A tetradentate ring metal platinum (II) complex, electronic device and application thereof

Abstract

The present invention belongs to the field of organic electroluminescence, and in particular relates to a tetradentate ring metal platinum (II) complex, an electronic device and its application. The present invention increases the dihedral angle between the pyridine unit by introducing 2,6-di(phenyl) tert-butylphenyl at the appropriate position of the ligand, thereby reducing the accumulation between molecules. At the same time, the charge distribution of its excited state is improved, so that its material excited state has more metal to pyridyl and carbene charge transfer states, thereby improving the device life. It has good chemical stability and thermal stability and is easy to prepare vapor-deposited OLED devices. After being combined with a fluorescent doping material, it can balance the transmission of holes and electrons, making the energy transfer between the host and the guest more efficient. When used as an organic electroluminescent device, there is a significant improvement in current efficiency and life, and the light-on voltage is significantly reduced. It has great application prospects in the field of OLED display and lighting.

Description

Technical Field

[0001] The present invention belongs to the field of organic electroluminescence, and in particular relates to a tetradentate ring metal platinum (II) complex, an electronic device and applications thereof. Background Art

[0002] Organic light-emitting diodes (OLEDs) are a new generation of full-color display and lighting technology. Compared to liquid crystal displays, which have shortcomings such as slow response speed, small viewing angle, need for backlight, and high energy consumption, OLED, as an autonomous light-emitting device, does not require a backlight and is energy-efficient. It also has low driving voltage, fast response speed, high resolution and contrast, wide viewing angle, and outstanding low-temperature performance. OLED devices can be made thinner and can be made into flexible structures. In addition, it has the advantages of low production cost, simple production process, and large-scale production. Therefore, OLED has broad and huge application prospects in high-end electronic products and aerospace. With the gradual increase in investment, further in-depth research and development, and the upgrading and transformation of production equipment, OLEDs will have very broad application scenarios and development prospects in the future.

[0003] The core of OLED development lies in the design and development of luminescent materials. The luminescent layers of currently used OLED devices almost all utilize a host-guest luminescence mechanism. This involves doping a guest luminescent material into a host material. The host material generally has a higher energy system than the guest luminescent material. Energy is transferred from the host material to the guest material, exciting the guest material to emit light. Commonly used organic phosphorescent guest materials are heavy metal atoms such as iridium(III), platinum(II), and palladium(II). Commonly used phosphorescent organic materials, mCBP (3,3′-bis(9-carbazolyl)-biphenyl) and 2,6-mCPy (2,6-bis(9-carbazolyl)-pyridine), possess high efficiency and high triplet energy levels. When used as organic materials, triplet energy can be efficiently transferred from the luminescent organic material to the guest phosphorescent luminescent material. However, due to the easy hole transport properties of mCBP and the poor hole transport properties of 2,6-mCPy, the charge imbalance in the luminescent layer reduces the current efficiency of the device. In addition, the number of heavy metal phosphorescent organic complex molecules and cyclometallated iridium (III) complex molecules currently in use is limited. The content of metallic platinum in the earth's crust and the annual production worldwide are both about ten times that of metallic iridium. IrCl3 used to prepare iridium (III) complex phosphorescent materials .The price of H2O is also much higher than PtCl2 used to prepare 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 conversion of mer- to fac-iridium (III) complex isomers, which greatly reduces the overall yield and the cost of raw material IrCl3. . The increased utilization of H₂O increases the preparation cost of iridium (III) complex phosphorescent materials. In contrast, the preparation of platinum (II) complex phosphorescent materials only involves the final step of metallization of the ligand and the design of the platinum salt reaction. This high utilization of the platinum element can further reduce the preparation cost of platinum (II) complex phosphorescent materials. In summary, the preparation cost of platinum (II) complex phosphorescent materials is much lower than that of iridium (III) complex phosphorescent materials. However, the development of platinum complex materials and devices still faces several technical difficulties. Improving device efficiency and lifespan is a relatively important research issue. Therefore, the development of new phosphorescent metal platinum (II) complexes is urgently needed. Summary of the Invention

[0004] In light of this, the present invention aims to provide a tetradentate cyclic metal platinum (II) complex, an electronic device, and its applications. The tetradentate cyclic metal platinum (II) complex of the present invention can be used as a guest phosphorescent material in the light-emitting layer to impart excellent device performance. Furthermore, combining it with specific host materials can improve the current efficiency of electronic devices, particularly organic electroluminescent devices, improve device lifespan, and reduce the operating voltage of the device.

[0005] The present invention provides a tetradentate cyclic metal platinum (II) complex, wherein the tetradentate cyclic metal platinum (II) complex is selected from any one of the chemical structures shown below, wherein "D" represents deuterium and "Ph" represents a phenyl group:

[0006]

[0007]

[0008]

[0009] Furthermore, the present invention also provides the use of the tetradentate ring metal platinum (II) complex having the structure shown as Pt1-Pt45 above in electronic devices.

[0010] Furthermore, the electronic devices include organic electroluminescent devices (OLEDs), organic integrated circuits (O-ICs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light emitting electrochemical cells (LECs) and organic laser diodes (O-lasers).

[0011] In another aspect, the present invention further provides an organic electroluminescent device comprising a tetradentate metal platinum (II) complex having the structure shown as Pt1-Pt45 as described above.

[0012] Furthermore, the organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises the tetradentate ring metal platinum (II) complex having a structure represented by formula (I) or formula (II) as described above.

[0013] Preferably, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the tetradentate ring metal platinum (II) complex having a structure represented by the formula Pt1-Pt45 as described above.

[0014] Furthermore, the light-emitting layer further comprises a fluorescent doping material; the fluorescent doping material is selected from any one or more compounds represented by formula (BN1) to formula (BN5):

[0015]

[0016] Wherein, X is O, S, Se or NR 300 ;

[0017] X 1 、X 2 、X 3 、X 4 Each independently represents O, S, Se or N;

[0018] R b -R e Each independently represents mono-, di-, tri-, tetra- or unsubstituted; R b -R e Each independently selected from the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, C6-C60 aryl; the R4-R 11 Each independently represents the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, and C6-C60 aryl.

[0019] Preferably, R4, R5, R6, and R9 are each independently selected from a substituted or unsubstituted diphenylamine group, a substituted or unsubstituted carbazole group; the substitution may be multiple substitutions, and when containing a substituent, the substituent is selected from deuterium, a C1-C30 alkyl group, and a C6-C30 aryl group.

[0020] Preferably, the R7-R8, R 10 -R 11 Each is independently selected from the group consisting of hydrogen, C1-C30 alkyl, and C6-C60 aryl.

[0021] Further preferably, the R4-R 11 At least one hydrogen in may be substituted by deuterium.

[0022] Furthermore, the fluorescent doping material is selected from any one of the chemical structures shown below, wherein Ph represents a phenyl group, and D4 and D5 mean substitution by 4 and 5 deuterium atoms, respectively:

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030] In another aspect, the present invention further provides an organic optoelectronic device comprising: a substrate layer; a first electrode on the substrate; an organic light-emitting functional layer on the first electrode; and a second electrode on the organic light-emitting functional layer. The organic light-emitting functional layer comprises a tetradentate ring metal platinum (II) complex having a structure represented by the formula Pt1-Pt45. For example, the platinum (II) complex can be included in the organic light-emitting functional layer as a luminescent material.

[0031] Furthermore, the organic light-emitting functional layer further comprises any one or more fluorescent doping materials of the compounds represented by formula (BN1) to formula (BN5) as above.

[0032] The present invention also provides a composition comprising a tetradentate cyclic platinum (II) complex having a structure represented by formulae Pt1-Pt45. Preferably, the composition further comprises a fluorescent dopant material comprising one or more of the compounds represented by formulae (BN1)-(BN5).

[0033] The present invention also provides a preparation comprising a tetradentate ring metal platinum (II) complex having a structure shown in the formula Pt1-Pt45 as above or a composition as described above and at least one solvent. The solvent is not particularly limited, and those skilled in the art may use unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decahydronaphthalene, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, hexyl chloride, bromohexane, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, ether solvents such as tetrahydrofuran and tetrahydropyran, and ester solvents such as alkyl benzoate.

[0034] Preferably, the composition further comprises any one or more fluorescent doping materials of the compounds represented by formula (BN1) to formula (BN5) above.

[0035] The present invention also provides a display or lighting device, which comprises one or more of the organic photoelectric devices described above.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] The present invention provides a phosphorescent material of a tetradentate ring metal platinum (II) complex. By introducing 2,6-di(phenyl) tert-butylphenyl at an appropriate position of its ligand, the dihedral angle between the pyridine unit is increased, reducing the stacking between molecules. At the same time, the charge distribution of its excited state is improved, so that the excited state of the material has more metal to pyridocarbene charge transfer states ( 3 MLCT) helps increase its radiation rate, thereby extending device life. The materials involved in this invention all have excellent chemical and thermal stability, making them easy to prepare vapor-deposited OLED devices. When combined with fluorescent doping materials, they can balance the transmission of holes and electrons, making the energy transfer between host and guest more efficient. Organic electroluminescent devices fabricated using the compounds of this invention as the light-emitting layer have significantly improved current efficiency and lifespan, and significantly reduced the turn-on voltage. In particular, their combined use with phosphorescent boron-containing compounds can improve the device's light color purity. DETAILED DESCRIPTION

[0038] The following describes the present invention in detail. The description of the components described below may be based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.

[0039] The term "substituted" as used herein is intended to include 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 suitable organic compounds, permissible substituents may be one or more, identical or different. For the purposes of the present invention, heteroatoms (e.g., nitrogen) can have hydrogen substituents and / or any permissible substituents of the organic compounds described herein that satisfy the valence of the heteroatoms. The present invention is not intended to impose any restrictions in any way on the permissible substituents of organic compounds. Similarly, the terms "substituted" or "substituted with" include the implicit condition that such substitution conforms to the permissible valence 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 transformation (e.g., by rearrangement, cyclization, elimination, etc.)). It is also contemplated that, in certain aspects, unless explicitly stated to the contrary, individual substituents can be further optionally substituted (ie, further substituted or unsubstituted).

[0040] In defining various terms, “R1”-“R 11 " are used as general symbols in the present invention to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed in the present invention, and when they are limited to certain substituents in one instance, they may be limited to some other substituents in other instances.

[0041] The "R1", "R2", "R3" ... "R n " " (wherein n is an integer) may independently have one or more of the groups listed above. For example, if R 1 If the alkyl group is a straight chain alkyl group, then one of the hydrogen atoms of the alkyl group may be optionally substituted with a hydroxyl group, an alkoxy group, an alkyl group, a halogen group, or the like. Depending on the group selected, the first group may be incorporated into the second group, or alternatively, the first group may be suspended, i.e., attached to the second group. For example, for the phrase "an alkyl group comprising an amino group," the amino group may be incorporated into the main chain of the alkyl group. Alternatively, the amino group may be attached to the main chain of the alkyl group. The nature of the selected group will determine whether the first group is embedded in or attached to the second group.

[0042] The term "alkyl" as used herein refers to a saturated hydrocarbon group of 1 to 60 carbon atoms, which is branched or unbranched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups, including but not limited to the optionally substituted alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxyl, nitro, silyl, sulfo-oxo or sulfhydryl groups of the present invention.

[0043] The term "aryl" used in the present invention is a group containing any carbon-based aromatic group of 5 to 60 carbon atoms, and the carbon-based aromatic group includes but is not limited to phenyl, naphthyl, phenyl, biphenyl, phenoxyphenyl, anthracenyl, phenanthrenyl, etc. The term "aryl" also includes "heteroaryl", which is defined as a group containing an aromatic group, and the aromatic group has 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. Similarly, the term "non-heteroaryl" (which is also included in the term "aryl") defines a group containing an aromatic group, and the aromatic group does not contain heteroatoms. Aryl can be substituted or unsubstituted. The aryl group may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, sulfo-oxo, or mercapto groups as described herein.

[0044] The term "amine" or "amino" as used herein refers to an amino group of the formula -NR 1 R 2 Indicates that R 1 and R 2 They may be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl.

[0045] The compounds of the present invention may contain "optionally substituted" parts. Typically, the term "substituted" (whether or not the term "optionally" is present in the preceding) means that one or more hydrogens of the part indicated are replaced by a suitable substituent. Unless otherwise stated, "optionally substituted" groups may have a suitable substituent at each substitutable position of the group, and when more than one position may be substituted with more than one substituent selected from a specified group in any given structure, the substituent at each position may be the same or different. The substituent combinations envisioned by the present invention are preferably those that form stable or chemically feasible compounds. In some aspects, unless clearly indicated otherwise, it is also contemplated that each substituent may further be optionally substituted (that is, further substituted or unsubstituted).

[0046] The structure of the compound can be represented by the following formula:

[0047]

[0048] It is understood to be equivalent to the following formula:

[0049]

[0050] Where n is usually an integer. That is, R n is understood to mean five individual substituents R a(1) 、R a(2) 、R a(3) 、R a(4) 、R a (5) "Individual substituent" means that each R substituent can be defined independently. For example, if in one case R a(m) is a halogen, then in this case R a(n) Not necessarily halogen.

[0051] The compounds disclosed herein can exhibit desirable properties and have emission and / or absorption spectra that can be tuned by selecting appropriate ligands. In another aspect, the invention can exclude any one or more compounds, structures, or portions thereof specifically recited herein.

[0052] 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.

[0053] It should be noted that the above general description and the following detailed description are merely exemplary and explanatory and are not restrictive.

[0054] The present application may be understood more readily by reference to the following detailed description and the Examples included therein.

[0055] 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 otherwise indicated), or specific reagents (otherwise otherwise indicated), as these can of course vary. It should also be understood that the terms used in the present invention are only for the purpose of describing specific aspects and are not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing, exemplary methods and materials are described below. All raw materials and solvents in the synthetic examples were purchased commercially unless otherwise specified, and the solvents were used directly without further processing.

[0056] The substrate described in the present invention can be any substrate typically used in organic optoelectronic devices. It can be glass or transparent plastic, or an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have varying mechanical strength, thermal stability, transparency, surface smoothness, and water resistance, and their applications vary depending on the properties of the substrate. The materials used in the hole injection layer, hole transport layer, and electron injection layer can be any material from among those known to be used in OLED devices, and the present invention does not impose any specific limitations thereon.

[0057] Synthesis Example

[0058] The following examples of compound syntheses, compositions, devices, or methods are intended only to provide a general approach to the industry and are not intended to limit the scope of protection of this patent. While the data (quantities, temperatures, etc.) mentioned in the patent are as accurate as possible, some errors may exist. Unless otherwise noted, all weighings are separate, temperatures are in °C or at room temperature, and pressures are near atmospheric pressure.

[0059] The following examples provide methods for preparing novel compounds, but the preparation of such compounds is not limited to these methods. In this area of expertise, since the compounds protected herein are easily modified and prepared, they can be prepared using the methods listed below or other methods. The following examples are provided as examples only 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 for different reactants.

[0060] 1 H NMR (500 MHz), 1 H NMR (400 MHz), 13 C NMR (126 MHz) spectra were measured on an ANANCE III (500M) nuclear magnetic resonance spectrometer. Unless otherwise specified, DMSO-d6 or CDCl3 containing 0.1% TMS was used as the solvent for NMR. 1When CDCl3 was used as the solvent, TMS (δ = 0.00 ppm) was used as the internal standard for H NMR spectra. When DMSO-d6 was used as the solvent, TMS (δ = 0.00 ppm), the residual DMSO peak (δ = 2.50 ppm), or the residual water peak (δ = 3.33 ppm) was used as the internal standard. 13 In the C NMR spectra, CDCl3 (δ = 77.00 ppm) or DMSO-d6 (δ = 39.52 ppm) was used as the internal standard. HPLC-MS was measured on an Agilent 6210TOF LC / MS mass spectrometer; HRMS spectra were measured on an Agilent 6210TOF LC / MS liquid chromatography-time of flight mass spectrometer. 1 In H NMR spectrum data: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad.

[0061] Example 1: The synthetic route of the intermediate (dPh-tBuNH2) is as follows

[0062]

[0063] Synthesis of the intermediate (dBr-tBuNH2): To a reaction flask, p-tert-butylaniline (15.0 g, 100 mmol, 1.0 equivalent) and dichloromethane (150 mL) were added to dissolve N-bromosuccinimide (37.7 g, 210 mmol, 2.1 equivalents). The reaction was allowed to react at room temperature for 48 hours. The organic phase was separated, concentrated, and purified by silica gel column chromatography to obtain 25.6 g of a red liquid in 84% yield. The product was used directly in the next step without structural characterization.

[0064] Synthesis of the intermediate (dBr-tBuNO2): dBr-tBuNH2 (5 g, 16.3 mmol, 1.0 eq) was added to a reaction flask and dissolved in N-methylpyrrolidone (50 mL). Sodium hydride (1.96 g, 49 mmol, 3.0 eq) was added, followed by o-fluoronitrobenzene (3.45 g, 24.5 mmol, 1.5 eq). The reaction was allowed to stand at room temperature for 48 hours. The organic phase was separated, concentrated, and purified by silica gel column chromatography to give 5.08 g of a yellow solid in a 73% yield. The product was used directly in the next step without structural characterization.

[0065] Synthesis of the intermediate (dBr-tBu2NH2): To a reaction flask, add dBr-tBuNO2 (4.8 g, 11.2 mmol, 1.0 equiv) and stannous chloride (10.1 g, 44.8 mmol, 4.0 equiv), followed by ethyl acetate (50 mL) and ethanol (50 mL). The reaction was allowed to stand at 78°C for 24 hours, cooled to room temperature, and the organic phase was separated, concentrated, and purified by silica gel column chromatography to afford 3.43 g of a white solid in 82% yield. The product was used directly in the next step without structural characterization.

[0066] Synthesis of the intermediate (dPh-tBuNH2): To a reaction flask were added dBr-tBu2NH2 (3.2 g, 8 mmol, 1.0 equiv), phenylboronic acid (2.93 g, 24 mmol, 3.0 equiv), tetrakistriphenylphosphine palladium (185 mg, 0.16 mmol, 0.02 equiv), potassium carbonate (2.8 g, 20 mmol, 2.5 equiv), dioxane (40 mL), and water (15 mL). The reaction was allowed to proceed at 90°C for 24 hours, then cooled to room temperature. The organic phase was separated, concentrated, and purified by silica gel column chromatography to afford 2.66 g of a white solid in 84% yield. 1 H NMR (500MHz, DMSO) δ1.35(s,9H),4.44(s,2H),5.57(s,1H),6.05(dd,J=8.0,1.5Hz,1H),6.12(td,J=7.5,1.5Hz,1H),6.25 (td,J=7.5,1.5Hz,1H),6.31(dd,J=7.5,1.5Hz,1H),7.16–7.20(m,2H),7.23–7.26(m,4H),7.28(s,2H),7.41–7.43(m,4H).

[0067] Example 2: The synthetic route of Pt1 is as follows

[0068]

[0069] Synthesis of intermediate (M1-OMe): To a reaction flask, 4-(tert-butyl)-2-chloropyridine (20.6 g, 121.2 mmol, 1.2 equiv), 2-methoxycarbazole (20 g, 101 mmol, 1.0 equiv), trisdibenzylideneacetone dipalladium (925 mg, 1.01 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (904 mg, 3.03 mmol, 3 mol%), and sodium tert-butoxide (19.41 g, 202 mmol, 2.0 equiv) were added. Toluene (200 mL) was added. The reaction was allowed to stand at 110°C for 48 hours, cooled to room temperature, and the organic phase was separated, concentrated, and purified by silica gel column chromatography to give 32.71 g of a white solid in a 98% yield. The product was not structurally characterized and was used directly in the next step.

[0070] Synthesis of Intermediate (M1-OH): Add M1-OMe and hydrogen bromide (80.91 g, 990 mmol, 10.0 equivalents) to a reaction flask. Incubate at 120°C for 24 hours to terminate the reaction. Cool to room temperature, separate the organic phase, concentrate, and purify by silica gel column chromatography to afford 30.6 g of a white solid in 97% yield. The product was used directly in the next step without structural characterization.

[0071] Synthesis of intermediate (M1-Cl): To a reaction flask were added M1-OH (5 g, 15.8 mmol, 1.0 equiv), 3-chloro-5-bromo-tert-butylbenzene (4.3 g, 17.4 mmol, 1.1 equiv), 2-picolinic acid (390 mg, 3.16 mmol, 20 mmol%), cuprous iodide (301 mg, 1.58 mmol, 10 mmol%), potassium phosphate (522 mg, 2.46 mmol, 2.0 equiv), and dimethyl sulfoxide (50 mL). The reaction was continued at 100°C for 12 hours, cooled to room temperature, and the organic phase was separated, concentrated, and purified by silica gel column chromatography to afford 6.94 g of a white solid in a 91% yield.

[0072]

[0073] Synthesis of intermediate (LNH-Pt1): dPh-tBuNH2 (400 mg, 1.02 mmol, 1.0 equiv) was added to a reaction flask, followed by M1-Cl (492 mg, 1.02 mmol, 1.0 equiv), trisdibenzylideneacetone dipalladium (28 mg, 0.03 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (19 mg, 0.06 mmol, 6 mol%), and sodium tert-butoxide (167 mg, 1.74 mmol, 2.0 equiv). Toluene (5 mL) was added. The reaction was terminated by heating at 100°C for 17 hours, cooling to room temperature, separating the organic phase, concentrating, and performing silica gel column chromatography to obtain 760 mg of a white solid in 89% yield. The product was used directly in the next step without structural characterization.

[0074] Synthesis of Ligand (L-Pt1): To a reaction flask, add LNH-Pt1 (730 mg, 0.87 mmol, 1.0 equiv), followed by ammonium hexafluorophosphate (284 mg, 1.74 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). The reaction was incubated at 80°C for 8 hours, cooled to room temperature, and the organic phase was separated, concentrated, and purified by silica gel column chromatography to afford 320 mg of a white solid (39% yield). 1H NMR (500MHz, CDCl3) δ1.27(s,9H),1.29(s,9H),1.43(s,9H),6.81(t,J=2.0Hz,1H),6 .95(t,J=1.5Hz,1H),7.08–7.13(m,6H),7.13–7.16(m,5H),7.34–7.35(m,1H),7.45– 7.49(m,5H),7.51–7.57(m,2H),7.65–7.69(m,2H),7.72(s,2H),7.76(d,J=7.5Hz,1H ),8.27(d,J=7.5Hz,1H),8.35(d,J=8.5Hz,1H),8.58(d,J=6.0Hz,1H),10.24(s,1H).

[0075] Synthesis of Pt1: L-Pt1 (200 mg, 0.2 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (79 mg, 0.21 mmol, 1.05 equiv), and sodium acetate (50 mg, 0.60 mmol, 3.0 equiv) were added to a reaction flask. Diethylene glycol dimethyl ether (10 mL) was added. The reaction was allowed to proceed at 120°C for 72 hours, then cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 172 mg of a light yellow solid (83% yield). 1 H NMR(500MHz,DMSO)δ1.22(s,9H),1.41(s,9H),1.42(s,9H),6.51–6.68(m,3H),6.85–7.23(m,9H),7.31–7.69(m,9H),7.82(d,J =8.0Hz,1H),7.91(d,J=2.0Hz,1H),8.04(d,J=8.0Hz,1H),8.12(d,J=8.5Hz,1H),8.19(d,J=3.5Hz,1H),8.93(d,J=6.5Hz,1H).

[0076] Example 3: The synthetic route of Pt2 is as follows

[0077]

[0078] Synthesis of intermediate (M2-Cl): To a reaction flask were added M1-OH (8.0 g, 25.3 mmol, 1.0 equiv), m-chlorobromobenzene (5.34 g, 27.8 mmol, 1.1 equiv), 2-pyridinecarboxylic acid (623 mg, 5.06 mmol, 20 mmol%), cuprous iodide (481 mg, 2.53 mmol, 10 mmol%), potassium phosphate (10.74 g, 50.6 mmol, 2.0 equiv), and dimethyl sulfoxide (80 mL). The reaction was allowed to proceed at 100°C for 12 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 6.94 g of a white solid in a 93% yield. The product was used directly in the next step without structural characterization.

[0079]

[0080] Synthesis of intermediate (LNH-Pt2): dPh-tBuNH2 (5 g, 12.7 mmol, 1.0 equiv) was added to a reaction flask, followed by M2-Cl (5.43 mg, 12.7 mmol, 1.0 equiv), trisdibenzylideneacetone dipalladium (349 mg, 0.38 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (230 mg, 0.76 mmol, 6 mol%), and sodium tert-butoxide (2.44 g, 25.4 mmol, 2.0 equiv). Toluene (50 mL) was added. The reaction was terminated by heating at 100°C for 9 hours, cooling to room temperature, separating the organic phase, concentrating, and performing silica gel column chromatography to afford 8.85 g of a white solid in 87% yield. The product was not structurally characterized and used directly in the next step.

[0081] Synthesis of Ligand (L-Pt2): To a reaction flask, add LNH-Pt2 (4.19 g, 5.4 mmol, 1.0 equiv), followed by ammonium hexafluorophosphate (1.76 g, 10.8 mmol, 2.0 equiv), and triethyl orthoformate (20 mL). The reaction was incubated at 80°C for 7 hours, then cooled to room temperature. The organic phase was separated, concentrated, and purified by silica gel column chromatography to yield 3.67 g of a white solid (72% yield). 1 H NMR (500MHz, DMSO) δ1.30(s,9H),1.45(s,9H),6.98(t,J=2.5Hz,1H),7.11–7.19(m,12H),7.36–7.42(m,2H),7.47– 7.59(m,6H),7.69–7.79(m,6H),8.29(d,J=7.5Hz,1H),8.37(d,J=8.5Hz,1H),8.60(d,J=5.0Hz,1H),10.27(s,1H).

[0082] Synthesis of Pt2: To a reaction flask, L-Pt2 (500 mg, 0.53 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (194 mg, 0.56 mmol, 1.05 equiv), and sodium acetate (130 mg, 1.59 mmol, 3.0 equiv) were added, followed by diethylene glycol dimethyl ether (10 mL). The reaction was allowed to proceed at 120°C for 72 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 173 mg of a light yellow solid (33% yield). 1 H NMR (500MHz, CDCl3) δ1.20(s,9H),1.41(s,9H),6.29(d,J=8.5Hz,1H),6.35–7.19(m,11H),7.21–7.25(m,2H),7.31(d,J=8.5Hz,2H ),7.39–7.65(m,6H),7.80(d,J=8.5Hz,1H),7.89–7.92(m,2H),7.99(d,J=8.0Hz,1H),8.12(d,J=7.0Hz,1H),9.09(d,J=6.0Hz,1H).

[0083] Example 4: The synthetic route of Pt3 is as follows

[0084]

[0085] Synthesis of intermediate (M3-OH): 4-(tert-butyl)-2-bromopyridine (20.6 g, 46.7 mmol, 1.1 equivalents), 2-bromocarbazole (10.43 g, 42.4 mmol, 1.0 equivalents), cuprous iodide (807 mg, 4.24 mmol, 10 mol%), N-methylimidazole (696 mg, 8.48 mmol, 20 mol%), and lithium tert-butoxide (6.78 g, 84.8 mmol, 2.0 equivalents) were added to a reaction flask. Toluene (80 mL) was added. The reaction was allowed to stand at 120° C. for 48 hours, cooled to room temperature, and the organic phase was separated, concentrated, and subjected to silica gel column chromatography to afford 14.5 g of a white solid in a 90% yield. The product was not structurally characterized and was used directly in the next step.

[0086]

[0087] Synthesis of intermediate (A3): A1 (20 g, 82.9 mmol, 1.0 equivalent), A2 (24.7 g, 133 mmol, 1.6 equivalent), n-butyl lithium (40 mL, 99.48 mmol, 1.2 equivalent), N-methylimidazole (696 mg, 8.48 mmol, 20 mol%), and lithium tert-butoxide (6.78 g, 84.8 mmol, 2.0 equivalent) were added to a reaction flask. Tetrahydrofuran (200 mL) was added. The reaction was allowed to react at room temperature for 24 hours, cooled to room temperature, and the organic phase was separated, concentrated, and purified by silica gel column chromatography to obtain A3 as a white solid (13.4 g, 75% yield). The product was not structurally characterized and was used directly in the next step.

[0088] Synthesis of the intermediate (diPr-Cl-OMe): To a reaction flask, add A3 (7.81 g, 27.1 mmol, 1.2 equiv), A4 (5.0 g, 22.6 mmol, 1.0 equiv), 1,1-bis(diphenylphosphino)diphenylferric palladium chloride (330 mg, 0.45 mmol, 2 mol%), and sodium hydroxide (1.81 g, 45.2 mmol, 2.0 equiv). Dioxane (50 mL) and water (10 mL) were added. The reaction was terminated by heating at 100°C for 24 hours, then cooled to room temperature. The organic phase was separated, concentrated, and purified by silica gel column chromatography to afford 4.79 g of diPr-Cl-OMe as a white solid in a 70% yield. The product was used directly in the next step without structural characterization.

[0089] Synthesis of the intermediate (diPr-Cl-OH): DiPr-Cl-OMe (6.93 g, 22.9 mmol, 1.0 equiv) and boron tribromide (11.48 g, 45.8 mmol, 2.0 equiv) were added to a reaction flask. Dichloromethane (10 mL) was added and the reaction was allowed to proceed at room temperature for 8 hours to terminate the reaction. The mixture was cooled to room temperature, the organic phase was separated, concentrated, and purified by silica gel column chromatography to afford 4.5 g of diPr-Cl-OH as a white solid in an 81% yield. The product was used directly in the next step without structural characterization.

[0090] Synthesis of intermediate (M3-Cl): To a reaction flask were added diPr-Cl-OH (4.5 g, 15.6 mmol, 1.5 equiv), M3-Br (3.94 g, 10.4 mmol, 1.0 equiv), 2-pyridinecarboxylic acid (256 mg, 2.08 mmol, 20 mmol%), cuprous iodide (198 mg, 1.04 mmol, 10 mmol%), and potassium phosphate (4.42 g, 20.8 mmol, 2.0 equiv), followed by dimethyl sulfoxide (50 mL). The reaction was allowed to proceed at 110°C for 12 hours, cooled to room temperature, and the organic phase was separated, concentrated, and purified by silica gel column chromatography to afford 4.45 g of M3-Cl as a white solid in a 73% yield. The product was used directly in the next step without structural characterization.

[0091]

[0092] Synthesis of intermediate (LNH-Pt3): dPh-tBuNH2 (5.5 g, 1.4 mmol, 1.0 equiv) was added to a reaction flask, followed by M3-Cl (8.22 g, 14 mmol, 1.0 equiv), trisdibenzylideneacetone dipalladium (384 mg, 0.42 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (250 mg, 0.84 mmol, 6 mol%), and sodium tert-butoxide (2.7 g, 28 mmol, 2.0 equiv). Toluene (100 mL) was added. The reaction was stopped at 100°C for 12 hours, cooled to room temperature, and the organic phase was separated, concentrated, and subjected to silica gel column chromatography to give 9.24 g of a white solid in a 70% yield. The product was not structurally characterized and was used directly in the next step.

[0093] Synthesis of Ligand (L-Pt3): To a reaction flask, add LNH-Pt3 (13.6 g, 14.4 mmol, 1.0 equiv), followed by ammonium hexafluorophosphate (4.7 g, 28.8 mmol, 2.0 equiv), and triethyl orthoformate (50 mL). The reaction was incubated at 80°C for 10 hours, then cooled to room temperature. The organic phase was separated, concentrated, and purified by silica gel column chromatography to afford 8.42 g of a white solid (61% yield). 1 H NMR(500MHz,DMSO)δ0.87(d,J=6.9Hz,6H),1.06(d,J=6.9Hz,6H),1.28(s,9H),1.44(s,9H),2.39–2.45(m,2H) ,7.02(dd,J=2.5,1.5Hz,1H),7.04–7.07(m,2H),7.10–7.14(m,4H),7.18–7.23(m,8H),7.32–7.36(m,2H),7.4 2(t,J=2.0Hz,1H),7.43–7.46(m,2H),7.48–7.50(m,2H),7.53–7.57(m,1H),7.59–7.62(m,1H),7.69(d,J=2.5 Hz,1H),7.73–7.76(m,4H),8.25(d,J=7.5Hz,1H),8.34(d,J=8.5Hz,1H),8.55(d,J=5.5Hz,1H),10.28(s,1H).

[0094] Synthesis of Pt3: To a reaction flask, add L-Pt3 (5.0 g, 4.5 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (1.64 g, 4.72 mmol, 1.05 equiv), and sodium acetate (1.11 g, 13.5 mmol, 3.0 equiv), followed by diethylene glycol dimethyl ether (50 mL). The reaction was allowed to stand at 120°C for 72 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 3.61 g of a pale yellow solid of Pt3 (70% yield). The product was confirmed by NMR.

[0095] Example 5: The synthetic route of Pt4 is as follows

[0096]

[0097]

[0098] Synthesis of intermediate (LNH-Pt4): dPh-CN-NH2 (500 mg, 1.38 mmol, 1.2 equiv) was added to a reaction flask, followed by M1-Br (861 mg, 1.38 mmol, 1.0 equiv), trisdibenzylideneacetone dipalladium (37 mg, 0.04 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (33 mg, 0.08 mmol, 6 mol%), and sodium tert-butoxide (265 mg, 2.76 mmol, 2.0 equiv). Toluene (5 mL) was added. The reaction was allowed to stand at 110°C for 12 hours, cooled to room temperature, and the organic phase was separated, concentrated, and purified by silica gel column chromatography to give 726 mg of a white solid in a 65% yield. The product was not structurally characterized and was used directly in the next step.

[0099] Synthesis of Ligand (L-Pt4): To a reaction flask, add LNH-Pt4 (726 mg, 0.90 mmol, 1.0 equiv), followed by ammonium hexafluorophosphate (293 mg, 1.80 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). The reaction was incubated at 80°C for 11 hours, cooled to room temperature, and the organic phase was separated, concentrated, and purified by silica gel column chromatography to afford 342 mg of a white solid (56% yield). 1H NMR (500MHz, DMSO) δ1.28(s,9H),1.30(s,9H),6.85(t,J=2.0Hz,1H),6.93(t,J=2.0Hz,1H),7.14–7.19(m,11H),7.36(t,J=8.0Hz,1H),7.46–7.49( m,4H),7.54–7.58(m,3H),7.66–7.70(m,2H),7.75(d,J=9.0Hz,1H),8.27 (d,J=8.0Hz,1H),8.34–8.36(m,3H),8.58(d,J=6.0Hz,1H),10.31(s,1H).

[0100] Synthesis of Pt4: To a reaction flask, add L-Pt4 (150 mg, 0.16 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (59 mg, 0.17 mmol, 1.05 equiv), and sodium acetate (40 mg, 0.48 mmol, 3.0 equiv), followed by diethylene glycol dimethyl ether (10 mL). The reaction was allowed to proceed at 120°C for 72 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 96 mg of a light yellow solid (60% yield). 1 H NMR (500MHz, DMSO) δ1.34(s,9H),1.42(s,9H),5.99–6.83(m,6H),6.87–7.70(m,14H),7.80(d,J=8 .2Hz,1H),8.08(d,J=2.0Hz,1H),8.12–8.34(m,3H),8.40(d,J=8.0Hz,1H),8.80(d,J=6.0Hz,1H).

[0101] Example 6: The synthetic route of Pt5 is as follows

[0102]

[0103] Synthesis of intermediate (LNH-Pt5): dPh-tBuNH2 (5.0 g, 12.7 mmol, 1.2 equiv) was added to a reaction flask, followed by M2-Br (6.0 g, 12.7 mmol, 1.0 equiv), trisdibenzylideneacetone dipalladium (349 mg, 0.40 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (230 mg, 0.80 mmol, 6 mol%), and sodium tert-butoxide (2.44 mg, 25.4 mmol, 2.0 equiv). Toluene (5 mL) was added. The reaction was continued at 110°C for 11 h, and the reaction was stopped. The reaction was cooled to room temperature, the organic phase was separated, concentrated, and subjected to silica gel column chromatography to obtain 5.97 g of a white solid in a 60% yield. The product was not structurally characterized and was used directly in the next step.

[0104] Synthesis of ligand (L-Pt5): LNH-Pt5 (7.84 g, 10.0 mmol, 1.0 equivalent) was added to the reaction flask, followed by the addition of ammonium hexafluorophosphate (3.26 mg, 20.0 mmol, 2.0 equivalent) and triethyl orthoformate (20 mL). The reaction was continued at 75°C for 5 hours to stop the reaction. The mixture was cooled to room temperature, and the organic phase was separated, concentrated, and purified by silica gel column chromatography to give 3.08 mg of a white solid in a yield of 52%. 1 H NMR (500MHz, DMSO) δ1.30(s,9H),1.45(s,9H),6.97(t,J=2.0Hz,1H),7.10–7.19(m,13H),7.41(dd,J=8.5,3.5Hz,1H),7.46–7. 51(m,3H),7.52–7.59(m,2H),7.67–7.71(m,2H),7.72–7.74(m,3H),8.37(d,J=8.5Hz,1H),8.59(d,J=4.5Hz,1H),10.26(s,1H).

[0105] Synthesis of Pt5: To a reaction flask, L-Pt5 (5.64 g, 6.0 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (1.96 g, 6.3 mmol, 1.05 equiv), and sodium acetate (1.48 mg, 18 mmol, 3.0 equiv) were added, followed by diethylene glycol dimethyl ether (10 mL). The reaction was allowed to proceed at 120°C for 72 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 1.30 g of a light yellow solid (34% yield). 1 H NMR(500MHz, CDCl3)δ1.20(s,9H),1.41(s,9H),6.19–7.18(m,15H),7.22–7.24(m,2H),7.31(d,J=8.5Hz,1H),7 .48(d,J=8.5Hz,2H),7.80(d,J=8.0Hz,1H),7.92(d,J=2.0Hz,1H),7.99(d,J=8.5Hz,1H),9.09(d,J=6.0Hz,1H).

[0106] Example 7: Synthesis of Pt6

[0107] Pt6 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (562 mg) with a yield of 75%. Molecular weight [M+H] + :994.1.

[0108] Example 8: Synthesis of Pt7

[0109] Pt7 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (624 mg) with a yield of 58%. Molecular weight [M+H] + :1212.5.

[0110] Example 9: Synthesis of Pt8

[0111] Pt8 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (661 mg) with a yield of 72%. Molecular weight [M+H] + :1216.5.

[0112] Example 10: Synthesis of Pt9

[0113] Pt9 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (484 mg) with a yield of 66%. Molecular weight [M+H] + :1218.5.

[0114] Example 11: Synthesis of Pt10

[0115] Pt10 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (455 mg) with a yield of 69%. Molecular weight [M+H] + :1219.5.

[0116] Example 12: Synthesis of Pt11

[0117] Pt11 was synthesized using the same synthesis steps and reaction conditions as Pt1. 410 mg of the target product was obtained as a yellow solid with a yield of 67%. Molecular weight [M+H] + :1045.2.

[0118] Example 13: Synthesis of Pt12

[0119] Pt12 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (369 mg) with a yield of 58%. Molecular weight [M+H] + :989.1.

[0120] Example 14: Synthesis of Pt13

[0121] Pt13 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (492 mg) with a yield of 82%. Molecular weight [M+H] + :1149.4.

[0122] Example 15: Synthesis of Pt14

[0123] Pt14 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (471 mg) with a yield of 80%. Molecular weight [M+H] + :1006.1.

[0124] Example 16: Synthesis of Pt15

[0125] Pt15 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (596 mg) with a yield of 74%. Molecular weight [M+H] + :993.1.

[0126] Example 17: Synthesis of Pt16

[0127] Pt16 was synthesized using the same synthesis steps and reaction conditions as Pt1. The target product was obtained as a yellow solid (615 mg) with a yield of 68%. Molecular weight [M+H] + :995.1.

[0128] Example 18: Synthesis of Pt17

[0129] Pt17 was synthesized using the same synthesis steps and reaction conditions as Pt1. 582 mg of the target product was obtained as a yellow solid with a yield of 66%. Molecular weight [M+H] + :1213.5.

[0130] Example 19: Synthesis of Pt18

[0131] Pt18 was synthesized using the same synthesis steps and reaction conditions as Pt1. 471 mg of the target product was obtained as a yellow solid with a yield of 76%. Molecular weight [M+H] + :1217.6.

[0132] Example 20: Synthesis of Pt19

[0133] Pt19 was synthesized using the same synthesis steps and reaction conditions as Pt1. 596 mg of the target product was obtained as a yellow solid with a yield of 78%. Molecular weight [M+H] + :1218.6.

[0134] Example 21: Synthesis of Pt20

[0135] Pt20 was synthesized using the same synthesis steps and reaction conditions as compound Pt1. 597 mg of the target product was obtained as a yellow solid with a yield of 72%. Molecular weight [M+H] + :1275.7.

[0136] Example 22: Synthesis of Pt21

[0137] Pt21 was synthesized using the same synthesis steps and reaction conditions as Pt1. 576 mg of the target product was obtained as a yellow solid with a yield of 74%. Molecular weight [M+H] + :1010.1.

[0138] Example 23: Synthesis of Pt22

[0139] Pt22 was synthesized using the same synthesis steps and reaction conditions as Pt1. The target product was obtained as a yellow solid (615 mg) with a yield of 68%. Molecular weight [M+H] + :1228.6.

[0140] Example 24: Synthesis of Pt23

[0141] Pt23 was synthesized using the same synthesis steps and reaction conditions as Pt1. 592 mg of the target product was obtained as a yellow solid with a yield of 66%. Molecular weight [M+H] + :1232.6.

[0142] Example 25: Synthesis of Pt24

[0143] Pt24 was synthesized using the same synthesis steps and reaction conditions as compound Pt1. 571 mg of the target product was obtained as a yellow solid with a yield of 76%. Molecular weight [M+H] + :1234.6.

[0144] Example 26: Synthesis of Pt25

[0145] Pt25 was synthesized using the same synthesis steps and reaction conditions as compound Pt1. 596 mg of the target product was obtained as a yellow solid with a yield of 78%. Molecular weight [M+H] + :1235.6.

[0146] Example 27: Synthesis of Pt26

[0147] Pt26 was synthesized using the same synthesis steps and reaction conditions as Pt1. 597 mg of the target product was obtained as a yellow solid with a yield of 72%. Molecular weight [M+H] + :1003.1.

[0148] Example 28: Synthesis of Pt27

[0149] Pt27 was synthesized using the same synthesis steps and reaction conditions as Pt1. 696 mg of the target product was obtained as a yellow solid with a yield of 74%. Molecular weight [M+H] + :1005.1.

[0150] Example 29: Synthesis of Pt28

[0151] Pt28 was synthesized using the same synthesis steps and reaction conditions as compound Pt1. 615 mg of the target product was obtained as a yellow solid with a yield of 68%. Molecular weight [M+H] + :1061.3.

[0152] Example 30: Synthesis of Pt34

[0153] Pt34 was synthesized using the same synthesis steps and reaction conditions as Pt1. 582 mg of the target product was obtained as a yellow solid with a yield of 66%. Molecular weight [M+H] + :1025.4.

[0154] Example 31: Synthesis of Pt39

[0155] Pt39 was synthesized using the same synthesis steps and reaction conditions as compound Pt1. 471 mg of the target product was obtained as a yellow solid with a yield of 76%. Molecular weight [M+H] + :1235.6.

[0156] Photophysical properties:

[0157] Table 1. Photophysical properties of some metal complexes in dichloromethane solution

[0158] Complex Maximum emission wavelength Half-peak width Pt1 461nm 25nm Pt7 455.6nm 20nm Pt13 461.6nm 22.8nm Pt19 479.6nm 34.2nm Pt23 456nm 21.2nm

[0159] As can be seen from Table 1, the metal complexes provided by the present invention are all in the blue and deep blue light emitting regions and have a narrow half-peak width, and are good blue light phosphorescent materials.

[0160] Fabrication of OLED devices:

[0161] As a reference preparation method for a device embodiment, the present invention deposits a p-type dopant material onto the surface of an ITO glass or anode with a luminescent area of 2mm×2mm, or co-evaporates the p-type dopant material with a hole injection material at a concentration of 1% to 50% to form a 5-100nm hole injection layer (HIL) and a 5-200nm hole transport layer (HTL). Subsequently, a 10-100nm light-emitting layer (EML) (which may contain the compound described herein) is formed on the hole transport layer, followed by a 20-200nm electron transport layer (ETL) and a 50-200nm 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 cathode to produce an OLED device. The OLED device is then tested using standard methods. Unless otherwise specified, the device materials involved in this invention can be obtained by known synthesis methods.

[0162] In a preferred specific embodiment, the structure of device example 1 provided by the present invention is: ITO / P-4 (10 nm) / NPD (60 nm) / HTH-85 (5 nm) / platinum (II) complex: HTH-85:ETH-45 (25 nm) (Pt1:HTH-85:ETH-45 mass ratio is 10:60:30) / ETH-5 (5 nm) / ET-14 (40 nm) / LiQ (1 nm) / Al (100 nm).

[0163] Device Examples 2 to 30 and Comparative Example 1 were prepared using structures similar to those of Device Example 1, with the only difference being that Pt1 in Device Example 1 was replaced with Pt2, Pt3, Pt4, Pt5, Pt-6, Pt7, Pt8, Pt9, Pt10, Pt11, Pt12, Pt13, Pt14, Pt15, Pt16, Pt17, Pt18, Pt19, Pt20, Pt21, Pt22, Pt23, Pt24, Pt25, Pt26, Pt27, Pt28, Pt34, Pt39, and R1, respectively. The luminescence properties of the comparative examples and device examples prepared above were tested using standard methods, and the data are shown in Table 2. The device structures involved are as follows: where P-4 is HATCN and ET-14 is BPyTP.

[0164]

[0165]

[0166] Table 2. Device luminescence characteristics data table

[0167]

[0168]

[0169] As can be seen from Table 2, compared with Comparative Example 1, Device Examples 1 to 30 prepared in the present application all exhibited good device performance in terms of driving voltage, current efficiency, and device life. The improvement in the performance of each device example is based on the fact that the specific compound material of the present invention has better electron transport capability. It can be seen that when it is used as a light-emitting layer material to prepare an electronic device, it has higher current efficiency and device life while reducing the driving voltage. In addition, the devices prepared by the present invention are all deep blue light devices, and the CIEy values are all less than 0.20. This shows that the compound provided by the present invention has certain commercial application value.

[0170] In a preferred specific embodiment, the structure of device example 31 provided by the present invention is: ITO / P-4 (10nm) / NPD (60nm) / HTH-85 (5nm) / platinum (II) complex: boron-containing compound: HTH-85:ETH-45 (25nm) (Pt1:BN1-8:HTH-85:ETH-45 mass ratio is 10:1:59:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0171] Device Examples 32-38 were prepared using structures similar to those of Device Example 31, differing only in that the platinum (II) complex and the boron-containing compound in Device Example 23 were replaced with the compounds listed in Table 3. The device structures and luminescence characteristics are shown in Table 3.

[0172] Table 3. Device structure and luminescence characteristics data

[0173]

[0174] As shown in Table 3, the compounds of the present invention, when used as sensitizing materials in devices along with boron-containing compounds as luminescent materials, significantly improved the performance of each device. This further demonstrates that the compounds provided by the present invention have considerable commercial application value. Furthermore, the addition of boron-containing compounds to sensitize the device structure can further reduce the CIEy value, thereby further improving the color purity of the device's luminescent light.

[0175] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. A tetradentate ring metal platinum (II) complex, characterized in that The tetradentate ring metal platinum (II) complex is selected from the chemical structure shown below, wherein "D" represents deuterium and "Ph" represents a phenyl group:

2. Use of the tetradentate ring metal platinum (II) complex according to claim 1 in the preparation of electronic devices.

3. The use according to claim 2, characterized in that The electronic devices include organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quenching devices, light emitting electrochemical cells and organic laser diodes.

4. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a cathode, an anode, and an organic functional layer interposed therebetween; the organic functional layer comprises a light-emitting layer, the light-emitting layer comprises a tetradentate ring metal platinum (II) complex, and the light-emitting layer further comprises a fluorescent dopant material; the fluorescent dopant material is selected from any one or more compounds represented by formula (BN1) to formula (BN3): Wherein, X is O, S, Se; X 1 、X 2 、X 3 Each is independently represented by N, X 4 Indicated as O or N; R b -R e Each independently represents mono-, di-, tri-, tetra- or unsubstituted; R b -R e Each independently selected from the group consisting of hydrogen, deuterium, methyl, tert-butyl, and phenyl; R4-R6, R9 are each independently selected from a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted carbazolyl group; the substitution may be multiple substitutions, and when containing a substituent, the substituent is selected from deuterium, a C1-C30 alkyl group, a C6-C30 aryl group, and the R7-R8, R 10 -R 11 Each independently represents the group consisting of hydrogen, deuterium, and C6–C30 aryl; The tetradentate ring metal platinum (II) complex is selected from the chemical structure shown below, wherein "D" represents deuterium and "Ph" represents a phenyl group:

5. The organic electroluminescent device according to claim 4, characterized in that: The R4-R6 and R9 are each independently selected from substituted or unsubstituted diphenylamino groups, substituted or unsubstituted carbazolyl groups; the substitution may be multiple substitutions, and when containing substituents, the substituents are selected from deuterium, methyl, ethyl, propyl, tert-butyl, and phenyl; the R7-R8, R 10 -R 11 Each is independently selected from the group consisting of hydrogen and phenyl.

6. The organic electroluminescent device according to claim 4, characterized in that: The fluorescent doping material is selected from any one of the chemical structures shown below, wherein Ph represents a phenyl group, and D4 and D5 respectively mean substitution by 4 and 5 deuterium atoms:

7. An organic optoelectronic device, characterized in that: The organic photoelectric device includes: a substrate layer; a first electrode, the first electrode being on the substrate; an organic light-emitting functional layer, the organic light-emitting functional layer being on the first electrode; and a second electrode, the second electrode being on the organic light-emitting functional layer. The organic light-emitting functional layer includes a tetradentate metal platinum (II) complex, and the organic light-emitting functional layer further includes a fluorescent dopant material. The tetradentate metal platinum (II) complex is selected from the following chemical structure, wherein "D" represents deuterium and "Ph" represents a phenyl group: The fluorescent doping material is selected from any one or more compounds represented by formula (BN1) to formula (BN3): Wherein, X is O, S, Se; X 1 、X 2 、X 3 Each is independently represented by N, X 4 Indicated as O or N; R b -R e Each independently represents mono-, di-, tri-, tetra- or unsubstituted; R b -R e Each independently selected from the group consisting of hydrogen, deuterium, methyl, tert-butyl, and phenyl; R4-R6, R9 are each independently selected from a substituted or unsubstituted diphenylamino group, a substituted or unsubstituted carbazolyl group; the substitution may be multiple substitutions, and when containing a substituent, the substituent is selected from deuterium, a C1-C30 alkyl group, a C6-C30 aryl group; R7-R8, R 10 -R 11 Each independently represents the group consisting of hydrogen, deuterium, and C6-C30 aryl groups.

8. A composition, characterized in that The composition comprises the tetradentate platinum (II) complex according to claim 1.

9. A preparation, characterized in that The preparation contains the tetradentate platinum (II) complex according to claim 1.

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

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