Tetradentate cyclometalated platinum (II) complex based on 4-carbazolyl carbene structure, electronic device and apparatus, and use thereof

Abstract

The present invention belongs to the technical field of the preparation of organic electroluminescent materials, and specifically relates to a tetradentate cyclometalated platinum (II) complex based on a 4-carbazolyl carbene structure, an electronic device and apparatus, and the use thereof. In the present invention, the steric hindrance of material molecules can be increased by introducing a 4-carbazolyl group having large steric hindrance at a carbene site, such that molecular aggregation can be avoided, and intermolecular interaction and luminescence quenching can be inhibited, which are beneficial for improving the luminescence efficiency and the color purity. The present invention has significant application prospects in the fields of OLED display and illumination.

Description

Tetradentate cyclic platinum(II) complexes based on the 4-carbazole 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 cyclic platinum(II) metal complex based on a 4-carbazole 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, 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%.

[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 generally has a higher energy level than the guest material, transferring energy from the host to the guest material, thus exciting it to emit light. Commonly used organic phosphorescent guest materials are typically 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, used to prepare iridium(III) complex phosphorescent materials, is also significantly higher than that of PtCl2 used to prepare platinum(II) complex phosphorescent materials. Furthermore, the preparation of iridium(III) complex phosphorescent materials involves four steps: iridium(III) 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. 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. Therefore, the preparation cost of platinum(II) complex phosphorescent materials is far lower than that of iridium(III) complex phosphorescent materials. However, the development of platinum complex materials and devices still faces some technical challenges. Improving the chemical and thermal stability of materials, avoiding redshift or luminescence quenching caused by molecular aggregation, and thus extending device lifespan remain key technical problems that need to be solved. There is an urgent need to develop novel phosphorescent platinum(II) complexes. Summary of the Invention

[0005] In view of this, one of the objectives of this invention is to provide a tetradentate cyclic platinum(II) complex based on a 4-carbazole carbene structure. The provided complex, with a highly sterically hindered 4-carbazole group at the carbene site, increases the steric hindrance of the material molecules, preventing molecular aggregation, inhibiting intermolecular interactions and luminescence quenching, thereby improving luminous efficiency and color purity, and showing great promise for applications in OLED displays and lighting.

[0006] The objective of this invention is achieved through the following technical solutions;

[0007] In many embodiments, the present invention provides a platinum(II) complex with the structural formula shown in formula (I):

[0008] In equation (I), R 1 R 2 and R 3Each can be used independently to represent monosubstituted to the maximum amount of substitution, or no substitution; R 1 R 2 and R 3 Whether identical or different, each is independently selected from hydrogen or deuterium, halogen, CN, C1-C30 alkyl, C1-C30 haloalkyl, C1-C30 deuteralkyl, C6-C60 aryl, C6-C60 deuterated aryl, C6-C60 alkylaryl, C5-C60 heteroaryl, C6-C60 arylsilane, C6-C60 diarylamine and combinations thereof, and two adjacent substituents can be linked to form a ring; R a R b R c R d R e Each can be independently represented as monosubstituted, disubstituted, trisubstituted, or tetrasubstituted; R a R b R c R d R e Each can be independently represented as hydrogen or deuterium, halogen, CN, C1-C30 alkyl, C1-C30 haloalkyl, C1-C30 deuteralkyl, C6-C60 aryl, C6-C60 deuterated aryl, C6-C60 alkylaryl, C5-C60 heteroaryl, C6-C60 arylsilyl, C6-C60 diarylamino and combinations thereof; and two adjacent substituents can be linked to form a ring.

[0009] Furthermore, R 1 R 2 and R 3 Each 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, isonyl, sec-nonyl, tert-nonyl, n-decyl, isodel, sec-decyl, tert-decyl, cyclopentane, cyclohexane, phenyl, indene, and combinations thereof.

[0010] Furthermore, R a R b R c R d R e Each can be independently represented as monosubstituted, disubstituted, trisubstituted, or tetrasubstituted; R a -R eEach can be independently represented as hydrogen, deuterium, CN, 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, phenyl, terphenyl, triphenyl, triarylsilyl, carbazole, and combinations thereof.

[0011] Preferably, at least one hydrogen atom in formula (I) can be replaced by deuterium.

[0012] Furthermore, the platinum(II) complex is selected from any of the following chemical structures: where "D" represents deuterium:

[0013] Furthermore, the present invention also provides the application of the metal platinum (II) complex having the structure shown in formula (I) above in the fabrication of electronic devices.

[0014] Furthermore, the electronic device includes one or more of the following: organic electroluminescent device, organic integrated circuit, organic optoelectronic device, organic field-effect transistor, organic thin-film transistor, organic optoelectronic device, organic light-emitting transistor, organic solar cell, organic optical detector, organic photoreceptor, organic field quenching device, luminescent electrochemical cell, or organic laser diode.

[0015] Another exemplary embodiment of the present invention provides an organic electroluminescent device comprising: a cathode, an anode, and an organic functional layer therebetween; wherein the organic functional layer contains a platinum (II) complex having the structure shown in formula (I) above.

[0016] Preferably, the organic functional layer includes a light-emitting layer containing a platinum(II) complex having the structure shown in formula (I) as described above.

[0017] Furthermore, the light-emitting layer also contains a fluorescent dopant material; the fluorescent dopant material is preferably a boron-containing organic luminescent material.

[0018] In another aspect, the present invention also provides an organic optoelectronic device comprising: a substrate layer; a first electrode on the substrate; an organic light-emitting functional layer on the first electrode; and a second electrode on the organic light-emitting functional layer; wherein the organic light-emitting functional layer comprises a tetradentate ring platinum(II) complex having the structure shown in formula (I) as described above. For example, the platinum(II) complex can be included as a light-emitting material in the organic light-emitting functional layer.

[0019] 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.

[0020] 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 layer, and anode onto a substrate in that order. The organic layer can also 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 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.

[0021] The present invention also provides a composition comprising a 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.

[0022] The present invention also provides a formulation comprising a 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.

[0023] 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.

[0024] The organic electroluminescent device described in this 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.

[0025] The materials used in the organic electroluminescent devices according to the present invention can be classified as top-emitting, low-emitting, or bifacial-emitting. 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 principles similar to those of organic light-emitting devices.

[0026] The beneficial effects of this invention are as follows: By introducing a highly sterically hindered 4-carbazole group into the carbene site, this invention can increase the steric hindrance of the material molecules, thereby preventing molecular aggregation, inhibiting intermolecular interactions and luminescence quenching, and thus improving luminous efficiency and color purity. Therefore, the tetradentate ring platinum(II) complex based on the 4-carbazole carbene structure provided by this invention has great application prospects in the fields of OLED displays and lighting. Attached Figure Description

[0027] Figure 1 shows the room temperature emission spectrum of the platinum(II) complex Pt5 in toluene solution. Detailed Implementation

[0028] 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.

[0029] 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).

[0030] When defining various terms, R 1 R 2 R 3 R a -R e 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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).

[0041] 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.

[0042] 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.

[0043] The compounds provided in 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 the aforementioned tetradentate cyclic platinum metal complex based on phenylcarbazole. 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.

[0044] It should be noted that the general instructions above and the detailed instructions below are merely illustrative and explanatory, and are not restrictive.

[0045] This disclosure can be more readily understood by referring to the following detailed description and the embodiments contained therein.

[0046] 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.

[0047] Synthesis Examples

[0048] 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.

[0049] 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.

[0050] 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.

[0051] Synthetic route

[0052] Example 1: Tetradentate ring platinum(II) complex Pt5

[0053] The synthesis route is as follows:

[0054] Synthesis of the intermediate (Cl-NO2): Cl-B (5.00 g, 32.00 mmol, 1.1 equivalents), Br-NO2 (5.87 g, 29.00 mmol, 1.0 equivalents), tetrakis(triphenylphosphine)palladium (670 mg, 0.58 mmol, 2 mol%), and potassium carbonate (8.01 g, 58.00 mmol, 2.0 equivalents) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was then purged with nitrogen three times. Under nitrogen protection, dioxane (40 mL) and water (10 mL) were added. The reaction was carried out in an oil bath at 80 °C for 20 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 silica gel column chromatography. The eluent was petroleum ether / dichloromethane = 10:1-5:1, yielding 6.25 g of a yellow liquid, with a yield of 83%. 1 H NMR (500MHz, CDCl3) δ7.26–7.29(m,1H),7.33–7.36(m,2H),7.37(dd,J=8.0,1.5Hz,1H),7.4 4–7.48(m,1H),7.55–7.60(m,1H),7.68(td,J=7.5,1.0Hz,1H),8.10(dd,J=8.5,1.5Hz,1H).

[0055] Synthesis of intermediate (Cl-NH): Cl-NO2 (6.20 g, 26.75 mmol, 1.0 equivalent) and triphenylphosphine (21.00 g, 80.20 mmol, 3.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was then purged with nitrogen three times, and o-dichlorobenzene (40 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 180 °C for 20 hours, then cooled to room temperature. The solvent was removed by vacuum distillation, and the crude product was separated and filtered using a silica gel column chromatography. The eluent was petroleum ether / dichloromethane = 10:1–6:1, yielding 4.3 g of a white solid, 81% yield. 1 H NMR (500MHz, CDCl3) δ7.22 (dd, J=6.5, 1.5Hz, 1H), 7.29 (ddd, J=8.0, 6.5, 2.0Hz ,1H),7.31–7.36(m,2H),7.43–7.50(m,2H),8.20(s,1H),8.59(d,J=8.0Hz,1H).

[0056] Synthesis of the intermediate (tBu-Cl): Cl-NH (4.00 g, 19.80 mmol, 1.0 equivalent), tBuBr (6.93 g, 25.70 mmol, 1.3 equivalent), cuprous iodide (754 mg, 3.96 mmol, 20 mol%), L-proline (912 mg, 7.92 mmol, 40 mol%), and potassium carbonate (5.47 g, 39.60 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, and dimethyl sulfoxide (40 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 140 °C for 27 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, yielding 6.26 g of a white solid (81% yield). 1 H NMR (500MHz, CDCl3) δ1.39 (s, 18H), 7.26 (dd, J = 2.5Hz, 1H), 7.28–7.34 (m, 3H), 7.35 (d, J = 1.5Hz, 2H), 7.40(d,J=8.5Hz,1H),7.46(ddd,J=8.0,7.0,1.0Hz,1H),7.52(t,J=2.0Hz,1H),8.69(d,J=8.0Hz,1H).

[0057] Synthesis of intermediate (CzNO2): tBu-Cl (6.00 g, 15.40 mmol, 1.0 equivalent), NHNO2 (2.33 g, 16.90 mmol, 1.1 equivalent), tris(dibenzylacetone)palladium (422 mg, 0.46 mmol, 3 mol%), 2-biscyclohexylphosphine-2',4',6'-triisopropylbiphenyl (XPhos) (384 mg, 0.92 mmol, 6 mol%), and cesium carbonate (10.00 g, 30.70 mmol, 2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The flask was purged with nitrogen three times, and toluene (60 mL) was added under nitrogen protection. After reacting in an oil bath at 90℃ for 22 hours and cooling to room temperature, the mixture was filtered, and the solvent was removed by vacuum distillation. The crude product was then separated by silica gel chromatography with petroleum ether / dichloromethane = 15:1 as the eluent, yielding 6.77 g of a yellow solid, with a yield of 89%. 1 H NMR (500MHz, CDCl3) δ1.40 (s, 18H), 6.79 (ddd, J=8.5, 6.5, 1.0Hz, 1H), 7.15 (dd, J=8.5, 1. 5Hz,1H),7.20(dt,J=4.0Hz,1H),7.25(d,J=7.5Hz,1H),7.31(ddd,J=9.0,7.5,2.0Hz,1H) ,7.34(d,J=8.0Hz,1H),7.39(d,J=1.5Hz,2H),7.41(d,J=4.0Hz,2H),7.44(t,J=8.0Hz,1H ),7.54(t,J=1.5Hz,1H),8.04(d,J=8.0Hz,1H),8.32(dd,J=8.5,1.5Hz,1H),10.07(s,1H).

[0058] Synthesis of intermediate (CzNH): CzNO2 (6.74 g, 13.70 mmol, 1.0 equivalent) and palladium on carbon (437 mg, 0.40 mmol, 3 mol%) were added to a three-necked flask equipped with a magnetic stirrer. Ethanol (60 mL) and ethyl acetate (100 mL) were added, and the mixture was purged with hydrogen three times. After reacting at room temperature under a hydrogen atmosphere for 21 hours, the mixture was cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated by silica gel column chromatography with petroleum ether / dichloromethane at a ratio of 10:1 to 3:1, yielding 6.10 g of a gray solid (96% yield). 1H NMR (500MHz, CDCl3) δ1.39 (s, 18H), 4.03 (br, 2H), 6.07 (br, 1H), 6.53 (dd, J = 8.0, 1.0 Hz,1H),6.82(td,J=7.5,1.5Hz,1H),6.91(dd,J=7.9,1.4Hz,1H),6.96(dd,J=8.2,0.8 Hz,1H),7.07(td,J=8.0,1.5Hz,1H),7.15(dd,J=8.0,1.5Hz,1H),7.25(t,J=8.0Hz,1H ),7.26–7.29(m,1H),7.37–7.44(m,4H),7.51(t,J=2.0Hz,1H),8.10(d,J=8.0Hz,1H).

[0059] Synthesis of intermediate (Cz2NH): CzNH (5.83 g, 12.60 mmol, 1.0 equivalent), Cl1 (5.66 g, 13.26 mmol, 1.05 equivalent), tris(dibenzylacetone)palladium (346 mg, 0.37 mmol, 3 mol%), 2-biscyclohexylphosphine-2',6'-dimethoxy-1,1'-diphenyl (SPhos) (311 mg, 0.75 mmol, 6 mol%), and sodium tert-butoxide (2.43 g, 25.25 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, and toluene (70 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 80 °C for 5 hours, then cooled to room temperature. The product was extracted with ethyl acetate, washed with water, dried over sodium sulfate, and the solvent was removed by vacuum distillation. The crude product was then separated and filtered using a silica gel column chromatography. Petroleum ether / ethyl acetate ratio of 20:1 yielded 9.28 g of a gray solid, with a yield of 86%. This solid was used directly in the next step.

[0060] Synthesis of ligand L1: Cz₂NH (9.28 g, 10.90 mmol, 1.0 equivalent) and ammonium hexafluorophosphate (3.55 g, 21.70 mmol, 2.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. Nitrogen gas was purged three times, and triethyl orthoformate (30 mL) was added under nitrogen protection. 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, and the mixture was separated by silica gel column chromatography with dichloromethane / methanol as the eluent (100:1-50:1). 8.54 g of a gray solid was obtained, with a yield of 78%.

[0061] Synthesis of Pt5: L1 (8.00 g, 7.93 mmol, 1.0 equivalent), (1,5-cyclooctadiene)diplatinum chloride (2.97 g, 7.93 mmol, 1.0 equivalent), and sodium acetate (1.95 g, 23.80 mmol, 3.0 equivalent) were added to a three-necked flask equipped with a magnetic stirrer. The mixture was purged with nitrogen three times. Under nitrogen protection, N,N-dimethylformamide (300 mL) was added, 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 25 h. 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 3.60 g of a yellow solid, yield 43%. MS: m / z 1054.39 (M+H) +

[0062] Example 2: Tetradentate ring platinum(II) complex Pt1

[0063] Complex Pt1 was prepared using the same synthetic method as complex Pt5 in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 1.14 g of a yellow solid, with a yield of 40%. (MS: m / z 942.26 M+H) + .

[0064] Example 3: Tetradentate ring platinum(II) complex Pt6

[0065] Complex Pt6 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final yield was 1.08 g of a yellow solid, with a yield of 44%. MS: m / z 1130.42 (M+H) + .

[0066] Example 4: Tetradentate ring platinum(II) complex Pt9

[0067] Complex Pt9 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final result was 1.21 g of a yellow solid, with a yield of 46%. MS: m / z 1170.45 (M+H) + .

[0068] Example 5: Tetradentate ring platinum(II) complex Pt10

[0069] Complex Pt10 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.24 g of a yellow solid, with a yield of 46%. MS: m / z 1114.39 (M+H) + .

[0070] Example 6: Tetradentate ring platinum(II) complex Pt11

[0071] Complex Pt11 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.16 g of a yellow solid, with a yield of 42%. MS: m / z 1240.53 (M+H) + .

[0072] Example 7: Tetradentate ring platinum(II) complex Pt16

[0073] Complex Pt16 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.07 g of a yellow solid, with a yield of 39%. MS: m / z 1282.58 (M+H) + .

[0074] Example 8: Tetradentate ring platinum(II) complex Pt23

[0075] Complex Pt23 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.00 mg of a yellow solid, with a yield of 41%. MS: m / z 998.33 (M+H) + .

[0076] Example 9: Tetradentate ring platinum(II) complex Pt24

[0077] Complex Pt24 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.14 g of a yellow solid, with a yield of 32%. MS: m / z 1018.30 (M+H) + .

[0078] Example 10: Tetradentate ring platinum(II) complex Pt28

[0079] Complex Pt28 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final yield was 0.98 g of a yellow solid, with a yield of 46%. MS: m / z 1242.55 (M+H) + .

[0080] Example 11: Tetradentate ring platinum(II) complex Pt30

[0081] Complex Pt30 was prepared using the same synthetic method as complex Pt5 in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 1.28 g of a yellow solid, with a yield of 48%. MS: m / z 1262.51 (M+H) + .

[0082] Example 12: Tetradentate ring platinum(II) complex Pt32

[0083] Complex Pt32 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.24 g of a yellow solid, with a yield of 45%. MS: m / z 1374.64 (M+H) + .

[0084] Example 13: Tetradentate ring platinum(II) complex Pt34

[0085] Complex Pt34 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.05 g of a yellow solid, with a yield of 38%. MS: m / z 1372.62 (M+H) + .

[0086] Example 14: Tetradentate ring platinum(II) complex Pt38

[0087] Complex Pt38 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.31 g of a yellow solid, with a yield of 48%. MS: m / z 1375.65 (M+H) + .

[0088] Example 15: Tetradentate ring platinum(II) complex Pt40

[0089] Complex Pt40 was prepared using the same synthetic method as complex Pt5 in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 1.35 g of a yellow solid, with a yield of 39%. MS: m / z 1378.67 (M+H) + .

[0090] Example 16: Tetradentate ring platinum(II) complex Pt41

[0091] Complex Pt41 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final yield was 1.10 g of a yellow solid, with a yield of 37%. MS: m / z 1381.68 (M+H)+ .

[0092] Example 17: Tetradentate ring platinum(II) complex Pt59

[0093] Complex Pt59 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 1.23 g of a yellow solid, with a yield of 43%. MS: m / z 1388.72 (M+H) + .

[0094] Example 18: Tetradentate ring platinum(II) complex Pt70

[0095] Complex Pt70 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final result was 1.18 g of a yellow solid, with a yield of 40%. MS: m / z 1278.55 (M+H) + .

[0096] Example 19: Tetradentate ring platinum(II) complex Pt71

[0097] Complex Pt71 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.25 g of a yellow solid, with a yield of 36%. MS: m / z 1018.30 (M+H) + .

[0098] Example 20: Tetradentate ring platinum(II) complex Pt75

[0099] Complex Pt75 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final product was a yellow solid, 1.06 mg, with a yield of 42%. MS: m / z 1130.42 (M+H) + .

[0100] Example 4: Tetradentate ring platinum(II) complex Pt76

[0101] Complex Pt76 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.24 g of a yellow solid, with a yield of 46%. MS: m / z 959.30 (M+H) + .

[0102] Example 21: Tetradentate ring platinum(II) complex Pt78

[0103] Complex Pt78 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final yield was 1.32 g of a yellow solid, with a yield of 36%. MS: m / z 1099.45 (M+H) + .

[0104] Example 22: Tetradentate ring platinum(II) complex Pt90

[0105] Complex Pt90 was prepared using the same synthetic method as complex Pt5 in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 1.21 g of a yellow solid, with a yield of 38%. MS: m / z 1278.55 (M+H) + .

[0106] Example 23: Tetradentate ring platinum(II) complex Pt91

[0107] Complex Pt91 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.25 g of a yellow solid, with a yield of 46%. MS: m / z 956.28 (M+H) + .

[0108] Example 24: Tetradentate ring platinum(II) complex Pt102

[0109] Complex Pt102 was prepared using the same synthetic method as complex Pt5 in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 1.15 g of a yellow solid, with a yield of 38%. MS: m / z 956.28 (M+H) + .

[0110] Example 25: Tetradentate ring platinum(II) complex Pt105

[0111] Complex Pt105 was synthesized using the same method as in Example 1, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.35 g of a yellow solid, with a yield of 42%. MS: m / z 1130.42 (M+H) + .

[0112] Example 26: Tetradentate ring platinum(II) complex Pt111

[0113] Complex Pt111 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.51 g of a yellow solid, with a yield of 47%. MS: m / z 1052.36 (M+H)+ .

[0114] Example 27: Tetradentate ring platinum(II) complex Pt114

[0115] Complex Pt114 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.13 g of a yellow solid, with a yield of 41%. MS: m / z 1245.57 (M+H) + .

[0116] Example 28: Tetradentate ring platinum(II) complex Pt116

[0117] The complex Pt116 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.06 g of a yellow solid, with a yield of 43%. MS: m / z 1071.42 (M+H) + .

[0118] Example 29: Tetradentate ring platinum(II) complex Pt120

[0119] Complex Pt120 was prepared using the same synthetic method as complex Pt5 in Example 1, except that the ligand precursor of the corresponding fragment was replaced. The final yield was 1.26 g of a yellow solid, with a yield of 39%. MS: m / z 1144.60 (M+H) + .

[0120] Example 30: Tetradentate ring platinum(II) complex Pt121

[0121] Complex Pt121 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.12 g of a yellow solid, with a yield of 41%. MS: m / z 1296.59 (M+H) + .

[0122] Example 31: Tetradentate ring platinum(II) complex Pt124

[0123] Complex Pt124 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.18 g of a yellow solid, with a yield of 50%. MS: m / z 1428.69 (M+H) + .

[0124] Example 32: Tetradentate ring platinum(II) complex Pt126

[0125] Complex Pt126 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.02 g of a yellow solid, with a yield of 35%. MS: m / z 1257.57 (M+H) + .

[0126] Example 33: Tetradentate ring platinum(II) complex Pt128

[0127] Complex Pt128 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.23 g of a yellow solid, with a yield of 47%. MS: m / z 1344.59 (M+H) + .

[0128] Example 34: Tetradentate ring platinum(II) complex Pt129

[0129] Complex Pt129 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.30 g of a yellow solid, with a yield of 47%. MS: m / z 1392.59 (M+H) + .

[0130] Example 35: Tetradentate ring platinum(II) complex Pt134

[0131] Complex Pt134 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.07 g of a yellow solid, with a yield of 31%. MS: m / z 1321.59 (M+H) + .

[0132] Example 36: Tetradentate ring platinum(II) complex Pt145

[0133] Complex Pt145 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.15 g of a yellow solid, with a yield of 33%. MS: m / z 1278.55 (M+H) + .

[0134] Example 37: Tetradentate ring platinum(II) complex Pt155

[0135] Complex Pt155 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.21 g of a yellow solid, with a yield of 37%. MS: m / z 1431.71 (M+H) + .

[0136] Example 38: Tetradentate ring platinum(II) complex Pt157

[0137] Complex Pt157 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final result was 1.20 g of a yellow solid, with a yield of 41%. MS: m / z 1013.34 (M+H) + .

[0138] Example 39: Tetradentate ring platinum(II) complex Pt158

[0139] Complex Pt158 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.33 g of a yellow solid, with a yield of 40%. MS: m / z 1091.39 (M+H) + .

[0140] Example 40: Tetradentate ring platinum(II) complex Pt159

[0141] Complex Pt159 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.31 g of a yellow solid, with a yield of 47%. MS: m / z 1141.39 (M+H) + .

[0142] Example 41: Tetradentate ring platinum(II) complex Pt160

[0143] Complex Pt160 was prepared using the same synthetic method as complex Pt5 in Example 1, with the only difference being the replacement of the corresponding ligand precursor in Example 1. The final yield was 1.02 g of a yellow solid, with a yield of 44%. MS: m / z 1068.29 (M+H) + .

[0144] Example 42: Tetradentate ring platinum(II) complex Pt161

[0145] Complex Pt161 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.24 g of a yellow solid, with a yield of 46%. MS: m / z 1091.39 (M+H) + .

[0146] Example 43: Tetradentate ring platinum(II) complex Pt163

[0147] Complex Pt163 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.27 g of a yellow solid, with a yield of 31%. MS: m / z 1223.49 (M+H) + .

[0148] Example 44: Tetradentate ring platinum(II) complex Pt168

[0149] Complex Pt168 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.13 g of a yellow solid, with a yield of 37%. MS: m / z 1444.57 (M+H) + .

[0150] Example 45: Tetradentate ring platinum(II) complex Pt171

[0151] Complex Pt171 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.31 g of a yellow solid, with a yield of 40%. MS: m / z 959.30 (M+H) + .

[0152] Example 46: Tetradentate ring platinum(II) complex Pt172

[0153] Complex Pt172 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.07 g of a yellow solid, with a yield of 40%. MS: m / z 1214.51 (M+H) + .

[0154] Example 47: Tetradentate ring platinum(II) complex Pt173

[0155] Complex Pt173 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.15 g of a yellow solid, with a yield of 42%. MS: m / z 1146.45 (M+H)+ .

[0156] Example 48: Tetradentate ring platinum(II) complex Pt176

[0157] Complex Pt176 was synthesized using the same method as in Example 1 for complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.13 g of a yellow solid, with a yield of 51%. MS: m / z 967.26 (M+H) + .

[0158] Example 49: Tetradentate ring platinum(II) complex Pt177

[0159] Complex Pt177 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.17 g of a yellow solid, with a yield of 46%. MS: m / z 1130.42 (M+H) + .

[0160] Example 50: Tetradentate ring platinum(II) complex Pt178

[0161] Complex Pt178 was synthesized using the same method as in Example 1 for synthesizing complex Pt5, with the only difference being the substitution of the corresponding ligand precursor in Example 1. The final yield was 1.01 g of a yellow solid, with a yield of 41%. MS: m / z 1235.48 (M+H) + .

[0162] Photophysical properties:

[0163] Figure 1 shows the room-temperature emission spectrum of the platinum(II) complex Pt5 in toluene solution. Table 1 shows the photophysical properties of the platinum(II) complex Pt5 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 around 460 nm; the full width at half maximum (FWHM) is small, all 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 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.

[0164] Table 1. Photophysical properties of platinum(II) complexes in toluene solution at room temperature.

[0165] Fabrication of OLED devices:

[0166] An organic light-emitting element (OLED) is fabricated by depositing p-doped materials P-1 to P-5 onto the surface or anode of an ITO glass with a light-emitting area of ​​2 mm × 2 mm, or by co-evaporating the p-doped materials with the compounds described in the table at a concentration of 1% to 50%. This forms 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 compounds described) is formed on the hole transport layer. Finally, an electron transport layer (ETL) of 20-200 nm and a cathode of 50-200 nm are formed sequentially using the compounds described. 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.

[0167] 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) / ET100 (40nm) / Liq (1nm) / Al (100nm).

[0168] Device Examples 2-42 and Comparative Example 1 were fabricated using structures similar to those in Device Example 1, the only difference being that the Pt5 in Device Example 1 was replaced with the platinum(II) complex 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.

[0169] Table 2. Device luminescence characteristic data table

[0170] As shown in Table 2, compared with Comparative Example 1, Device Examples 1-42 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 compound 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.

[0171] In a preferred embodiment, the structure of device example 43 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) / ET100 (40nm) / Liq (1nm) / Al (100nm).

[0172] Devices 44-49 were fabricated using a structure similar to that of Device 43, the only difference being that the platinum(II) complex and boron-containing compound in Device 43 were replaced with compounds listed in Table 3. Device structure and luminescence properties data are shown in Table 3.

[0173] Table 3. Device Structure and Luminescent Properties Data

[0174] As shown in Table 3, when the compounds 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 emitted color.

[0175] 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 metal platinum (II) complex characterized in that, It has the structural formula shown in equation (I): In equation (I), R 1 R 2 and R 3 Each can be used independently to represent monosubstituted to the maximum amount of substitution, or no substitution; R 1 R 2 and R 3 Whether identical or different, each is independently selected from hydrogen or deuterium, halogen, CN, C1-C30 alkyl, C1-C30 haloalkyl, C1-C30 deuteralkyl, C6-C60 aryl, C6-C60 deuterated aryl, C6-C60 alkylaryl, C5-C60 heteroaryl, C6-C60 arylsilane, C6-C60 diarylamine and combinations thereof, and two adjacent substituents can be linked to form a ring; R a R b R c R d R e Each can be independently represented as monosubstituted, disubstituted, trisubstituted, or tetrasubstituted; R a R b R c R d R e Each can be independently represented as hydrogen or deuterium, halogen, CN, C1-C30 alkyl, C1-C30 haloalkyl, C1-C30 deuteralkyl, C6-C60 aryl, C6-C60 deuterated aryl, C6-C60 alkylaryl, C5-C60 heteroaryl, C6-C60 arylsilyl, C6-C60 diarylamino and combinations thereof; and two adjacent substituents can be linked to form a ring.

2. The metal platinum (II) complex according to claim 1, characterized in that, R 1 R 2 and R 3 Each 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, isonyl, sec-nonyl, tert-nonyl, n-decyl, isodel, sec-decyl, tert-decyl, cyclopentane, cyclohexane, phenyl, indene, and combinations thereof.

3. The metal platinum (II) complex of claim 1, wherein R a R b R c R d R e Each can be independently represented as monosubstituted, disubstituted, trisubstituted, or tetrasubstituted; R a -R e Each can be independently represented as hydrogen, deuterium, CN, 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, phenyl, terphenyl, triphenyl, triarylsilyl, carbazole, and combinations thereof.

4. The metal platinum (II) complex of claim 1, wherein Platinum(II) complexes are selected from any of the chemical structures shown below, where "D" represents deuterium:

5. The use of the platinum(II) complex according to any one of claims 1-4 in the preparation of electronic devices.

6. An organic electroluminescent device, characterized by The organic electroluminescent device comprises a cathode, an anode, and an organic functional layer between them; the organic functional layer contains the platinum(II) complex as described in any one of claims 1-4.

7. The organic electroluminescent device according to claim 6, characterized in that The organic functional layer includes a light-emitting layer, which contains the platinum(II) complex according to any one of claims 1-4.

8. The organic electroluminescent device according to claim 7, characterized in that The light-emitting layer also contains a fluorescent dopant material, which is a boron-containing compound.

9. 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 platinum(II) complex as described in any one of claims 1-4.

10. The organic optoelectronic device according to claim 9, characterized in that The organic light-emitting functional layer also contains a fluorescent dopant material, which is a boron-containing organic luminescent material.

11. A composition characterized in that, The composition comprises the platinum(II) complex according to any one of claims 1-4.

12. A formulation characterized in that, The formulation comprises the platinum(II) complex according to any one of claims 1-4.

13. A display or illumination device, characterized in that The device comprises one of the organic electroluminescent device of claim 6 or the organic optoelectronic device of claim 9.

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