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 at a ratio of 2:1 to 1:1, yielding 132 mg of a yellow solid (32% yield). MS: m / z 1022.45 (M+H) + .

[0074] Example 3: Tetradentate ring platinum(II) complex Pt91

[0075] The synthesis route is as follows:

[0076] Synthesis of intermediate (3-1): DBr-Cl (1.0 equivalent), DtBu-Bpin (2.4 equivalent), tetraphenylphosphine palladium (3 mol%), and potassium carbonate (4.0 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, ethylene glycol dimethyl ether (4 mL) and water (4 mL) were added. The reaction was carried out in an oil bath at 90 °C for 16 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. Eluent: petroleum ether, yielding 503 mg of a white solid, 91% yield. MS: m / z 488.33 (M+H) + .

[0077] Synthesis of intermediate (3-2): 3-1 (1.0 equivalent), D-Bpin (1.5 equivalent), tris(dibenzylacetone) dipalladium (2 mol%), 2-bis(cyclohexylphosphine)-2',4',6'-triisopropylbiphenyl (XPhos) (4 mol%), and potassium acetate (3.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was purged with nitrogen three times, and 1,4-dioxane (5 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 100 °C for 14 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 at a ratio of 30:1 to 20:1, yielding 480 mg of a white solid in 82% yield. MS: m / z 580.44 (M+H) + .

[0078] Synthesis of intermediate (3-3): tBu-Br (1.0 equivalent), 3-2 (1.0 equivalent), tetra(triphenylphosphine)palladium (3 mol%), and potassium 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. Under nitrogen protection, ethylene glycol dimethyl ether (3 mL) and water (3 mL) were added. The reaction was carried out in an oil bath at 90 °C for 45 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. Eluent: petroleum ether, yielding 560 mg of a white solid, 91% yield. MS: m / z 601.43 (M+H) + .

[0079] Synthesis of intermediates (3-4): Br-NO2 (1.1 equivalents), 3-3 (1.0 equivalents), tris(dibenzylacetone) dipalladium (3 mol%), 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-diphenyl (SPhos) (12 mol%), and cesium carbonate (2.0 equivalents) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was then purged with nitrogen three times, and toluene (6 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 110 °C for 52 hours, cooled to room temperature, 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 (30:1) to give 780 mg of a yellow solid, in 80% yield. MS: m / z 722.47 (M+H) + .

[0080] Synthesis of intermediates (3-5): 3-4 (1.0 equivalent) and stannous chloride (4.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was then purged with nitrogen three times. Ethanol (6 mL) and ethyl acetate (6 mL) were added under nitrogen protection. The reaction was carried out in an oil bath at 45°C for 48 hours. After cooling to room temperature, the solvent was removed by vacuum distillation, yielding 721 mg of a gray solid (91% yield). MS: m / z 692.53 (M+H) + .

[0081] Synthesis of intermediates (3-6): 3-5 (1.0 equivalent), D-Cl (1.05 equivalent), tris(dibenzylacetone)palladium (1.5 mol%), 2-(di-tert-butylphosphine)biphenyl (JohnPhos) (3 mol%), 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 (10 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 100 °C for 52 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 (30:1) to give 830 mg of a brown solid, yield 75%. MS: m / z 1083.68 (M+H) + .

[0082] Synthesis of ligand L91: 3-6 (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 (5 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 75°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 dichloroethyl / ethyl acetate as the eluent (10:1), yielding 420 mg of a brown solid (56% yield). MS: m / z 1094.67 (M+H) + .

[0083] Synthesis of Pt91: L91 (1.0 equivalent), (1,5-cyclooctadiene)platinum dichloride (1.0 equivalent), and sodium acetate (3.0 equivalent) were added to a sealed tube equipped with a magnetic stirrer. Nitrogen was purged three times. Diethylene glycol dimethyl ether (4 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 at a ratio of 2:1 to 1:1, yielding 136 mg of a yellow solid (30% yield). MS: m / z 1287.64 (M+H) + .

[0084] Example 4: Tetradentate ring platinum(II) complex Pt3

[0085] Complex Pt3 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 100 mg of a yellow solid, with a yield of 42%. MS: m / z 1026.45 (M+H) + .

[0086] Example 5: Tetradentate ring platinum(II) complex Pt4

[0087] Complex Pt4 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final result was 114 mg of a yellow solid, with a yield of 31%. MS: m / z 1024.44 (M+H) + .

[0088] Example 6: Tetradentate ring platinum(II) complex Pt5

[0089] 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 98 mg of a yellow solid, with a yield of 46%. MS: m / z 1025.44 (M+H) + .

[0090] Example 7: Tetradentate ring platinum(II) complex Pt6

[0091] Complex Pt6 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 128 mg of a yellow solid, with a yield of 30%. MS: m / z 1027.46 (M+H) + .

[0092] Example 8: Tetradentate ring platinum(II) complex Pt7

[0093] Complex Pt7 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 164 mg of a yellow solid, with a yield of 25%. MS: m / z 1025.43 (M+H) + .

[0094] Example 9: Tetradentate ring platinum(II) complex Pt8

[0095] Complex Pt8 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 105 mg of a yellow solid, with a yield of 38%. MS: m / z 1025.44 (M+H) + .

[0096] Example 10: Tetradentate ring platinum(II) complex Pt9

[0097] 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 135 mg of a yellow solid, with a yield of 39%. MS: m / z 1028.46 (M+H) + .

[0098] Example 11: Tetradentate ring platinum(II) complex Pt10

[0099] Complex Pt10 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 137 mg of a yellow solid, with a yield of 43%. MS: m / z 1032.49 (M+H) + .

[0100] Example 12: Tetradentate ring platinum(II) complex Pt19

[0101] Complex Pt19 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 178 mg of a yellow solid, with a yield of 30%. MS: m / z 1030.49 (M+H) + .

[0102] Example 13: Tetradentate ring platinum(II) complex Pt21

[0103] Complex Pt21 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 125 mg of a yellow solid, with a yield of 36%. MS: m / z 1031.48 (M+H) + .

[0104] Example 14: Tetradentate ring platinum(II) complex Pt31

[0105] Complex Pt31 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 136 mg of a yellow solid, with a yield of 42%. MS: m / z 1078.49 (M+H) + .

[0106] Example 15: Tetradentate ring platinum(II) complex Pt32

[0107] 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 122 mg of a yellow solid, with a yield of 38%. MS: m / z 1079.49 (M+H) + .

[0108] Example 16: Tetradentate ring platinum(II) complex Pt33

[0109] Complex Pt33 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 38%. MS: m / z 1082.51 (M+H) + .

[0110] Example 17: Tetradentate ring platinum(II) complex Pt35

[0111] Complex Pt35 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 148 mg of a yellow solid, with a yield of 32%. MS: m / z 1082.51 (M+H) + .

[0112] Example 18: Tetradentate ring platinum(II) complex Pt41

[0113] 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 153 mg of a yellow solid, with a yield of 47%. MS: m / z 1082.52 (M+H) + .

[0114] Example 19: Tetradentate ring platinum(II) complex Pt43

[0115] Complex Pt43 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 133 mg of a yellow solid, with a yield of 48%. MS: m / z 1111.55 (M+H) + .

[0116] Example 20: Tetradentate ring platinum(II) complex Pt44

[0117] Complex Pt44 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 142 mg of a yellow solid, with a yield of 51%. MS: m / z 1125.56 (M+H) + .

[0118] Example 21: Tetradentate ring platinum(II) complex Pt45

[0119] Complex Pt45 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 125 mg of a yellow solid, with a yield of 42%. MS: m / z 1055.98 (M+H)+ .

[0120] Example 22: Tetradentate ring platinum(II) complex Pt46

[0121] Complex Pt46 was synthesized using the same method as in Example 1 for synthesizing complex Pt1, the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 156 mg of a yellow solid, with a yield of 36%. MS: m / z 1187.58 (M+H) + .

[0122] Example 23: Tetradentate ring platinum(II) complex Pt48

[0123] Complex Pt48 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 118 mg of a yellow solid, with a yield of 33%. MS: m / z 1145.54 (M+H) + .

[0124] Example 24: Tetradentate ring platinum(II) complex Pt50

[0125] Complex Pt50 was prepared using the same synthetic method as complex Pt1 in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 126 mg of a yellow solid, with a yield of 42%. MS: m / z 1103.47 (M+H) + .

[0126] Example 25: Tetradentate ring platinum(II) complex Pt51

[0127] 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 126 mg of a yellow solid, with a yield of 39%. MS: m / z 995.40 (M+H) + .

[0128] Example 26: Tetradentate ring platinum(II) complex Pt52

[0129] Complex Pt52 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 106 mg of a yellow solid, with a yield of 21%. MS: m / z 1291.66 (M+H) + .

[0130] Example 27: Tetradentate ring platinum(II) complex Pt53

[0131] Complex Pt53 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 117 mg of a yellow solid, with a yield of 40%. MS: m / z 1083.52 (M+H) + .

[0132] Example 28: Tetradentate ring platinum(II) complex Pt54

[0133] Complex Pt54 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 140 mg of a yellow solid, with a yield of 49%. MS: m / z 1111.54 (M+H) + .

[0134] Example 29: Tetradentate ring platinum(II) complex Pt55

[0135] Complex Pt55 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 103 mg of a yellow solid, with a yield of 28%. MS: m / z 971.39 (M+H) + .

[0136] Example 30: Tetradentate ring platinum(II) complex Pt56

[0137] Complex Pt56 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 118 mg of a yellow solid, with a yield of 50%. MS: m / z 1179.52 (M+H) + .

[0138] Example 31: Tetradentate ring platinum(II) complex Pt61

[0139] Complex Pt61 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 29%. MS: m / z 1013.44 (M+H) + .

[0140] Example 32: Tetradentate ring platinum(II) complex Pt64

[0141] Complex Pt63 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 133 mg of a yellow solid, with a yield of 48%. MS: m / z 1036.50 (M+H) +.

[0142] Example 33: Tetradentate ring platinum(II) complex Pt65

[0143] Complex Pt65 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 117 mg of a yellow solid, with a yield of 32%. MS: m / z 985.41 (M+H) + .

[0144] Example 34: Tetradentate ring platinum(II) complex Pt69

[0145] Complex Pt69 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 112 mg of a yellow solid, with a yield of 35%. MS: m / z 1027.45 (M+H) + .

[0146] Example 35: Tetradentate ring platinum(II) complex Pt71

[0147] Complex Pt71 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 120 mg of a yellow solid, with a yield of 41%. MS: m / z 1047.64 (M+H) + .

[0148] Example 36: Tetradentate ring platinum(II) complex Pt72

[0149] Complex Pt72 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 138 mg of a yellow solid, with a yield of 47%. MS: m / z 1131.52 (M+H) + .

[0150] Example 37: Tetradentate ring platinum(II) complex Pt75

[0151] Complex Pt75 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 121 mg of a yellow solid, with a yield of 42%. MS: m / z 1089.47 (M+H) + .

[0152] Example 38: Tetradentate ring platinum(II) complex Pt77

[0153] 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 yield was 107 mg of a yellow solid, with a yield of 31%. MS: m / z 1291.64 (M+H) + .

[0154] Example 39: Tetradentate ring platinum(II) complex Pt81

[0155] 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 result was 103 mg of a yellow solid, with a yield of 27%. MS: m / z 1319.68 (M+H) + .

[0156] Example 40: Tetradentate ring platinum(II) complex Pt88

[0157] Complex Pt88 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 132 mg of a yellow solid, with a yield of 44%. MS: m / z 1119.45 (M+H) + .

[0158] Example 41: Tetradentate ring platinum(II) complex Pt90

[0159] 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 1063.37 (M+H) + .

[0160] Example 42: Tetradentate ring platinum(II) complex Pt92

[0161] Complex Pt92 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 122 mg of a yellow solid, with a yield of 37%. MS: m / z 1290.64 (M+H) + .

[0162] Example 43: Tetradentate ring platinum(II) complex Pt94

[0163] Complex Pt94 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 113 mg of a yellow solid, with a yield of 35%. MS: m / z 1289.63 (M+H)+ .

[0164] Example 44: Tetradentate ring platinum(II) complex Pt95

[0165] Complex Pt95 was prepared using the same synthetic method as complex Pt1 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 44%. MS: m / z 1290.64 (M+H) + .

[0166] Example 45: Tetradentate ring platinum(II) complex Pt96

[0167] 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 127 mg of a yellow solid, with a yield of 31%. MS: m / z 1290.64 (M+H) + .

[0168] Example 46: Tetradentate ring platinum(II) complex Pt103

[0169] Complex Pt103 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 103 mg of a yellow solid, with a yield of 32%. MS: m / z 1060.66 (M+H) + .

[0170] Example 47: Tetradentate ring platinum(II) complex Pt106

[0171] Complex Pt106 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 113 mg of a yellow solid, with a yield of 38%. MS: m / z 1289.61 (M+H) + .

[0172] Example 48: Tetradentate ring platinum(II) complex Pt110

[0173] Complex Pt110 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 38%. MS: m / z 1236.57 (M+H) + .

[0174] Photophysical properties:

[0175] Figure 1 shows the room-temperature emission spectra of platinum(II) complex Pt1 in toluene and dichlorosol solutions. Table 1 shows the photophysical performance test results of some tetradentate ring platinum(II) complexes of the present invention in toluene solution at room temperature. From the data in Table 1, it can be seen that the emission wavelength of the platinum metal complex phosphorescent material is in the blue light emission region of about 460 nm; the half-width at half-maximum (WHM) is small, all at or below 35 nm, indicating high color purity; its quantum efficiency in polymethyl methacrylate (PMMA) is high, mostly above 80%, and even reaching 95% or higher; the deuteration of the ligand periphery can ensure improved material stability while having almost no effect on the emission wavelength and WHM; 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.

[0176] Table 1. Photophysical properties of some platinum(II) complexes of the present invention in toluene solution at room temperature.

[0177] Fabrication of OLED devices:

[0178] A p-doped material is deposited on the surface or anode of an ITO glass with a light-emitting area of ​​2 mm × 2 mm, or the p-doped material is co-evaporated with a hole injection material at a concentration of 1% to 50% to form a 5-100 nm hole injection layer (HIL) and a 5-200 nm hole transport layer (HTL). Subsequently, a 10-100 nm light-emitting layer (EML) (which may contain the complex 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, thereby fabricating an OLED organic light-emitting element. The OLED is then tested using standard methods. Unless otherwise specified, the device materials involved in this invention can be obtained by known synthesis methods.

[0179] In a preferred embodiment, the structure of the device Example 1 provided by the present invention is: ITO / P-4 (10nm) / HT1 (60nm) / HTH-85D (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).

[0180] Device Examples 2-43 and Comparative Example 1 were fabricated using structures similar to those in Device Example 1, the only difference being that the Pt1 in Device Example 1 was replaced with the platinum(II) complex shown in Table 2. The luminescence properties of each device example and comparative example were tested using standard methods. The data are shown in Table 2. The device structural formulas involved are as follows: where P-4 is HATCN and ET-14 is BPyTP.

[0181] Table 2. Device luminescence characteristic data table

[0182] As shown in Table 2, compared with Comparative Example 1, Device Examples 1-45 prepared in this application exhibit superior 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 the complexes of this invention as the light-emitting layer material to prepare electronic devices can reduce the driving voltage while improving current efficiency, device lifetime, and color purity. This indicates that the complexes provided by this invention have certain commercial application value. Furthermore, all devices prepared in this invention are deep blue light devices with CIEy values ​​less than 0.2.

[0183] In a preferred embodiment, the structure of device example 46 provided by the present invention is as follows: ITO / P-4 (10nm) / HT1 (60nm) / HTH-85D (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).

[0184] Device Examples 46-52 were fabricated using structures similar to those in Device Example 46, the only difference being that the platinum(II) complex and boron-containing compound (Pt1:BN1-8) in Device Example 46 were replaced with compounds listed in Table 3. The structural formulas of the compounds involved are as follows, and the device structures and luminescence properties are shown in Table 3.

[0185] Table 3. Device Structure and Luminescent Properties Data

[0186] 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 complexes 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 emitted color.

[0187] 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 ring platinum(II) complex guest phosphorescent material, characterized in that, The phosphorescent material has the general structure shown in formula (I): In equation (I), R 1 R 2 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 of the following can be independently represented as hydrogen, deuterium, C1–C30 alkyl, C1–C30 deuterated alkyl, C3–C30 cycloalkyl, substituted or unsubstituted C6–C60 aryl; when substituted, the substituent can be monosubstituted or polysubstituted, and each substituent can be independently selected from one or more of deuterium, C1–C14 alkyl, and C6–C60 aryl.

2. The tetradentate ring platinum(II) complex guest phosphorescent material according to claim 1, characterized in that, In the tetradentate ring platinum (II) complex guest phosphorescent material with the general structure shown in formula (I), hydrogen atoms can be partially or completely replaced by deuterium.

3. The tetradentate ring platinum(II) complex guest phosphorescent material according to claim 1, characterized in that, R 1 R 2 and R 3 Each of the following is independently selected from one or a combination of 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, phenyl, and pyridyl.

4. The tetradentate ring platinum(II) complex guest phosphorescent material according to claim 1, characterized in that, R a R b R c R e R f and R g Each can be independently represented as hydrogen or deuterium; R d It is independently selected from one or a combination of 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, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodel, sec-decyl, tert-decyl, adamantyl, C1-C10 alkyl-substituted or unsubstituted phenyl groups.

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

6. The application of the tetradentate ring platinum(II) complex guest phosphorescent material according to any one of claims 1-5 in the fabrication 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 a tetradentate ring platinum(II) complex guest phosphorescent material 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 includes a light-emitting layer, wherein the light-emitting layer contains the tetradentate ring platinum(II) complex guest phosphorescent material as described in 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, wherein the light-emitting layer contains a tetradentate ring platinum(II) complex guest phosphorescent material as described in any one of claims 1-5; the light-emitting layer further includes a fluorescent dopant material, wherein the fluorescent dopant material 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 a tetradentate ring platinum(II) complex guest phosphorescent material as described in any one of claims 1-5.

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

13. A formulation, characterized in that, The formulation comprises a tetradentate cyclic platinum(II) complex guest phosphorescent material as described in 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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