Ring-fused carbazole tetradentate platinum (II) complex and use thereof

Abstract

The present invention belongs to the field of organic electroluminescence, and specifically relates to a ring-fused carbazole tetradentate platinum (II) complex and the use thereof. In the present invention, a five-membered heterocyclic system such as benzofuran or benzothiophene is introduced to position 5,6- of carbazole to obtain a tetradentate platinum (II) complex phosphorescent material. The composition proportion of a locally-excited state (LE) in a triplet state excited by the ring-fused tetradentate platinum (II) complex is increased, thereby enabling same to have a low shoulder peak, and improving the color purity of the molecular luminescence of the material. Therefore, the lifetime of a device is prolonged. The material provided by the present invention has a very good chemical stability and thermal stability, which facilitates the preparation of an evaporation-type OLED device. Both the current efficiency and the lifetime of an organic electroluminescence device fabricated by using the compound of the present invention as a luminous layer are obviously improved, and the lighting voltage thereof is significantly reduced. After being combined with a fluorescent doping material, the transport of holes and electrons can be balanced; therefore, the energy transfer between a host and a guest is more efficient, and the photochromic purity of a device can be improved.

Description

A cyclic carbazole tetradentate metal platinum (II) complex and its application Technical Field

[0001] The invention belongs to the field of organic electroluminescence, and particularly relates to a cyclic carbazole tetradentate metal platinum (II) complex 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 with a host material. The host material generally has a higher energy system than the guest luminescent material, and 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 material. However, due to the easy hole transport properties of mCBP and the poor hole transport properties of 2,6-mCPy, charge imbalance in the luminescent layer results in reduced device current efficiency. Furthermore, the currently used heavy metal phosphorescent organic complex molecules are cyclometallated iridium (III) complex molecules, and their quantity 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 high utilization rate of H2O increases the preparation cost of iridium (III) complex phosphorescent materials. In contrast, the preparation of platinum (II) complex phosphorescent materials only requires the final step of metallization of the ligand to design the reaction of the platinum salt. The high utilization rate 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 some technical difficulties. How to reduce the height of the shoulder peak in the emission spectrum to improve the color purity of the luminescence of the material molecules? This problem is particularly important for blue and deep blue light-emitting materials, as they have a significant impact on the efficiency and energy utilization of commercial top-emitting devices. Therefore, the development of new phosphorescent metal platinum (II) complexes is urgently needed.

[0004] Summary of the Invention

[0005] In light of this, the present invention aims to provide a tetradentate platinum(II) complex containing a cyclic carbazole and its applications. By introducing a five-membered heterocyclic ring system, such as benzofuran or benzothiophene, at the 5,6-positions of the carbazole, the present invention can increase the proportion of localized states (LEs) in the excited triplet state of the tetradentate platinum(II) complex, resulting in a low shoulder peak and improved luminescent color purity. The provided complex, when used as a light-emitting layer in an organic electroluminescent device, can impart excellent device performance. This can improve the current efficiency and device life of the organic electroluminescent device, while also reducing the device's operating voltage.

[0006] In order to achieve the above technical objectives, the technical solutions of the present invention are as follows:

[0007] The present invention provides a tetradentate metal platinum (II) complex of a cyclic carbazole, the structure of which is shown in formula (I):

[0008] In formula (I), X is selected from O or S; R 1 -R 9 Each independently represents a single substitution to the maximum number of substitutions, or no substitution; R 1 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, halogen, CN, C1-C30 alkyl, C1-C30 haloalkyl, C1-C30 deuterated alkyl, C6-C60 aryl, C6-C60 arylsilane, and combinations thereof.

[0009] Furthermore, R 1 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, CF3, 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, isononyl, sec-nonyl, tert-nonyl, phenyl, biphenyl, triphenylsilane, and combinations thereof.

[0010] Furthermore, R 3 、R 4 、R 9 Each is independently selected from the group consisting of hydrogen, deuterium, F, CN, methyl, tert-butyl, phenyl, and combinations thereof.

[0011] Preferably, the tetradentate metal platinum (II) complex of cyclic carbazole is selected from any one of the chemical structures shown below: wherein "D" represents deuterium:

[0012] Furthermore, the present invention also provides a tetradentate metal platinum (II) complex of cyclic carbazole having a structure as shown in formula (I) in an electronic device.

[0013] application.

[0014] 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).

[0015] In another aspect, the present invention further provides an organic electroluminescent device comprising the cyclic carbazole tetradentate metal platinum (II) complex having the structure shown in formula (I) as described above.

[0016] Furthermore, the organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises the above-mentioned cyclic carbazole tetradentate metal platinum (II) complex having a structure represented by formula (I).

[0017] Preferably, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the cyclic carbazole tetradentate metal platinum (II) complex having the structure shown in formula (I) as described above.

[0018] Furthermore, the light-emitting layer further comprises a fluorescent doping material; the fluorescent doping material is preferably a boron-containing organic molecular light-emitting material.

[0019] 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 metal platinum (II) complex of a cyclic carbazole having a structure represented by formula (I). For example, the platinum (II) complex can be included in the organic light-emitting functional layer as a luminescent material.

[0020] Furthermore, the organic light-emitting functional layer further comprises any one or more fluorescent doping materials, and the fluorescent doping material is preferably a boron-containing organic molecular light-emitting material, preferably a phosphorescence-sensitized boron-containing compound.

[0021] In the present invention, the organic photoelectric device can be prepared by depositing metal or conductive oxides and their alloys on a substrate using methods such as sputtering, electron beam evaporation, and vacuum evaporation to form an anode; depositing a hole injection layer, a hole transport layer, a light-emitting layer, an air barrier layer, and an electron transport layer on the surface of the prepared anode in sequence, and then depositing a cathode. In addition to the above methods, an organic electroluminescent device is prepared by depositing a cathode, an organic layer, and an anode on a substrate in sequence. The organic layer can also include a multilayer structure such as a hole injection layer, a hole transport layer, a light-emitting layer, a hole barrier layer, and an electron transport layer. In the present invention, the organic layer is prepared using polymer materials according to solvent engineering (spin-coating, tape-casting, doctor-blading, screen-printing, inkjet printing, or thermal-imaging, etc.) instead of the evaporation method, which can reduce the number of device layers.

[0022] The present invention also provides a composition comprising a tetradentate platinum(II) complex of a cyclic carbazole having a structure represented by formula (I). Preferably, the composition further comprises a fluorescent dopant material, wherein the fluorescent dopant material is preferably a boron-containing organic molecular luminescent material, preferably a phosphorescence-sensitized boron-containing compound.

[0023] The present invention also provides a preparation comprising the tetradentate metal platinum (II) complex of cyclic carbazole having the structure shown in formula (I) or the composition as described above and at least one solvent.

[0024] The solvent is not particularly limited and may be used, for example, unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, 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.

[0025] The present invention also provides a display or lighting device, which comprises one or more of the organic photoelectric devices described above.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The present invention obtains a tetradentate metal platinum (II) complex phosphorescent material by introducing a five-membered heterocyclic ring system such as benzofuran or benzothiophene at the 5,6-position of carbazole. The component ratio of the localized state (LE) in the excited triplet state of the tetradentate platinum (II) complex is increased, resulting in a low shoulder peak, thereby improving the luminescent color purity of the material molecule. This in turn improves the device lifespan. The materials provided by the present invention all have excellent chemical and thermal stability and are easy to prepare vapor-deposited OLED devices. Organic electroluminescent devices made using the compounds of the present invention as the light-emitting layer have significantly improved current efficiency and lifespan, and significantly reduced the lighting voltage. When combined with a fluorescent doping material (boron-containing compound), the transmission of holes and electrons can be balanced, making the energy transfer between the host and the guest more efficient and improving the light color purity of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG1 is a room temperature emission spectrum of R1 and PtO2 in dichloromethane solution;

[0029] FIG2 is a room temperature emission spectrum of R1 and PtO6 in dichloromethane solution;

[0030] FIG3 is a room temperature emission spectrum of R1 and PtS1 in dichloromethane solution;

[0031] FIG4 is a room temperature emission spectrum of R1 and PtS2 in dichloromethane solution;

[0032] FIG5 is a room temperature emission spectrum of R1 and PtS6 in dichloromethane solution;

[0033] FIG6 is a room temperature emission spectrum of R1 and PtO37 in dichloromethane solution;

[0034] FIG7 is a room temperature emission spectrum of R1 and PtO38 in dichloromethane solution;

[0035] FIG8 is a room temperature emission spectrum of R1 and PtO107 in dichloromethane solution;

[0036] FIG9 is a room temperature emission spectrum of R1 and PtO33 in dichloromethane solution;

[0037] Figure 10 is a room temperature emission spectrum of R1 and PtO34 in dichloromethane solution;

[0038] FIG11 is a room temperature emission spectrum of R1 and PtO5 in dichloromethane solution;

[0039] FIG12 is a room temperature emission spectrum of R1 and PtS5 in dichloromethane solution;

[0040] FIG13 is a room temperature emission spectrum of R1 and PtO109 in dichloromethane solution. DETAILED DESCRIPTION

[0041] 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.

[0042] 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, 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 otherwise, a single substituent can further optionally be substituted (i.e., further substituted or unsubstituted).

[0043] In defining various terms, “R 1 ”-“R 9 " are used as general symbols in the present invention to represent various specific substituents. These symbols can be any substituents, not limited to those disclosed in the present invention, and when they are limited to certain substituents in one case, they can be limited to some other substituents in other cases. The "R" used in the present invention 1 ”, “R 2 ”…“R n ”(wherein n is an integer) may independently have one or more of the groups listed above. For example, if R 1 If it 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, etc. Depending on the groups selected, the first group may be incorporated within the second group, or alternatively, the first group may be pendant, ie, attached to the second group.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] It should be noted that the above general description and the following detailed description are only exemplary and explanatory and are not limiting. The present application can be more easily understood by referring to the following specific embodiments and the examples contained therein.

[0049] 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.

[0050] 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.

[0051] Synthesis Example

[0052] 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 occur. Unless otherwise noted, all weights are weighed separately, temperatures are in degrees Celsius or at room temperature, and pressures are near atmospheric pressure.

[0053] 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.

[0054] 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. 1 When 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. 13In 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 6210 TOF LC / MS mass spectrometer; HRMS spectra were measured on an Agilent 6210 TOF 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.

[0055] Synthesis route

[0056] The synthetic route of the intermediate dPh-tBuNH2 is as follows

[0057] Synthesis of the intermediate dBr-tBuNH2: To a reaction flask, add p-tert-butylaniline (15.0 g, 100 mmol, 1.0 equivalent) and dissolve in dichloromethane (150 mL). Then, add N-bromosuccinimide (37.7 g, 210 mmol, 2.1 equivalents) and allow to react at room temperature for 48 hours. The reaction is then concentrated and purified by silica gel column chromatography to yield 25.6 g of a red liquid (84% yield). This was used directly in subsequent reactions.

[0058] 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 reaction was then concentrated and purified by silica gel column chromatography to give 5.08 g of a yellow solid in a 73% yield. This was used directly in subsequent reactions.

[0059] Synthesis of intermediate dBr-tBu2NH2: Add dBr-tBuNO2 (4.8 g, 11.2 mmol, 1.0 equivalent), stannous chloride (10.1 g, 44.8 mmol, 4.0 equivalent) to the reaction flask, add ethyl acetate (50 mL) and ethanol (50 mL). ℃ The oil was reacted for 24 hours, then the reaction was stopped, cooled to room temperature, concentrated, and subjected to silica gel column chromatography to obtain 3.43 g of a white solid (yield 82%), which was used directly in the subsequent reaction.

[0060] 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), tetrakis(triphenylphosphine)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 stirred at 90°C for 24 hours, then cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 2.66 g of a white solid (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).

[0061] The synthetic route of the intermediate dPh-5tBuNH2 is as follows

[0062] Synthesis of the intermediate dPh-5tBuNH2: To a reaction flask were added dBr-tBu2NH2 (1.0 g, 2.5 mmol, 1.0 equiv), 3,5-di-tert-butylphenylboronic acid pinesyl ester (2.37 g, 7.5 mmol, 3.0 equiv), tetrakis(triphenylphosphine)palladium (87 mg, 0.075 mmol, 3 mol%), potassium carbonate (691 mg, 5 mmol, 2.0 equiv), dioxane (40 mL), and water (10 mL). The reaction was stirred at 90°C for 24 hours, then stopped. The mixture was cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 1.54 g of a white solid in a 92% yield. 1 H NMR (500MHz, DMSO) δ1.17(s,36H),1.37(s,9H),4.35(s,2H),5.50(s,1H),6.03(dd,J=8.0,1.5Hz,1H),6.14(td,J=7.5,1.5 Hz,1H),6.26(td,J=7.0,1.0Hz,1H),6.34(dd,J=7.5,1.5Hz,1H),7.19(t,J=1.5Hz,2H),7.22(d,J=2.0Hz,4H),7.29(s,2H).

[0063] The synthetic route of the intermediate dPh-NH2 is as follows

[0064] Synthesis of the intermediate dBr-NO2: To a reaction flask, add dBr-NH2 (20 g, 80 mmol, 1.0 equivalent), dissolve in N-methylpyrrolidone (150 mL), sodium hydride (9.6 g, 240 mmol, 3.0 equivalent), and o-fluoronitrobenzene (16.9 g, 120 mmol, 1.5 equivalent). The reaction was allowed to react at room temperature for 24 hours. The mixture was concentrated and purified by silica gel column chromatography to afford 21.6 g of a yellow solid in a 73% yield. This was used directly in subsequent reactions.

[0065] Synthesis of intermediate dBr-2NH2: Add dBr-NO2 (21.6 g, 58 mmol, 1.0 equivalent), stannous chloride (52.4 g, 232 mmol, 4.0 equivalent), ethyl acetate (150 mL) and ethanol (150 mL) to the reaction flask. ℃ The reaction was stopped after 24 hours, concentrated, and purified by silica gel column chromatography to obtain 18.2 g of a white solid (91% yield), which was used directly in subsequent reactions.

[0066] Synthesis of intermediate dPh-NH2: To a reaction flask, add dBr-2NH2 (12 g, 35 mmol, 1.0 equiv), phenylboronic acid (12.7 g, 105 mmol, 3.0 equiv), tetrakis(triphenylphosphine)palladium (809 mg, 0.75 mmol, 0.02 equiv), sodium carbonate (12.1 g, 87.5 mmol, 2.5 equiv), dioxane (120 mL), and water (30 mL). Incubate at 90°C for 24 hours to terminate the reaction. Concentrate and purify by silica gel column chromatography to obtain 10.1 g of a white solid (86% yield). Use directly in subsequent reactions.

[0067] The synthetic route of the intermediate dPh-4tBuNH2 is as follows

[0068] Synthesis of the intermediate dPh-4tBuNH2: To a reaction flask, add dBr-2NH2 (9.92 g, 29 mmol, 1.0 equiv), 3,5-di-tert-butylphenylboronic acid pinesyl ester (27.5 g, 86.9 mmol, 3.0 equiv), tetrakis(triphenylphosphine)palladium (1.0 g, 0.87 mmol, 3 mol%), potassium carbonate (10.0 g, 72.5 mmol, 2.5 equiv), dioxane (40 mL), and water (10 mL). After incubation at 90°C for 24 hours, the reaction was stopped, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 14.8 g of a white solid (91% yield). This was used directly in subsequent reactions.

[0069] Example 1: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtO6 is as follows:

[0070] Synthesis of intermediate 4O-NO2: To a reaction flask were added A-4O-B(OH)2 (5.8 g, 25.4 mmol, 1.2 eq), B (4.5 g, 21.2 mmol, 1.0 eq), tetrakis(triphenylphosphine)palladium (734 g, 0.64 mmol, 3 mol%), potassium carbonate (5.86 g, 85.2 mmol, 2.0 eq), dioxane (40 mL), and water (10 mL). The reaction was terminated by incubation at 90°C for 24 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 4.5 g of a yellow solid in a 68% yield. 1 H NMR(500MHz,DMSO)δ3.95(s,3H),7.42(td,J=7.5,1.0Hz,1H),7.47(dd,J=8.5,2.5Hz,1H),7.49–7.54(m ,3H),7.59(d,J=8.5Hz,1H),7.67(d,J=8.65Hz,1H),7.71(d,J=3.0Hz,1H),8.18(dd,J=6.5,2.0Hz,2H).

[0071] Synthesis of intermediate 4O-NH: To a reaction flask, add 4O-NO (4.5 g, 14.1 mmol, 1.0 equiv) and triphenylphosphine (11.1 g, 42.3 mmol, 3.0 equiv), followed by o-dichlorobenzene (60 mL). The reaction was incubated at 110°C for 24 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 2.61 g of a brown solid (65% yield). This was used directly in subsequent reactions.

[0072] Synthesis of intermediate 4O-OMe: To a reaction flask, add 4O-NH (2.4 g, 8 mmol, 1.0 equiv), 4-(tert-butyl)-2-chloropyridine (1.63 g, 9.6 mmol, 1.2 equiv), tris(dibenzylideneacetone)dipalladium (220 mg, 0.24 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (143 mg, 0.48 mmol, 6 mol%), and sodium tert-butoxide (1.54 g, 16 mmol, 2.0 equiv). Toluene (50 mL) was added. The reaction was allowed to stand at 110°C for 48 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 1.75 g of a brown solid (74% yield). This was used directly in subsequent reactions.

[0073] Synthesis of intermediate 4O-OH: To a reaction flask, add 4O-OMe (1.05 g, 2.5 mmol, 1.0 equiv), pyridine hydrochloride (4.5 g, 25 mmol, 10.0 equiv), and 1,3-dimethyl-2-imidazolidinone (60 mL). Incubate at 180°C for 48 hours, cool to room temperature, concentrate, and purify by silica gel column chromatography to afford 862 g of a brown solid (85% yield). Use directly in subsequent reactions.

[0074] Synthesis of intermediate tBu-4O-Cl: To a reaction flask were added 4O-OH (500 mg, 1.23 mmol, 1.0 equiv), 3-chloro-5-bromo-tert-butylbenzene (455 mg, 1.84 mmol, 1.5 equiv), 2-picolinic acid (30 mg, 0.25 mmol, 20 mmol%), cuprous iodide (23 mg, 0.125 mmol, 10 mmol%), potassium phosphate (522 mg, 2.46 mmol, 2.0 equiv), and dimethyl sulfoxide (10 mL). The reaction was terminated at 110°C for 12 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 540 mg of a white solid (70% yield). 1 H NMR (500MHz, DMSO) δ1.24(s,9H),1.31(s,9H),6.96(t,J=2.0Hz,1H),7.13(t,J=1.5 Hz,1H),7.21(t,J=2.0Hz,1H),7.24(dd,J=8.5,2.0Hz,1H),7.32(d,J=2.0Hz,1H),7. 44–7.47(m,1H),7.51–7.54(m,2H),7.71(d,J=2.0Hz,1H),7.78(d,J=8.5Hz,1H),7. 87(d,J=8.0Hz,1H),8.16–8.19(m,2H),8.44(d,J=8.5Hz,1H),8.62(d,J=5.5Hz,1H).

[0075] Synthesis of intermediate LNH-PtO6: To a reaction flask, add dPh-tBuNH2 (409 mg, 1.04 mmol, 1.2 eq), tBu-4O-Cl (500 mg, 0.87 mmol, 1.0 eq), tris(dibenzylideneacetone)dipalladium (24 mg, 0.03 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (16 mg, 0.06 mmol, 6 mol%), and sodium tert-butoxide (167 mg, 1.74 mmol, 2.0 eq). Toluene (5 mL) was added. The reaction was terminated by reacting at 85°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 460 mg of a white solid in a 57% yield. This was used directly in subsequent reactions.

[0076] Synthesis of the ligand L-PtO6: To a reaction flask, add LNH-PtO6 (370 mg, 0.4 mmol, 1.0 equiv), followed by ammonium hexafluorophosphate (130 mg, 0.8 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). The reaction was incubated at 80°C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 287 mg of a white solid (66% yield). 1 H NMR (500MHz, DMSO) δ1.30 (s, 9H), 1.31 (s, 9H), 1.43 (s, 9H), 6.88 (t, J = 2.5Hz, 1H), 6. 97(t,J=2.0Hz,1H),7.11–7.17(m,10H),7.33(dd,J=8.5,2.0Hz,1H),7.45–7.59(m,8 H),7.70–7.72(m,3H),7.78(d,J=1.5Hz,1H),7.80(d,J=9.0Hz,1H),7.87(d,J=7.5Hz ,1H),8.19–8.22(m,2H),8.52(d,J=8.0Hz,1H),8.65(d,J=5.0Hz,1H),10.26(s,1H).

[0077] Synthesis of PtO6: To a reaction flask, add L-PtO6 (220 mg, 0.2 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (73 mg, 0.21 mmol, 1.05 equiv), and sodium acetate (50 mg, 0.57 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 178 mg of a light yellow solid (78% yield). 1H NMR (400MHz, DMSO-d6) δ1.23 (s, 9H), 1.43 (s, 18H), 6.64 (dd, J = 6.4, 1.6Hz, 2H) ,6.95–7.05(m,5H),7.16(t,J=8.0Hz,2H),7.28–7.37(m,5H),7.46–7.60(m,6H) ,7.77(d,J=9.2Hz,1H),7.91(d,J=8.0Hz,1H),8.04(d,J=8.0Hz,2H),8.13(t,J= 7.2Hz, 2H), 8.27 (d, J = 7.2Hz, 1H), 8.35 (d, J = 8.4Hz, 1H), 8.95 (d, J = 6.4Hz, 1H).

[0078] Example 2: The synthesis route of the tetradentate platinum (II) complex phosphorescent material PtO2 is as follows:

[0079] Synthesis of intermediate LNH-PtO2: To a reaction flask, add dPh-NH2 (200 mg, 0.6 mmol, 1.0 equiv), followed by tBu-4O-Cl (361 mg, 0.63 mmol, 1.05 equiv), tris(dibenzylideneacetone)dipalladium (16 mg, 0.02 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (10 mg, 0.04 mmol, 6 mol%), and sodium tert-butoxide (115 mg, 1.2 mmol, 2.0 equiv). Toluene (5 mL) was added. The reaction was allowed to stand at 85°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 419 mg of a white solid (85% yield). This was used directly in subsequent reactions.

[0080] Synthesis of the ligand L-PtO2: To a reaction flask, add LNH-PtO2 (500 mg, 0.57 mmol, 1.0 equivalent), ammonium hexafluorophosphate (185 mg, 1.14 mmol, 2.0 equivalent), and triethyl orthoformate (5 mL). The reaction was incubated at 80°C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 500 mg of a white solid (80% yield). 1 H NMR (500MHz, DMSO) δ1.29(s,9H),1.31(s,9H),6.92(t,J=2.0Hz,1H),6.95(t,J=1.5Hz,1H) ,6.95(t,J=1.5Hz,1H),7.11–7.15(m,10H),7.33(dd,J=8.5,2.0Hz,1H),7.45–7.51(m,4H) ,7.52–7.59(m,4H),7.69–7.70(m,1H),7.75–7.81(m,4H),7.87(d,J=8.0Hz,1H),7.94(t,J =8.0Hz,1H),8.19–8.22(m,2H),8.52(d,J=8.5Hz,1H),8.64(d,J=5.0Hz,1H),10.33(s,1H).

[0081] Synthesis of PtPtO2: L-PtO2 (450 mg, 0.44 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (160 mg, 0.46 mmol, 1.05 equiv), and sodium acetate (108 mg, 1.32 mmol, 3.0 equiv) were added to a reaction flask. Diethylene glycol dimethyl ether (10 mL) was added and nitrogen was bubbled through the mixture for 30 min to deoxygenate. The reaction was terminated by reacting at 120°C for 72 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 368 mg of a light yellow solid in a 78% yield. 1H NMR (500MHz, CDCl3) δ1.31 (s, 9H), 1.47 (s, 9H), 6.24 (dd, J = 6.5, 2.0Hz, 2H), 6.75–7 .34(m,5H),6.89(d,J=7.5Hz,2H),7.06(t,J=8.0Hz,2H),7.15(d,J=1.5Hz,2H),7.41 –7.54(m,8H),7.77(d,J=8.0Hz,1H),7.98(d,J=8.5Hz,1H),8.04–8.07(m,2H),8.10( d,J=8.5Hz,1H),8.18(d,J=2.5Hz,1H),8.21(d,J=8.5Hz,1H),9.02(d,J=6.0Hz,1H).

[0082] Example 3: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtO5 is as follows:

[0083] Synthesis of intermediate LNH-PtO5: To a reaction flask, add dPh-tBuNH2 (502 mg, 1.28 mmol, 1.1 equiv), 4O-Cl (600 mg, 1.16 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (32 mg, 0.035 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (29 mg, 0.070 mmol, 6 mol%), and sodium tert-butoxide (223 mg, 2.32 mmol, 2.0 equiv). Toluene (5 mL) was added. The reaction was allowed to stand in an oil bath at 110°C for 12 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 1.04 g of a light green solid (96% yield). This was used directly in the subsequent reaction.

[0084] Synthesis of the ligand L-PtO5: To a reaction flask, add LNH-PtO5 (1.04 g, 1.2 mmol, 1.0 equiv), ammonium hexafluorophosphate (391 mg, 2.4 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). The reaction was incubated at 70°C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 961 mg of a white solid (78% yield). 1H NMR (500MHz, CDCl3) δ1.42(s,9H),1.45(s,9H),6.66(t,J=2.0Hz,1H),6.95(dd,J=8.0,2.0Hz,1H),7.05 –7.08(m,2H),7.10–7.16(m,8H),7.22(dd,J=8.5,2.0Hz,1H),7.25(s,1H),7.27(d,J=2.0Hz,1H),7.37–7 .44(m,3H),7.46–7.49(m,2H),7.52–7.55(m,2H),7.59(s,2H),7.64(d,J=2.0Hz,1H),7.68–7.72(m,2H) ,7.77(d,J=8.0Hz,1H),8.00(t,J=7.5Hz,2H),8.59(d,J=8.5Hz,1H),8.64(d,J=5.5Hz,1H),9.09(s,1H).

[0085] Synthesis of PtO5: To a reaction flask, add L-PtO5 (890 mg, 0.86 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (337 mg, 0.90 mmol, 1.05 equiv), and sodium acetate (212 mg, 2.58 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 283 mg of a light yellow solid (31% yield). 1 H NMR(500MHz,Chloroform-d)δ1.22(s,9H),1.44(s,9H),6.33–7.09(m,11H),7.23–7.24(m,2H),7.27(s,1H),7.42–7.5 3(m,7H),7.79(d,J=9.0Hz,1H),7.92(d,J=8.5Hz,1H),8.00–8.07(m,4H),8.26(d,J=8.0Hz,1H),9.12(d,J=6.5Hz,1H).

[0086] Example 4: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtO27 is as follows:

[0087] PtO27 was synthesized using the same synthesis steps and reaction conditions as those for compound PtO6 in Example 5. The target product, LNH-PtO27, was obtained as a light green foamy solid (1.24 g) with a yield of 85%. The target product, L-PtO27, was obtained as a light green foamy solid (881 mg) with a yield of 78%. Molecular weight [M] +:1100.5. Target product PtO27, yellow solid 425 mg, yield 56%. Molecular weight [M+H] + :1294.5.

[0088] Example 5: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtO33 is as follows:

[0089] Synthesis of intermediate 4O-Cl: To a reaction flask were added 4O-OH (200 mg, 0.49 mmol, 1.0 equiv), m-chlorobromobenzene (140 mg, 0.73 mmol, 1.5 equiv), 2-picolinic acid (12 mg, 0.098 mmol, 20 mmol%), cuprous iodide (9 mg, 0.049 mmol, 10 mmol%), potassium phosphate (208 mg, 0.98 mmol, 2.0 equiv), and dimethyl sulfoxide (5 mL). The reaction was terminated at 100°C for 12 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 164 mg of a white solid (65% yield). 1 H NMR(500MHz,DMSO)δ1.32(s,9H),7.09–7.12(m,1H),7.20–7.26(m,3H),7.33(d,J=2.0Hz,1H),7.40–7.48(m,2H),7.51–7.55(m,2H), 7.74(d,J=2.0Hz,1H),7.80(d,J=8.5Hz,1H),7.88(d,J=8.0Hz,1H),8.18–8.20(m,2H),8.45(d,J=8.5Hz,1H),8.64(d,J=5.45Hz,1H).

[0090] Synthesis of intermediate LNH-PtO33: To a reaction flask, add dPh-4tBuNH2 (477 mg, 0.85 mmol, 1.1 equiv), 4O-Cl (400 mg, 0.77 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (21 mg, 0.02 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (19 mg, 0.04 mmol, 6 mol%), and sodium tert-butoxide (149 mg, 1.4 mmol, 2.0 equiv). Toluene (5 mL) was added. The reaction was allowed to stand in an oil bath at 110°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 660 mg of a white solid (82% yield). This was used directly in subsequent reactions.

[0091] Synthesis of the ligand L-PtO33: To a reaction flask, add LNH-PtO33 (660 mg, 0.63 mmol, 1.0 equiv), ammonium hexafluorophosphate (206 mg, 1.27 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). The reaction was incubated at 70°C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 542 mg of a white solid (71% yield). 1 H NMR (500MHz, DMSO-d6) δ0.92 (s, 36H), 1.34 (s, 9H), 6.55 (t, J = 2.5Hz, 1H), 6.68 (ddd, J = 8.5 ,2.5,1.0Hz,1H),6.91(d,J=1.5Hz,4H),7.14(t,J=2.0Hz,2H),7.32(dd,J=8.0,2.0Hz,1H), 7.46–7.59(m,8H),7.69–7.73(m,2H),7.75(d,J=1.0Hz,1H),7.79–7.89(m,4H),7.94–7.97( m,1H),8.19–8.24(m,2H),8.49(d,J=8.5Hz,1H),8.65(dd,J=5.0,0.5Hz,1H),10.01(s,1H).

[0092] Synthesis of PtO33: To a reaction flask, L-PtO33 (500 mg, 0.42 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (156 mg, 0.42 mmol, 1.05 equiv), and sodium acetate (103 mg, 1.25 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, then cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 108 mg of a light yellow solid (34% yield). 1 H NMR(500MHz,DMSO-d6)δ0.26–1.19(br,36H),1.32(s,9H),6.53–7.37(m,14H),7.47–7.61(m,5H),7.9 0(d,J=8.0Hz,1H),8.06(d,J=8.0Hz,1H),8.15–8.20(m,2H),8.21–8.30(m,3H),9.04(d,J=6.5Hz,1H).

[0093] Example 6: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtO34 is as follows:

[0094] Synthesis of intermediate LNH-PtO34: To a reaction flask, add dPh-4tBuNH2 (430 mg, 0.77 mmol, 1.1 equiv), tBu-4O-Cl (400 mg, 0.70 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (19 mg, 0.02 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (17 mg, 0.04 mmol, 6 mol%), and sodium tert-butoxide (134 mg, 1.40 mmol, 2.0 equiv). Toluene (5 mL) was added. The reaction was allowed to stand in an oil bath at 110°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 591 mg of a white solid (78% yield). This was used directly in subsequent reactions.

[0095] Synthesis of the ligand L-PtO34: To a reaction flask, add LNH-PtO34 (591 mg, 0.54 mmol, 1.0 equiv), ammonium hexafluorophosphate (175 mg, 1.07 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). The reaction was allowed to stand at 70°C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 415 mg of a white solid (61% yield). 1 H NMR(500MHz,DMSO-d6)δ0.87(s,36H),1.29(s,9H),1.35(s,9H),6.40(t,J=2.0Hz,1H),6.69(t,J=2 .0Hz,1H),6.89(d,J=2.0Hz,4H),7.07(t,J=1.5Hz,2H),7.34(dd,J=8.5,2.5Hz,1H),7.44–7.59(m, 8H),7.68(d,J=8.5Hz,1H),7.74(d,J=1.0Hz,1H),7.77–7.82(m,2H),7.83(s,1H),7.86–7.89(m,1H ),7.93–7.96(m,1H),8.19–8.24(m,2H),8.49(d,J=8.0Hz,1H),8.65(d,J=5.5Hz,1H),10.07(s,1H).

[0096] Synthesis of PtO34: To a reaction flask, add L-PtO34 (350 mg, 0.28 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (104 mg, 0.29 mmol, 1.05 equiv), and sodium acetate (69 mg, 0.84 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 152 mg of a light yellow solid (41% yield). 1H NMR(500MHz,DMSO-d6)δ0.75(s,36H),1.32(s,9H),1.40(s,9H),6.64(dd,J=6 .0,2.0Hz,1H),6.80–7.12(m,9H),7.28–7.33(m,2H),7.45(s,1H),7.50(t,J=7 .5Hz,1H),7.57(t,J=7.5Hz,3H),7.90(d,J=8.0Hz,1H),8.05(d,J=8.0Hz,2H) ,8.17(s,1H),8.21(d,J=8.5Hz,1H),8.25–8.28(m,2H),9.00(d,J=6.0Hz,1H).

[0097] Example 7: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtO37 is as follows:

[0098] Synthesis of intermediate LNH-PtO37: To a reaction flask, add dPh-5tBuNH2 (666 mg, 1.08 mmol, 1.1 equiv), 4O-Cl (500 mg, 0.98 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (28 mg, 0.03 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (25 mg, 0.06 mmol, 6 mol%), and sodium tert-butoxide (188 mg, 1.96 mmol, 2.0 equiv). Toluene (5 mL) was added. The reaction was allowed to stand in an oil bath at 110°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 896 mg of a white solid (83% yield). This was used directly in subsequent reactions.

[0099] Synthesis of the ligand L-PtO37: To a reaction flask, add LNH-PtO37 (896 mg, 0.82 mmol, 1.0 equiv), ammonium hexafluorophosphate (267 mg, 1.64 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). The reaction was incubated at 70°C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 770 mg of a white solid (75% yield). 1H NMR(500MHz,DMSO)δ0.92(s,36H),1.34(s,9H),1.47(s,9H),6.54(s,1H),6.67(d, J=7.0Hz,1H),6.91(s,4H),7.14(s,2H),7.32(dd,J=8.0,2.0Hz,1H),7.45–7.57(m ,8H),7.68–7.72(m,2H),7.75(s,1H),7.81(d,J=7.5Hz,3H),7.87(d,J=8.0Hz,1H) ,8.21(t,J=8.5Hz,2H),8.49(d,J=8.0Hz,1H),8.65(d,J=5.5Hz,1H),9.93(s,1H).

[0100] Synthesis of PtO37: To a reaction flask, L-PtO37 (700 mg, 0.56 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (221 mg, 0.59 mmol, 1.05 equiv), and sodium acetate (138 mg, 1.68 mmol, 3.0 equiv) were added, followed by diethylene glycol dimethyl ether (5 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 124 mg of a light yellow solid (17% yield). 1 H NMR (500MHz, CDCl3) δ0.05–1.18(m,36H),1.20(s,9H),1.40(s,9H),6.45(dd,J=6.5,2.0Hz,1H),6.86(d,J=8.0Hz,3H),6.95–7.05(m,4H),7.20(t,J =8.0Hz,3H),7.37–7.59(m,7H),7.79(dd,J=8.0,2.0Hz,2H),7.92–8.00(m ,3H),8.05(d,J=7.5Hz,1H),8.25(d,J=8.5Hz,1H),9.25(d,J=6.5Hz,1H).

[0101] Example 8: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtO38 is as follows:

[0102] Synthesis of intermediate LNH-PtO38: To a reaction flask, add dPh-5tBuNH2 (592 mg, 0.96 mmol, 1.1 equiv), tBu-4O-Cl (500 mg, 0.87 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (24 mg, 0.03 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (26 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 allowed to stand in an oil bath at 110°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 887 mg of a white solid (88% yield). This was used directly in subsequent reactions.

[0103] Synthesis of the ligand L-PtO38: To a reaction flask, add LNH-PtO38 (887 mg, 0.77 mmol, 1.0 equiv), ammonium hexafluorophosphate (251 mg, 1.54 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). The reaction was incubated at 70°C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 700 mg of a white solid (70% yield). 1 H NMR (500MHz, DMSO) δ0.87 (s, 36H), 1.28 (s, 9H), 1.34 (s, 9H), 1.46 (s, 9H), 6.38 (t, J = 2.5Hz, 1H), 6.7 0(t,J=2.0Hz,1H),6.89(d,J=2.0Hz,4H),7.06(t,J=1.5Hz,2H),7.34(dd,J=8.5,2.0Hz,1H),7.42–7 .50(m,3H),7.52–7.58(m,5H),7.67(d,J=8.5Hz,1H),7.74(d,J=2.5Hz,1H),7.78–7.80(m,3H),7.86 (d,J=8.0Hz,1H),8.21(t,J=9.0Hz,2H),8.49(d,J=8.5Hz,1H),8.65(d,J=5.5Hz,1H),10.00(s,1H).

[0104] Synthesis of PtO38: To a reaction flask, L-PtO38 (622 mg, 0.48 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (189 mg, 0.54 mmol, 1.05 equiv), and sodium acetate (118 mg, 1.44 mmol, 3.0 equiv) were added, followed by diethylene glycol dimethyl ether (5 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 400 mg of a light yellow solid (61% yield). 1H NMR (500MHz, DMSO) δ1.23 (s, 45H), 1.40 (s, 18H), 6.68 (d, J = 8.0Hz, 2H), 6.83–6 .97(m,4H),7.08(t,J=7.5Hz,3H),7.24–7.35(m,3H),7.43–7.60(m,5H),7.87(d ,J=8.5Hz,1H),7.91(d,J=8.0Hz,1H),8.01(d,J=2.0Hz,1H),8.07(dd,J=11.5, 8.0Hz,2H),8.24(d,J=8.0Hz,1H),8.28(d,J=8.5Hz,1H),9.09(d,J=6.5Hz,1H).

[0105] Example 9: The synthesis route of the tetradentate platinum (II) complex phosphorescent material PtO93 is as follows:

[0106] PtS93 was synthesized using the same synthesis steps and reaction conditions as those for compound PtS6 in Example 12. The target product, LNH-PtO93, was obtained as a light green foamy solid (1.19 g, 77% yield). The target product, L-PtO93, was obtained as a light green foamy solid (891 mg, 78% yield). Molecular weight [M] + :881.2. Target product Pt O93, yellow solid 325 mg, yield 36%. Molecular weight [M+H] + :1072.2.

[0107] Example 10: The synthesis route of the tetradentate platinum (II) complex phosphorescent material PtO107 is as follows:

[0108] Synthesis of the intermediate dtBu-Me-4O-OMe: To a reaction flask, add 4O-NH (1.0 g, 3.5 mmol, 1.0 equiv), dtBu-Me-Cl (1.34 g, 4.2 mmol, 1.2 equiv), tris(dibenzylideneacetone)dipalladium (128 mg, 0.14 mmol, 4 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (115 mg, 0.28 mmol, 8 mol%), and sodium tert-butoxide (673 mg, 7 mmol, 2.0 equiv). Toluene (5 mL) was then added. The reaction was allowed to stand at 110°C for 48 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 1.92 g of a brown solid (95% yield). This solid was used directly in subsequent reactions.

[0109] Synthesis of the intermediate dtBu-Me-4O-OH: Add dtBu-Me-4O-OMe (1.84 g, 3.2 mmol, 1.0 equivalent) and hydrogen bromide (2.59 g, 32 mmol, 10.0 equivalent) to a reaction flask. Incubate at 120°C for 48 hours, cool to room temperature, concentrate, and purify by silica gel column chromatography to afford 1.58 g of a brown solid (89% yield). Use directly in subsequent reactions.

[0110] Synthesis of the intermediate dtBu-Me-4O-Cl: To a reaction flask were added dtBu-Me-4O-OH (600 mg, 1.09 mmol, 1.0 equiv), m-chlorobromobenzene (314 mg, 1.64 mmol, 1.5 equiv), 2-picolinic acid (134 mg, 1.10 mmol, 100 mmol%), cuprous iodide (105 mg, 0.55 mmol, 10 mmol%), potassium phosphate (463 mg, 2.18 mmol, 2.0 equiv), and dimethyl sulfoxide (10 mL). The reaction was terminated at 110°C for 12 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 566 mg of a white solid (78% yield). 1 H NMR (500MHz, DMSO) δ1.36 (s, 18H), 2.44 (s, 3H), 7.04 (dd, J = 8.0, 2.0Hz, 1H), 7.1 3(t,J=2.5Hz,1H),7.18–7.23(m,2H),7.35(d,J=2.0Hz,2H),7.41(t,J=8.0Hz,1 H),7.45–7.49(m,2H),7.51–7.55(m,1H),7.63(d,J=2.0Hz,1H),7.82(s,1H),7. 88(t,J=9.0Hz,1H),8.21(d,J=11.0Hz,2H),8.46(d,J=8.5Hz,1H),8.57(s,1H).

[0111] Synthesis of intermediate LNH-PtO107: To a reaction flask, add dPh-tBuNH2 (341 mg, 0.87 mmol, 1.1 equiv), dtBu-Me-4O-Cl (524 mg, 0.79 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (22 mg, 0.024 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (20 mg, 0.048 mmol, 6 mol%), and sodium tert-butoxide (152 mg, 1.58 mmol, 2.0 equiv). Toluene (5 mL) was added. The reaction was allowed to stand in an oil bath at 110°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 687 mg of a white solid (85% yield). This was used directly in subsequent reactions.

[0112] Synthesis of the ligand L-PtO107: To a reaction flask, add LNH-PtO107 (687 mg, 0.67 mmol, 1.0 equiv), ammonium hexafluorophosphate (218 mg, 1.34 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). Incubate at 70°C for 2 hours, cool to room temperature, concentrate, and purify by silica gel column chromatography to afford 755 mg of a white solid (96% yield). Use directly in subsequent reactions.

[0113] Synthesis of PtO107: To a reaction flask, add L-PtO107 (675 mg, 0.57 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (224 mg, 0.60 mmol, 1.05 equiv), and sodium acetate (140 mg, 1.71 mmol, 3.0 equiv), followed by diethylene glycol dimethyl ether (5 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 183 mg of a light yellow solid (26% yield). 1 H NMR (500MHz, CDCl3) δ1.17(s,18H),1.55(s,9H),2.05(s,3H),6.05(t,J=8.5Hz,2H),6.43(t t,J=8.0,1.5Hz,1H),6.50(s,2H),6.73(d,J=8.0Hz,1H),6.78(d,J=2.0Hz,2H),6.87–6.96( m,4H),7.05–7.10(m,2H),7.16–7.25(m,4H),7.39–7.54(m,6H),7.80(d,J=8.0Hz,1H),7.95 –7.97(m,2H),8.02(d,J=8.5Hz,1H),8.06–8.09(m,2H),8.27(d,J=8.0Hz,1H),9.19(s,1H).

[0114] Example 11: The synthesis route of the tetradentate platinum (II) complex phosphorescent material PtO109 is as follows:

[0115] Synthesis of intermediate PhF-Me-NH: To a reaction flask, add p-fluorophenylboric acid (2.7 g, 19.2 mmol, 1.2 eq), Br-Me-NH (3.0 g, 16 mmol, 1.0 eq), tetrakis(triphenylphosphine)palladium (371 mg, 0.32 mmol, 2 mol%), potassium carbonate (4.4 g, 32 mmol, 2.0 eq), dioxane (160 mL), and water (40 mL). The reaction was allowed to stand at 90°C for 12 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 3.1 g of a yellow solid (95% yield). This was used directly in subsequent reactions.

[0116] Synthesis of the intermediate PhF-Me-Cl: To a reaction flask, add PhF-Me-NH (3.1 g, 15.3 mmol, 1.0 equivalent), tert-butyl nitrite (15.7 g, 69 mmol, 5.0 equivalent), triethylbenzylammonium chloride (7.9 g, 76.6 mmol, 4.5 equivalent), dichloromethane (100 mL), and water (40 mL). The reaction was allowed to react at room temperature for 12 hours, then cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 3.1 g of a yellow solid (60% yield). This was used directly in subsequent reactions.

[0117] Synthesis of the intermediate PhF-Me-4O-OMe: To a reaction flask, add 4O-NH (1.0 g, 3.5 mmol, 1.0 equiv), PhF-Me-Cl (931 g, 3.5 mmol, 1.2 equiv), tris(dibenzylideneacetone)dipalladium (128 mg, 0.14 mmol, 4 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (115 mg, 0.28 mmol, 8 mol%), and sodium tert-butoxide (673 mg, 7 mmol, 2.0 equiv). Toluene (5 mL) was then added. The reaction was allowed to stand at 110°C for 48 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 1.42 g of a brown solid (86% yield). This was used directly in subsequent reactions.

[0118] Synthesis of the intermediate PhF-Me-4O-OH: PhF-Me-4O-OMe (1.42 g, 3.2 mmol, 1.0 equivalent) and hydrogen bromide (2.59 g, 32 mmol, 10.0 equivalent) were added to a reaction flask. The reaction was allowed to proceed at 120°C for 48 hours, then cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 1.21 g of a brown solid (85% yield). This solid was used directly in subsequent reactions.

[0119] Synthesis of the intermediate PhF-Me-4O-Cl: To a reaction flask, PhF-Me-4O-OH (3.0 g, 6.5 mmol, 1.0 equiv), m-chlorobromobenzene (1.88 g, 9.8 mmol, 1.5 equiv), 2-picolinic acid (800 mg, 6.5 mmol, 100 mmol%), cuprous iodide (619 mg, 3.3 mmol, 50 mmol%), and potassium phosphate (2.7 g, 13 mmol, 2.0 equiv) were added. Dimethyl sulfoxide (20 mL) was then added. The reaction was allowed to stand at 120°C for 12 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 644 mg of a white solid (49% yield). This was used directly in subsequent reactions.

[0120] Synthesis of intermediate LNH-PtO109: dPh-4tBuNH2 (470 mg, 1.2 mmol, 1.2 eq), PhF-Me-4O-Cl (620 mg, 1.09 mmol, 1.0 eq), tris(dibenzylideneacetone)dipalladium (30 mg, 0.03 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (27 mg, 0.06 mmol, 6 mol%), and sodium tert-butoxide (210 mg, 2.18 mmol, 2.0 eq) were added to a reaction flask, followed by toluene (8 mL). ℃ The reaction was stopped in an oil bath for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 925 mg of a white solid with a yield of 92%, which was used directly in the subsequent reaction.

[0121] Synthesis of the ligand L-PtO109: To a reaction flask, add LNH-PtO109 (925 mg, 1 mmol, 1.0 equivalent), ammonium hexafluorophosphate (326 mg, 2 mmol, 2.0 equivalent), and triethyl orthoformate (5 mL). The reaction was incubated at 70°C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 629 mg of a white solid (58% yield). 1 H NMR (500MHz, DMSO-d6) δ1.43(s,9H),2.42(s,3H),6.97(t,J=2.0Hz,1H),7.11–7.17(m,11H),7.32(dd,J=8.5,2.5Hz,1H),7.36–7.43(m ,3H),7.45–7.51(m,2H),7.52–7.61(m,5H),7.70–7.78(m,5H),7.87–7.93(m,3H),8.21–8.26(m,2H),8.53–8.56(m,2H),10.26(s,1H).

[0122] Synthesis of PtO109: To a reaction flask, L-PtO109 (591 mg, 0.55 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (205 mg, 0.58 mmol, 1.05 equiv), and sodium acetate (135 mg, 1.64 mmol, 3.0 equiv) were added, followed by diethylene glycol dimethyl ether (5 mL). 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 254 mg of a light yellow solid (41% yield). 1 H NMR (500MHz, DMSO-d6) δ1.48(s,9H),2.22(s,3H),6.10(t,J=7.5Hz,2H),6.47(t,J=7.5Hz,1H),6.52(d,J=7.5Hz,2H),6.7 9(d,J=8.0Hz,1H),6.83(t,J=9.0Hz,2H),6.94(dd,J=8.0,1.0Hz,1H),7.05–7.13(m,4H),7.16–7.32(m,8H),7.40(d,J=2.5 Hz,1H),7.52(td,J=7.5,1.0Hz,1H),7.59(ddd,J=8.0,7.0,1.5Hz,1H),7.64(d,J=7.5Hz,1H),7.92(d,J=8.0Hz,1H),8.06– 8.10(m,2H),8.17(d,J=8.5Hz,1H),8.22(d,J=8.5Hz,1H),8.29(dd,J=7.5,1.5Hz,1H),8.37(d,J=8.5Hz,1H),9.05(s,1H).

[0123] Example 12: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtS6 is as follows:

[0124] Synthesis of intermediate 4S-NO2: To a reaction flask were added A-4S-B(OH)2 (8.76 g, 38.4 mmol, 1.2 eq), B (6 g, 32 mmol, 1.0 eq), tetrakis(triphenylphosphine)palladium (1.11 g, 0.96 mmol, 3 mol%), and potassium carbonate (8.86 g, 64 mmol, 2.0 eq). Dioxane (80 mL) and water (20 mL) were then added. The reaction was allowed to stand at 90°C for 24 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 9.23 g of a yellow solid (80% yield). The product was used directly in subsequent reactions.

[0125] Synthesis of intermediate 4S-NH: To a reaction flask, add 4S-NO (6 g, 17.9 mmol, 1.0 equiv) and triphenylphosphine (14.08 g, 53.7 mmol, 3.0 equiv), followed by o-dichlorobenzene (60 mL). The reaction was incubated at 110°C for 24 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 4.45 g of a brown solid (82% yield). This was used directly in subsequent reactions.

[0126] Synthesis of intermediate 4S-OMe: To a reaction flask, add 4S-NH (3 g, 10 mmol, 1.0 equiv), 4-(tert-butyl)-2-chloropyridine (2.04 g, 12 mmol, 1.2 equiv), tris(dibenzylideneacetone)dipalladium (275 mg, 0.3 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (179 mg, 0.6 mmol, 6 mol%), and sodium tert-butoxide (1.92 g, 20 mmol, 2.0 equiv). Toluene (50 mL) was added. The reaction was allowed to stand at 110°C for 48 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 3.12 g of a brown solid (73% yield). This was used directly in subsequent reactions.

[0127] Synthesis of intermediate 4S-OH: To a reaction flask, add 4S-OMe (3.12 g, 7.1 mmol, 1.0 equiv), pyridine hydrochloride (8.53 g, 71 mmol, 10.0 equiv), and 1,3-dimethyl-2-imidazolidinone (60 mL). Incubate at 180°C for 48 hours, cool to room temperature, concentrate, and purify by silica gel column chromatography to afford 2.68 g of a brown solid (87% yield). Use directly in subsequent reactions.

[0128] Synthesis of intermediate tBu-4S-Cl: To a reaction flask were added 4S-OH (1 g, 2.4 mmol, 1.0 equiv), 3-chloro-5-bromo-tert-butylbenzene (1.78 g, 3.12 mmol, 1.3 equiv), 2-picolinic acid (60 mg, 0.48 mmol, 20 mmol%), cuprous iodide (46 mg, 0.24 mmol, 10 mmol%), potassium phosphate (1.02 g, 4.8 mmol, 2.0 equiv), and dimethyl sulfoxide (10 mL). The reaction was terminated at 110°C for 12 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 1.05 g of a white solid (75% yield). 1H NMR (500MHz, DMSO) δ1.24(s,9H),1.32(s,9H),6.95(t,J=2.0Hz,1H),7.14(t,J =2.5Hz,1H),7.21(t,J=1.5Hz,1H),7.28(dd,J=11.0,2.5Hz,1H),7.38(d,J=2.0 Hz,1H),7.52–7.60(m,3H),7.72(d,J=1.5Hz,1H),7.91(d,J=9.0Hz,1H),8.17(d ,J=6.5Hz,1H),8.23(d,J=8.5Hz,1H),8.42–8.45(m,2H),8.63(d,J=5.5Hz,1H).

[0129] Synthesis of intermediate LNH-PtS6: To a reaction flask, add dPh-tBuNH2 (125 mg, 0.32 mmol, 1.0 equiv), followed by tBu-4O-Cl (200 mg, 0.34 mmol, 1.05 equiv), tris(dibenzylideneacetone)dipalladium (9 mg, 0.001 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (6 mg, 0.002 mmol, 6 mol%), and sodium tert-butoxide (61 mg, 0.64 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, concentrated, and purified by silica gel column chromatography to afford 187 mg of a white solid (67% yield). This was used directly in subsequent reactions.

[0130] Synthesis of the ligand L-PtS6: To a reaction flask, add LNH-PtS6 (228 mg, 0.24 mmol, 1.0 equiv), followed by ammonium hexafluorophosphate (31 mg, 0.48 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). The reaction was incubated at 80°C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 184 mg of a white solid (74% yield). 1H NMR (500MHz, DMSO) δ1.30(s,9H),1.31(s,9H),1.42(s,9H),6.86(t,J=2.0Hz,1H),6.97(t, J=1.5Hz,1H),7.10–7.16(m,10H),7.37(dd,J=8.5,2.5Hz,1H),7.47–7.60(m,8H),7.70–7.7 1(m,3H),7.78(d,J=2.0Hz,1H),7.93(d,J=8.5Hz,1H),8.18(d,J=7.0Hz,1H),8.31(d,J=8. 5Hz,1H),8.44(d,J=7.0Hz,1H),8.48(d,J=9.0Hz,1H),8.65(d,J=5.5Hz,1H),10.26(s,1H).

[0131] Synthesis of PtS6: To a reaction flask, add PtS6 (140 mg, 0.13 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (48 mg, 0.14 mmol, 1.05 equiv), and sodium acetate (32 mg, 0.39 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 97 mg of a light yellow solid (65% yield). 1 H NMR (500MHz, CDCl3) δ1.22(s,9H),1.44(s,9H),1.47(s,9H),6.33(dd,J=6.0,2.0Hz,2H),6.67–7.18(m,10H),7.3 6–7.68(m,9H),7.95–8.01(m,3H),8.05(dd,J=8.5,3.5Hz,2H),8.29(dd,J=8.5,5.0Hz,2H),9.09(d,J=6.0Hz,1H).

[0132] Example 13: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtS2 is as follows:

[0133] Synthesis of intermediate LNH-PtS2: dPh-NH2 (200 mg, 0.6 mmol, 1.0 equiv) was added to a reaction flask, followed by tBu-4S-Cl (371 mg, 0.63 mmol, 1.05 equiv), tris(dibenzylideneacetone)dipalladium (34 mg, 0.04 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (22 mg, 0.08 mmol, 6 mol%), and sodium tert-butoxide (115 mg, 1.2 mmol, 2.0 equiv). Toluene (5 mL) was added. The reaction was stopped in an 85°C oil bath for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 374 mg of a white solid (65% yield). This was used directly in subsequent reactions.

[0134] Synthesis of the ligand L-PtS2: To a reaction flask, add LNH-2 (374 mg, 0.42 mmol, 1.0 equiv), followed by ammonium hexafluorophosphate (137 mg, 0.84 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). The reaction was incubated at 80°C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 372 mg of a white solid (83% yield). 1 H NMR (500MHz, DMSO) δ1.30(s,9H),1.32(s,9H),6.91(t,J=2.0Hz,1H),6.97(t,J=2.0Hz,1H),7.12–7. 15(m,9H),7.38(dd,J=8.5,2.0Hz,1H),7.47–7.49(m,1H),7.52–7.61(m,7H),7.70–7.72(m,1H),7.7 6(d,J=8.0Hz,2H),7.79(d,J=1.5Hz,1H),7.84(s,1H),7.92–7.96(m,2H),8.18(d,J=7.0Hz,1H),8.3 1(d,J=8.5Hz,1H),8.44(d,J=7.0Hz,1H),8.49(d,J=9.0Hz,1H),8.65(d,J=5.5Hz,1H),10.34(s,1H).

[0135] Synthesis of PtS2: L-PtS2 (250 mg, 0.24 mmol, 1.0 equivalent), (1,5-cyclooctadiene) platinum (II) dichloride (87 mg, 0.25 mmol, 1.05 equivalent) and sodium acetate (60 mg, 0.72 mmol, 3.0 equivalent) were added to the reaction flask, and diethylene glycol dimethyl ether (10 mL) was added. The reaction was stopped at 120 ° C for 72 hours, cooled to room temperature, concentrated, and silica gel column chromatography to obtain 136 mg of light yellow solid, with a yield of 52%. 1H NMR(500MHz,DMSO)δ1.33(s,9H),1.43(s,9H),6.25–6.90(m,6H),6.97–7.51(m,10H),7.53–7.90(m,7H),8.15(d ,J=8.5Hz,2H),8.21(d,J=8.0Hz,1H),8.54(dd,J=8.0,4.0Hz,2H),8.61(d,J=9.0Hz,1H),8.84(d,J=6.0Hz,1H).

[0136] Example 14: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtS1 is as follows:

[0137] Synthesis of intermediate 4S-Cl: To a reaction flask were added 4S-OH (1.0 g, 2.4 mmol, 1.0 equiv), m-chlorobromobenzene (689 mg, 3.6 mmol, 1.5 equiv), 2-picolinic acid (60 mg, 0.48 mmol, 20 mmol%), cuprous iodide (45 mg, 0.24 mmol, 10 mmol%), potassium phosphate (1.02 g, 4.8 mmol, 2.0 equiv), and dimethyl sulfoxide (10 mL). The reaction was terminated at 110°C for 12 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 868 mg of a white solid in a 71% yield. 1 H NMR (500MHz, DMSO) δ1.32(s,9H),7.08–7.10(m,2H),7.19–7.24(m,2H),7.29(dd,J=8.5,2.0Hz,1H),7.39–7.44(m,2H),7.52–7.60(m,3H),7.74(d,J =1.0Hz,1H),7.92(d,J=9.0Hz,1H),8.16–8.18(m,1H),8.23(d,J=8.5Hz,1H),8.42–8.46(m,2H),8.64–8.65(m,1H).

[0138] Synthesis of intermediate LNH-PtS1: To a reaction flask, dPh-NH2 (242 mg, 0.72 mmol, 1.0 equiv), 4S-Cl (400 mg, 0.75 mmol, 1.03 equiv), tris(dibenzylideneacetone)dipalladium (66 mg, 0.072 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (43 mg, 0.14 mmol, 6 mol%), and sodium tert-butoxide (119 mg, 1.44 mmol, 2.0 equiv) were added. Toluene (5 mL) was then added. The reaction was allowed to stand in an 85°C oil bath for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 505 mg of a white solid (78% yield). This was used directly in subsequent reactions.

[0139] Synthesis of the ligand L-PtS1: To a reaction flask, add LNH-PtS1 (505 mg, 0.61 mmol, 1.0 equiv), ammonium hexafluorophosphate (199 mg, 1.22 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). The reaction was incubated at 80°C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 416 mg of a white solid (63% yield). 1 H NMR (500MHz, DMSO) δ1.32 (s, 9H), 7.04 (t, J = 2.0Hz, 1H), 7.10–7.18 (m, 11H), 7.37(dd,J=8.5,2.0Hz,1H),7.44–7.48(m,2H),7.53–7.61(m,6H),7.71–7.7 7(m,4H),7.80(d,J=2.5Hz,1H),7.93–7.96(m,2H),8.18(d,J=7.0Hz,1H),8. 32(d,J=8.5Hz,1H),8.43–8.50(m,2H),8.66(d,J=6.0Hz,1H),10.35(s,1H).

[0140] Synthesis of PtS1: To a reaction flask, L-PtS1 (310 mg, 0.31 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (115 mg, 0.33 mmol, 1.05 equiv), and sodium acetate (76 mg, 0.93 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 108 mg of a light yellow solid (34% yield). 1H NMR (500MHz, CDCl3) δ1.31 (s, 9H), 6.25 (dd, J = 6.0, 1.5Hz, 1H), 6.30–6.97 (m, 8H),6.99–7.15(m,4H),7.18–7.24(m,1H),7.26–7.31(m,2H),7.47–7.57(m,7H ),7.96(d,J=8.0Hz,1H),8.00(d,J=8.5Hz,1H),8.04(d,J=8.0Hz,1H),8.17(d, J=2.0Hz,1H),8.23(d,J=8.5Hz,1H),8.29–8.31(m,2H),9.04(d,J=6.0Hz,1H).

[0141] Example 15: The synthesis route of the tetradentate platinum (II) complex phosphorescent material PtS5 is as follows:

[0142] Synthesis of intermediate LNH-PtS5: To a reaction flask, add dPh-NH2 (281 mg, 0.72 mmol, 1.1 equiv), 4S-Cl (344 mg, 0.65 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (24 mg, 0.03 mmol, 3 mol%), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (21 mg, 0.06 mmol, 6 mol%), and sodium tert-butoxide (125 mg, 1.30 mmol, 2.0 equiv). Toluene (5 mL) was added. The reaction was allowed to stand in an oil bath at 110°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 480 mg of a white solid (83% yield). This was used directly in subsequent reactions.

[0143] Synthesis of the ligand L-PtS5: To a reaction flask, add LNH-PtS5 (480 mg, 0.54 mmol, 1.0 equiv), ammonium hexafluorophosphate (176 mg, 1.08 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). The reaction was incubated at 70°C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 187 mg of a white solid (33% yield). 1H NMR (500MHz, DMSO) δ1.32 (s, 9H), 1.43 (s, 9H), 7.01 (t, J = 2.0Hz, 1H), 7.05–7.2 1(m,11H),7.37(dd,J=8.5,2.0Hz,1H),7.42–7.48(m,2H),7.51–7.61(m,6H),7.68–7.77(m,4H),7.80(d,J=1.5Hz,1H),7.94(d,J=9.0H z,1H),8.18(d,J=7.5Hz,1H),8.32(d,J=8.5Hz,1H),8.44(d,J=6.5Hz,1H),8.49(d,J=9.0Hz,1H),8.66(d,J=6.0Hz,1H),10.27(s,1H).

[0144] Synthesis of PtS5: To a reaction flask, add L-PtS5 (168 mg, 0.16 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (58 mg, 0.17 mmol, 1.05 equiv), and sodium acetate (39 mg, 0.48 mmol, 3.0 equiv), followed by diethylene glycol dimethyl ether (10 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 44 mg of a light yellow solid (25% yield). 1 H NMR (500MHz, DMSO-d6) δ1.22(s,9H),1.44(s,9H),6.34(dd,J=6.5,2.0Hz,1H),6.90(d,J=8.0Hz,7H),7.04–7.09(m,4H),7.24(d, J=7.5Hz,2H),7.27(s,1H),7.46–7.57(m,7H),7.99–8.01(m,3H),8.05(d,J=8.5Hz,2H),8.28–8.31(m,2H),9.11(d,J=5.0Hz,1H).

[0145] Example 16: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtS27 is as follows:

[0146] PtS27 was synthesized using the same synthesis steps and reaction conditions as those for compound PtS06 in Example 12. The target product, LNH-PtS27, was obtained as a light green foamy solid (1.07 g, 71% yield). The target product, L-PtS27, was obtained as a light green foamy solid (861 mg, 75% yield). Molecular weight [M] + :1116.5. Target product PtS27, yellow solid 325 mg, yield 66%. Molecular weight [M+H]+ :1310.7.

[0147] Example 17: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtS28 is as follows:

[0148] PtS28 was synthesized using the same synthesis steps and reaction conditions as those for compound PtS06 in Example 12. The target product, LNH-PtS28, was obtained as a light green foamy solid (1.19 g, 78% yield). The target product, L-PtS28, was obtained as a light green foamy solid (841 mg, 74% yield). Molecular weight [M] + :1145.6. Target product PtS28, yellow solid 385 mg, yield 46%. Molecular weight [M+H] + :1338.7.

[0149] Example 18: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtS13 is as follows:

[0150] PtS13 was synthesized using the same synthesis steps and reaction conditions as those for compound PtS06 in Example 12. The target product, LNH-PtS13, was obtained as a light green foamy solid (1.19 g, 76% yield). The target product, L-PtS13, was obtained as a light green foamy solid (891 mg, 78% yield). Molecular weight [M] + :929.2. Target product PtS28, yellow solid 325 mg, yield 36%. Molecular weight [M+H] + :1122.3.

[0151] Example 19: The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material PtS17 is as follows:

[0152] PtS17 was synthesized using the same synthesis steps and reaction conditions as those for compound PtS06 in Example 12. The target product, LNH-PtS17, was obtained as a light green foamy solid (1.19 g, 77% yield). The target product, L-PtS17, was obtained as a light green foamy solid (891 mg, 78% yield). Molecular weight [M] + :1041.5. Target product PtS17, yellow solid 325 mg, yield 36%. Molecular weight [M+H] + :1232.5.

[0153] Example 20: Synthesis of PtO52

[0154] PtO52 was synthesized using the same synthesis steps and reaction conditions as those for PtO6 in Example 1. 562 mg of the target product was obtained as a yellow solid with a yield of 35%. Molecular weight [M+H] + :1472.6.

[0155] Example 21: Synthesis of PtO74

[0156] PtO74 was synthesized using the same synthesis steps and reaction conditions as those for PtO6 in Example 1. The target product was obtained as a yellow solid (604 mg) with a yield of 58%. Molecular weight [M+H] + :1362.6.

[0157] Example 22: Synthesis of PtO88

[0158] PtO88 was synthesized using the same synthesis steps and reaction conditions as those for PtO6 in Example 1. The target product was obtained as a yellow solid (624 mg) with a yield of 58%. Molecular weight [M+H] + :1474.7.

[0159] Example 23: Synthesis of PtO89

[0160] PtO89 was synthesized using the same synthesis steps and reaction conditions as those for PtO6 in Example 1. The target product was obtained as a yellow solid (661 mg) with a yield of 72%. Molecular weight [M+H] + :1316.5.

[0161] Example 24: Synthesis of PtO140

[0162] PtO140 was synthesized using the same synthesis steps and reaction conditions as those for PtO6 in Example 1. 455 mg of the target product was obtained as a yellow solid with a yield of 69%. Molecular weight [M+H] + :1236.5.

[0163] Example 25: Synthesis of PtO144

[0164] PtO144 was synthesized using the same synthesis steps and reaction conditions as those for PtO6 in Example 1. 471 mg of the target product was obtained as a yellow solid with a yield of 80%. Molecular weight [M+H] + :1280.5.

[0165] Example 26: Synthesis of PtO150

[0166] PtO150 was synthesized using the same synthesis steps and reaction conditions as those for PtO6 in Example 1. 596 mg of the target product was obtained as a yellow solid with a yield of 56%. Molecular weight [M+H] + :1187.4.

[0167] Example 27: Synthesis of PtO158

[0168] PtO158 was synthesized using the same synthesis steps and reaction conditions as those for PtO6 in Example 1. 369 mg of the target product was obtained as a yellow solid with a yield of 58%. Molecular weight [M+H] + :1205.4.

[0169] Example 28: Synthesis of PtS47

[0170] PtS47 was synthesized using the same synthesis steps and reaction conditions as those for compound PtS6 in Example 12. 492 mg of the target product was obtained as a yellow solid with a yield of 82%. Molecular weight [M+H] + :1369.6.

[0171] Example 29: Synthesis of PtS87

[0172] PtS87 was synthesized using the same synthesis steps and reaction conditions as those for compound PtS6 in Example 12. The target product was obtained as a yellow solid (596 mg) with a yield of 74%. Molecular weight [M+H] + :1518.7.

[0173] Example 30: Synthesis of PtS93

[0174] PtS93 was synthesized using the same synthesis steps and reaction conditions as those for compound PtS6 in Example 12. The target product was obtained as a yellow solid (615 mg) with a yield of 68%. Molecular weight [M+H] + :1088.4.

[0175] Example 31: Synthesis of PtS135

[0176] PtS135 was synthesized using the same synthesis steps and reaction conditions as those for compound PtS6 in Example 12. 582 mg of the target product was obtained as a yellow solid with a yield of 66%. Molecular weight [M+H] + :1279.6.

[0177] Density functional theory (DFT) was used to optimize the ground state (S0) molecular geometry. DFT calculations were performed using the B3LYP functional with the 6-31G(d) basis set for C, H, O, and N atoms and the LANL2DZ basis set for Pt atoms.

[0178] Table 1. Electrons and holes in the T1 excited state of some metal complexes of the present invention

[0179] From the calculated data in Table 1, it can be seen that the introduction of cyclization at different positions of carbazole expands the conjugated system and increases the distribution of local excited states, making the emission shoulder lower and the half-peak width narrower, with higher color purity, which can meet the requirements of blue light materials.

[0180] Photophysical properties:

[0181] Table 2. Photophysical properties of some metal complexes in dichloromethane solution

[0182] Figures 1-13 show the room-temperature emission spectra of R1 and some compounds of the present invention in dichloromethane solutions, respectively. As shown in Figures 1-13 and Table 2, the complexes provided by the present invention introduce cyclization at different positions of the carbazole, expanding the conjugated system and increasing the distribution of localized excited states, significantly lowering the emission shoulder, narrowing the half-peak width, and achieving higher color purity.

[0183] Fabrication of OLED devices:

[0184] 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 x 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 was then tested using standard methods. Unless otherwise specified, the device materials involved in this invention can be obtained by known synthesis methods.

[0185] 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) (PtO6:HTH-85:ETH-45 mass ratio is 10:60:30) / ETH-5 (5 nm) / ET-14 (40 nm) / LiQ (1 nm) / Al (100 nm).

[0186] Device Examples 2 to 31 and Comparative Example 1 were prepared using structures similar to those of Device Example 1, with the only difference being that PtO2, PtO5, PtO27, PtO33, PtO34, PtO37, PtO38, PtO93, PtO107, PtO109, PtS6, PtS2, PtS1, PtS5, PtS27, PtS28, PtS13, PtS17, PtO52, PtO74, PtO88, PtO89, PO140, PtO144, PtO150, PtO158, PtS47, PtS87, PtS93, PtS135, and R1 were used to replace PO6 in Device Example 1. The luminescence characteristics of the comparative examples and device examples prepared above were tested by standard methods, and the data are shown in Table 3. The device structure involved is as follows: P-4 is HATCN, and ET-14 is BPyTP.

[0187] Table 3. Device luminescence characteristics data table

[0188] As can be seen from Table 3, compared with Comparative Example 1, Device Examples 1 to 31 prepared in the present application all showed good device performance in terms of driving voltage, current efficiency and device life; in addition, the color purity of the device was also greatly improved. The improvement in the performance of each device example is based on the fact that the specific compound material of the present invention has a small emission shoulder peak and 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, device life and color purity while reducing the driving voltage. This shows that the compound provided by the present invention has certain commercial application value. In addition, the devices prepared by the present invention are all deep blue light devices.

[0189] In a preferred specific embodiment, the structure of device example 32 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) (PtO6:BN1-8:HTH-85:ETH-45 mass ratio is 10:1:59:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0190] Device Examples 33 to 39 were prepared using structures similar to those of Device Example 32, differing only in that the platinum (II) complex and the boron-containing compound in Device Example 32 were replaced with the compounds listed in Table 4. The device structures are as follows, and the device structures and luminescence characteristics are shown in Table 4.

[0191] Table 4. Device structure and luminescence characteristics data

[0192] As shown in Table 4, 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. The addition of boron-containing compounds to sensitize the device structure can further reduce the CIEy value, thereby improving the color purity of the device's luminescent light.

[0193] 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 metal platinum (II) complex of cyclic carbazole, characterized in that: It has the general structure shown in formula (I): In formula (I), X is selected from O or S; R 1 -R 9 Each independently represents a single substitution to the maximum amount of substitution, or no substitution; R 1 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, halogen, CN, C1-C30 alkyl, C1-C30 halogenated alkyl, C1-C30 deuterated alkyl, C6-C60 aryl, C6-C60 arylsilane, and combinations thereof.

2. The tetradentate metal platinum (II) complex of cyclic carbazole according to claim 1, characterized in that: R 1 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, CF3, 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, isononyl, sec-nonyl, tert-nonyl, phenyl, biphenyl, triphenylsilane and combinations thereof.

3. The tetradentate metal platinum (II) complex of cyclic carbazole according to claim 1, characterized in that: R 3 , R 4 , R 9 Each is independently selected from the group consisting of hydrogen, deuterium, F, CN, methyl, isopropyl, tert-butyl, phenyl, and combinations thereof.

4. The tetradentate metal platinum (II) complex of cyclic carbazole according to claim 1, characterized in that: R 6 , R 7 , R 8 Each is independently selected from the group consisting of hydrogen, deuterium, methyl, tert-butyl, phenyl, and combinations thereof.

5. The tetradentate metal platinum (II) complex of cyclic carbazole according to any one of claims 1 to 4, characterized in that: Select any one of the chemical structures shown below, wherein "D" represents deuterium and Ph represents phenyl:

6. Use of the tetradentate metal platinum (II) complex of the cyclic carbazole according to any one of claims 1 to 5 in electronic devices, wherein the electronic devices include one or more of an organic electroluminescent device, an organic integrated circuit, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field quenching device, a light emitting electrochemical cell or an organic laser diode.

7. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a cathode, an anode and an organic functional layer between the cathode and the anode; the organic functional layer comprises the tetradentate metal platinum (II) complex of the cyclic carbazole according to any one of claims 1 to 5.

8. An organic electroluminescent device, characterized in that: The organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the tetradentate metal platinum (II) complex of the cyclic carbazole according to any one of claims 1 to 5.

9. The organic electroluminescent device according to claim 7, characterized in that: The light-emitting layer also contains a fluorescent doping material, and the fluorescent doping material is a boron-containing compound.

10. An organic optoelectronic device, characterized in that: The organic photoelectric device comprises: a substrate layer; a first electrode, which is on the substrate; an organic light-emitting functional layer, which is on the first electrode; and a second electrode, which is on the organic light-emitting functional layer; wherein the organic light-emitting functional layer contains the tetradentate metal platinum (II) complex of the cyclic carbazole according to any one of claims 1 to 5.

11. The organic optoelectronic device according to claim 10, characterized in that: The organic light-emitting functional layer further comprises a fluorescent doping material, and the fluorescent doping material is a boron-containing compound.

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

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

14. A display or lighting device, characterized in that: The device comprises one or more of the organic electroluminescent devices according to any one of claims 7 to 9.

Images