Fused-ring carbazole tetradentate metal platinum (II) complex and use thereof, and electronic device

Abstract

The present invention relates to the field of organic electroluminescence, and in particular to a fused-ring carbazole tetradentate metal platinum (II) complex and a use thereof, and an electronic device. According to the present invention, the interaction between molecules is reduced by means of the introduction of diphenyl, and a fused-ring carbazole system is introduced at different positions of carbazole to improve the component proportion of a localized state (LE) in an excited triplet state of a cyclic tetradentate platinum (II) complex, so that the cyclic tetradentate platinum (II) complex has a low shoulder peak to improve the purity of luminescence of material molecules. Materials involved in the present invention all have good chemical stability and thermal stability, and are easy to prepare evaporated OLED devices. The combination with a fluorescent doping material can balance transport of holes and electrons, and energy transfer between a subject and an object is more efficient. An organic electroluminescent device manufactured by using the compound of the present invention as a luminous layer has markedly improved current efficiency, markedly prolonged service life, and a markedly reduced turn-on voltage. In particular, the joint use with phosphorescent-sensitized boron-containing compounds can improve the purity of luminescence of devices.

Description

A cyclic carbazole tetradentate metal platinum (II) complex, electronic device and application thereof Technical Field

[0001] The invention belongs to the field of organic electroluminescence, and in particular relates to a cyclic carbazole tetradentate 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 cost of preparing 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 cost of preparing platinum(II) complex phosphorescent materials.

[0004] In summary, the preparation cost of platinum (II) complex phosphorescent materials is much lower than that of iridium (III) complex phosphorescent materials. Furthermore, how can the height of the shoulder peak in the emission spectrum be reduced to improve the color purity of the luminescence emitted by the material molecules? This issue is particularly important for blue and deep-blue luminescent materials, as they significantly impact the efficiency and energy utilization of commercial top-emitting devices. However, the development of platinum complex materials and devices still faces several technical difficulties, and improving device efficiency and lifespan is a relatively important research issue. Therefore, the development of new phosphorescent metal platinum (II) complexes is urgently needed.

[0005] Summary of the Invention

[0006] In view of this, the present invention aims to provide a tetradentate platinum(II) complex of a cyclic carbazole. When used as a light-emitting layer in an organic electroluminescent device (OLED), the tetradentate platinum(II) complex can provide excellent device performance. This can improve the device's current efficiency, extend its lifespan, and reduce its operating voltage.

[0007] In order to achieve the above technical objectives, the technical solutions of the present invention are as follows:

[0008] The present invention provides a tetradentate metal platinum (II) complex of a cyclic carbazole having a general structure as shown in formula (I) to formula (V):

[0009] In formula (I) to formula (V), X is selected from C, 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 9Each is independently selected from the group consisting of hydrogen, deuterium, halogen, CN, C1-C30 alkyl, C1-C30 deuterated alkyl, C1-C30 haloalkyl, C1-C30 cycloalkyl, C1-C30 heterocycloalkyl, C6-C60 aryl or condensed aromatic hydrocarbon group, C6-C60 heteroaryl or condensed heteroaromatic hydrocarbon group, C6-C60 arylamine group and combinations thereof; when containing heteroatoms, the heteroatoms are selected from N and O.

[0010] Furthermore, R 1 、R 6 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, 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, and combinations thereof.

[0011] Preferably, R 1 、R 6 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, and combinations thereof.

[0012] Furthermore, R 2 -R 5 Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, CF3, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, naphthyl, pyridyl, quinolyl, cyclopentane, cyclohexane, a five-membered heterocycle, diphenylamine, and combinations thereof.

[0013] 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:

[0014] Furthermore, the present invention also provides the use of the tetradentate metal platinum (II) complex of cyclic carbazole having the structures shown in formula (I) to formula (V) in electronic devices.

[0015] 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).

[0016] In another aspect, the present invention further provides an organic electroluminescent device comprising the above-mentioned cyclic carbazole tetradentate metal platinum (II) complex having the structures shown in formula (I) to formula (V).

[0017] Furthermore, the organic electroluminescent device includes a cathode, an anode and an organic functional layer therebetween; the organic functional layer contains the above-mentioned cyclic carbazole tetradentate metal platinum (II) complex having the structure shown in formula (I) to formula (V).

[0018] 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 structures shown in Formula (I) to Formula (V) as described above.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] The present invention also provides a composition comprising a tetradentate metal platinum (II) complex of a cyclic carbazole having a structure represented by Formula (I) to Formula (V). 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.

[0024] The present invention also provides a preparation comprising the above cyclic carbazole tetradentate metal platinum (II) complex having the structure shown in formula (I) to formula (V) or the above composition and at least one solvent.

[0025] 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.

[0026] The present invention also provides a display or lighting device, which comprises one or more of the organic photoelectric devices described above.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The present invention provides a method for introducing a benzofuran or benzothiophene system at different positions of a carbazole to increase the component ratio of the localized state (LE) in the excited triplet state of a cyclotetradentate platinum (II) complex, thereby providing a low shoulder peak and improving the luminescent color purity of the material molecules. The materials involved in the present invention all have excellent chemical and thermal stability and are easy to prepare vapor-deposited organic light-emitting diode (OLED) devices. When combined with fluorescent doping materials, they can balance the transmission of holes and electrons, making the energy transfer between the host and the guest more efficient. 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. In particular, their combined use with phosphorescence-sensitized boron-containing compounds can improve the light color purity of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] FIG1 is a room temperature emission spectrum of Pt150 and R1 in a dichloromethane solution;

[0030] FIG2 is a room temperature emission spectrum of Pt162 and R1 in dichloromethane solution;

[0031] Figure 3 is the room temperature emission spectrum of Pt166 and R1 in dichloromethane solution. DETAILED DESCRIPTION

[0032] 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.

[0033] 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).

[0034] 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.

[0035] 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.

[0036] 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.

[0037] The compounds disclosed herein can exhibit desired properties and have emission and / or absorption spectra that can be adjusted by selecting appropriate ligands. In another aspect, the present invention can exclude any one or more compounds, structures, or portions thereof specifically described herein. 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] Synthesis Example

[0042] 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 performed separately, at a temperature of 25°C or room temperature, and at a pressure close to atmospheric pressure.

[0043] 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.

[0044] 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. 13 In 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.

[0045] Synthesis route

[0046] Example 1: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt150

[0047] The synthetic route is as follows:

[0048] 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 react at room temperature for 48 hours. Concentration and silica gel column chromatography afforded 25.6 g of a red liquid (80% yield). This was used directly in subsequent reactions.

[0049] Synthesis of the intermediate dBr-tBuNO2: To a reaction flask, add dBr-tBuNH2 (5 g, 16.3 mmol, 1.0 eq) and dissolve in N-methylpyrrolidone (50 mL). Then add sodium hydride (1.96 g, 49 mmol, 3.0 eq) and o-fluoronitrobenzene (3.45 g, 24.5 mmol, 1.5 eq). The reaction was allowed to react at room temperature for 48 hours. The mixture was concentrated and purified by silica gel column chromatography to afford 5.08 g of a yellow solid (70% yield). This solid was used directly in subsequent reactions.

[0050] 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 reaction was stopped after 24 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to obtain 3.43 g of a white solid with a yield of 90%, which was used directly in the subsequent reaction.

[0051] Synthesis of the intermediate dPh-tBuNH2: To a reaction flask, add 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), sodium carbonate (2.8 g, 20 mmol, 2.5 equiv), dioxane (40 mL), and water (15 mL). The reaction was allowed to react 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 2.66 g of a white solid (90% yield). 1 H NMR(500MHz,DMSO)δ1.35(s,9H),4.4 4(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=7.6,1.5Hz,1 H),6.31(dd,J=7.5,1.5Hz,1H),7.20–7.16(m,2H),7.25(t,J=7.5Hz,4H),7.28(s,2H),7.43–7.41(m,4H).

[0052] Synthesis of Intermediate 1O-NO2: To a reaction flask were added A1 (13.55 g, 63.9 mmol, 1.5 eq), B (8 g, 42.6 mmol, 1.0 eq), tetrakis(triphenylphosphine)palladium (1.47 g, 1.28 mmol, 3 mol%), and potassium carbonate (11.78 g, 85.2 mmol, 2.0 eq). Dioxane (80 mL) and water (20 mL) were also added. The reaction was allowed to stand at 90°C for 24 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 10 g of a yellow solid in a 74% yield. 1 H NMR (400MHz, DMSO-d6) δ3.97(s,3H),6.97(d,J=7.2Hz,1H),7.20(td,J=7.6,0.8Hz,2H),7.46–7.51(m,2H),7.56–7.60(m,2H),7.72–7.77(m,3H).

[0053] Synthesis of Intermediate 1O-NH: To a reaction flask, add 1O-NO (10 g, 31.3 mmol, 1.0 equiv) and triphenylphosphine (32.84 g, 125.2 mmol, 3.0 equiv), followed by o-dichlorobenzene (60 mL). The reaction was allowed to react at 110°C for 24 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 6.89 g of a brown solid (78% yield). This was used directly in subsequent reactions.

[0054] Synthesis of intermediate 1O-OMe: To a reaction flask, add 1O-NH (5.3 g, 18.4 mmol, 1.0 equiv), 4-(tert-butyl)-2-chloropyridine (4.05 g, 23.9 mmol, 1.3 equiv), tris(dibenzylideneacetone)dipalladium (673 mg, 1.10 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (JohnPhos) (603 mg, 2.2 mmol, 6 mol%), and sodium tert-butoxide (3.54 g, 36.8 mmol, 2.0 equiv). Toluene (50 mL) was added. The reaction was allowed to stand in an oil bath at 110°C for 48 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 6.59 g of a brown solid (85% yield). This was used directly in the subsequent reaction.

[0055] Synthesis of Intermediate 1O-OH: To a reaction flask, add 1O-OMe (6 g, 14.3 mmol, 1.0 equiv), pyridine hydrochloride (16.53 g, 143 mmol, 10.0 equiv), and 1,3-dimethyl-2-imidazolidinone (60 mL). The reaction was allowed to stand in an oil bath at 180°C for 48 hours. The reaction was cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 5.43 g of a brown solid (88% yield). This solid was used directly in subsequent reactions.

[0056] Synthesis of intermediate tBu-1O-Cl: To a reaction flask were added 1O-OH (1.6 g, 3.9 mmol, 1.0 equiv), 3-chloro-5-bromo-tert-butylbenzene (1.25 g, 5.1 mmol, 1.3 equiv), 2-picolinic acid (96 mg, 0.78 mmol, 20 mmol%), cuprous iodide (74 mg, 0.39 mmol, 10 mmol%), and potassium phosphate (1.66 g, 7.8 mmol, 2.0 equiv). Dimethyl sulfoxide (10 mL) was then added. The reaction was allowed to stand at 100°C for 12 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 566 mg of a white solid (65% yield). 1 H NMR (500MHz, DMSO) δ1.24(s,9H),1.31(s,9H),6.99(t,J=2.0Hz,1H),7.15(t,J=2. 0Hz,1H),7.22–7.26(m,2H),7.30(d,J=2.5Hz,1H),7.54(dd,J=5.5,1.5Hz,1H),7.6 3–7.67(m,1H),7.58–7.61(m,1H),7.70(d,J=2.0Hz,1H),7.83–7.86(m,2H),7.91(d ,J=9.0Hz,1H),8.63(d,J=5.0Hz,1H),8.75(d,J=7.5Hz,1H),8.80(d,J=8.5Hz,1H).

[0057] Synthesis of Intermediate LNH-150: To a reaction flask, add dPh-tBuNH2 (411 mg, 1.04 mmol, 1.3 equiv), tBu-1O-Cl (460 mg, 0.8 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (22 mg, 0.03 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (20 mg, 0.05 mmol, 6 mol%), and sodium tert-butoxide (153 mg, 1.6 mmol, 2.0 equiv). Toluene (5 mL) was then added. The reaction was allowed to react at 85°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 631 mg of a white solid (85% yield). This was used directly in subsequent reactions.

[0058] Synthesis of Ligand L-150: To a reaction flask, add LNH-150 (631 mg, 0.68 mmol, 1.0 equivalent), followed by ammonium hexafluorophosphate (221 mg, 1.4 mmol, 2.0 equivalent) and triethyl orthoformate (5 mL). The reaction was allowed to react at 80°C for 2 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 435 mg of a white solid (61% yield). 1H NMR (500MHz, DMSO) δ1.28(s,9H),1.31(s,9H),1.43(s,9H),6.91(t,J=2.2Hz,1H),6.99(t,J =1.8Hz,1H),7.10–7.18(m,11H),7.33(dd,J=9.0,2.5Hz,1H),7.46–7.50(m,2H),7.52–7.57 (m,4H),7.59–7.62(m,1H),7.64–7.72(m,4H),7.75(s,1H),7.86–7.90(m,2H),7.93(d,J=9. 0Hz,1H),8.64(d,J=5.0Hz,1H),8.77(d,J=7.0Hz,1H),8.88(d,J=9.0Hz,1H),10.27(s,1H).

[0059] Synthesis of Pt150: To a reaction flask, add L-150 (200 mg, 0.19 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (75 mg, 0.20 mmol, 1.05 equiv), and sodium acetate (47 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 250 mg of a light yellow solid (80% yield). 1 H NMR(500MHz, CDCl3)δ1.20(s,9H),1.44(s,9H),1.47(s,9H),6.06–6.82(m,7H),6 .92(d,J=8.5Hz,1H),7.05(t,J=7.5Hz,1H),7.15–7.18(m,2H),7.24–7.48(m,4H) ,7.54–7.75(m,8H),7.93(d,J=2.0Hz,1H),7.98(d,J=8.5Hz,1H),8.03(d,J=9.0H z,1H),8.41(d,J=8.5Hz,1H),8.75(dd,J=7.0,4.0Hz,1H),9.07(d,J=6.5Hz,1H).

[0060] Example 2: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt166

[0061] The synthetic route is as follows:

[0062] Synthesis of Intermediate 2O-NO2: To a reaction flask were added A2 (25 g, 119.9 mmol, 1.5 eq), B (15 g, 79.7 mmol, 1.0 eq), tetrakis(triphenylphosphine)palladium (2.77 g, 2.4 mmol, 3 mol%), potassium carbonate (22.1 g, 159.9 mmol, 2.0 eq), dioxane (160 mL), and water (40 mL). The reaction was allowed to proceed at 90°C for 12 h, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 19 g of a yellow solid (76% yield), which was used directly in the subsequent reaction.

[0063] Synthesis of intermediate 2O-NH: To a reaction flask, add 2O-NO (19 g, 61.1 mmol, 1.0 equiv) and triphenylphosphine (48.1 g, 183.4 mmol, 3.0 equiv), followed by o-dichlorobenzene (60 mL). The reaction was incubated at 180°C for 11 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 10.5 g of a brownish-white solid (61% yield). 1 H NMR(400MHz, DMSO-d6)δ3.89(s,3H),6.88(dd,J=8.4,2.4Hz,1H),7.12(d,J=2.4Hz,1H),7.48–7.54(m, 3H),7.74–7.77(m,1H),8.07(d,J=8.4Hz,1H),8.17(d,J=8.4Hz,1H),8.59–8.61(m,1H),11.95(s,1H).

[0064] Synthesis of intermediate 2O-OMe: To a reaction flask, add 2O-NH (10 g, 34.8 mmol, 1.0 equiv), 4-(tert-butyl)-2-chloropyridine (7.67 g, 45.2 mmol, 1.3 equiv), tris(dibenzylideneacetone)dipalladium (1.27 g, 1.4 mmol, 4 mol%), 2-(di-tert-butylphosphino)biphenyl (830 mg, 2.8 mmol, 8 mol%), and sodium tert-butoxide (6.69 g, 69.6 mmol, 2.0 equiv). Toluene (100 mL) was added. The reaction was allowed to stand at 110°C for 11 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 10 g of a white solid in a 72% yield. This was used directly in subsequent reactions.

[0065] Synthesis of intermediate 2O-OH: To a reaction flask, add 2O-OMe (566 mg, 1.35 mmol, 1.0 equiv), pyridine hydrochloride (1.56 g, 13.5 mmol, 10.0 equiv), and 1,3-dimethyl-2-imidazolidinone (6 mL). Incubate at 180°C for 18 hours, then cool to room temperature, concentrate, and purify by silica gel column chromatography to afford 493 mg of a white solid (90% yield). Use directly in subsequent reactions.

[0066] Synthesis of intermediate tBu-2O-Cl: To a reaction flask, add 2O-OH (343 mg, 0.84 mmol, 1.0 equiv), 3-chloro-5-bromo-tert-butylbenzene (272 mg, 1.1 mmol, 1.3 equiv), 2-picolinic acid (21 mg, 0.17 mmol, 20 mmol%), cuprous iodide (16 mg, 0.08 mmol, 10 mmol%), and potassium phosphate (356 mg, 1.7 mmol, 2.0 equiv). Dimethyl sulfoxide (5 mL) was then added. The mixture was reacted in an oil bath at 110°C for 12 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 418 mg of a white solid (86% yield). This was used directly in the subsequent reaction.

[0067] Synthesis of Intermediate LNH-166: To a reaction flask, add dPh-tBuNH2 (211 mg, 0.54 mmol, 1.2 equiv), followed by tBu-2O-Cl (256 mg, 0.45 mmol, 1.0 equiv), tris(dibenzylideneacetone)dipalladium (24.7 mg, 0.03 mmol, 6 mol%), 2-(di-tert-butylphosphino)biphenyl (16 mg, 0.05 mmol, 12 mol%), and sodium tert-butoxide (129 mg, 1.3 mmol, 3.0 equiv). Toluene (5 mL) was added. The reaction was allowed to react at 85°C for 3 hours, then stopped. The mixture was cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 250 mg of a green solid (60% yield), which was used directly in the subsequent reaction.

[0068] Synthesis of Ligand L-166: To a reaction flask, add LNH-166 (237 mg, 0.26 mmol, 1.0 equiv), followed by ammonium hexafluorophosphate (84.8 mg, 0.52 mmol, 2.0 equiv), and triethyl orthoformate (5 mL). Incubate at 75°C for 25 minutes, then stop the reaction, cool to room temperature, concentrate, and purify by silica gel column chromatography to afford 180 mg of a white solid (75% yield).

[0069] Synthesis of Pt166: To a reaction flask, add L-166 (27 mg, 0.025 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (10 mg, 0.026 mmol, 1.05 equiv), sodium acetate (6.15 mg, 0.075 mmol, 3.0 equiv), and diethylene glycol dimethyl ether (3 mL). After reacting at 120°C for 72 hours, the reaction was stopped, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 18 mg of a light yellow solid (80% yield). 1H NMR (500MHz, DMSO) δ0.78(s,9H),1.43(s,9H),1.58(s,9H),6.49(t,J=8.0Hz,2H),6.66(t,J=7 .5Hz,1H),6.81(dd,J=6.0,2.0Hz,1H),6.95–7.0(m,5H),7.14(d,J=2.0Hz,1H),7.20(td,J=7.5 ,3.0Hz,2H),7.26–7.37(m,5H),7.46(d,J=2.5Hz,1H),7.55(d,J=1.5Hz,1H),7.59(d,J=7.0Hz, 2H),7.65(t,J=6.0Hz,1H),8.13(d,J=8.5Hz,1H),8.43(d,J=8.0Hz,1H),9.08(d,J=6.0Hz,1H).

[0070] Example 3: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt162

[0071] The synthetic route is as follows:

[0072] Synthesis of Intermediate 3O-NO2: To a reaction flask were added A3 (10 g, 43.8 mmol, 1.5 eq), B (6.2 g, 29.2 mmol, 1.0 eq), tetrakis(triphenylphosphine)palladium (1.01 g, 0.88 mmol, 3 mol%), potassium carbonate (8.07 g, 58.4 mmol, 2.0 eq), dioxane (60 mL), and water (15 mL). The reaction was allowed to proceed at 90°C for 24 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 7.34 g of a yellow solid in a 79% yield. 1 H NMR (500MHz, DMSO-d6) δ3.91(s,3H),7.30(dd,J=7.5,1.5Hz,1H),7.38(dd,J=8.5,2.5Hz,1H),7.44(td,J=7.5 ,0.5Hz,1H),7.59–7.61(m,2H),7.56(m,1H),7.69(d,J=1.0Hz,1H),7.73(d,J=8.0Hz,1H),8.18–8.20(m,2H).

[0073] Synthesis of intermediate 3O-NH: To a reaction flask, add 3O-NO (7.3 g, 30.6 mmol, 1.0 equiv) and triphenylphosphine (24.1 g, 91.8 mmol, 3.0 equiv), followed by o-dichlorobenzene (60 mL). Incubate at 180°C for 24 hours, cool to room temperature, concentrate, and chromatograph on a silica gel column to afford 6.03 g of a brown solid (76% yield). Use directly in subsequent reactions.

[0074] Synthesis of intermediate 3O-OMe: To a reaction flask, add 3O-NH (4.8 g, 16.7 mmol, 1.0 equiv), 4-(tert-butyl)-2-chloropyridine (3.68 g, 21.7 mmol, 1.3 equiv), tris(dibenzylideneacetone)dipalladium (421 mg, 1.00 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (822 mg, 2.0 mmol, 6 mol%), and sodium tert-butoxide (3.2 g, 33.4 mmol, 2.0 equiv). Toluene (50 mL) was added. The reaction was allowed to react at 110°C for 48 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 4.92 g of a brown solid (72% yield). This was used directly in subsequent reactions.

[0075] Synthesis of intermediate 3O-OH: To a reaction flask, add 3O-OMe (4.9 g, 6.7 mmol, 1.0 equiv), pyridine hydrochloride (7.74 g, 67 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 3.4 g of a brown solid (87% yield). Use directly in subsequent reactions.

[0076] Synthesis of intermediate tBu-3O-Cl: To a reaction flask were added 3O-OH (1.0 g, 2.5 mmol, 1.0 equiv), 3-chloro-5-bromo-tert-butylbenzene (804 mg, 3.25 mmol, 1.3 equiv), 2-picolinic acid (62 mg, 0.5 mmol, 20 mmol%), cuprous iodide (48 mg, 0.25 mmol, 10 mmol%), potassium phosphate (1.06 g, 5 mmol, 2.0 equiv), and dimethyl sulfoxide (10 mL). The reaction was allowed to stand at 100°C for 24 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 590 mg of a white solid in a 68% yield. 1H NMR (500MHz, DMSO) δ1.24(s,9H),1.37(s,9H),6.87(t,J=2.5Hz,1H),7.11(t,J=2.0Hz,1H),7. 14(dd,J=8.5,2.0Hz,1H),7.19(t,J=1.5Hz,1H),7.44(td,J=7.2,1.5Hz,1H),7.52–7.48(m,2H ),7.55(dd,J=5.5,2.0Hz,1H),7.58(d,J=2.0Hz,1H),7.80(d,J=2.0Hz,1H),8.12(d,J=8.5Hz, 1H), 8.24 (d, J = 7.5Hz, 1H), 8.30 (d, J = 8.0Hz, 1H), 8.38 (d, J = 8.5Hz, 1H), 8.57 (d, J = 4.5Hz, 1H).

[0077] Synthesis of Intermediate LNH-162: To a reaction flask, add dPh-tBuNH2 (300 mg, 0.76 mmol, 1.0 equiv), followed by tBu-3O-Cl (458 mg, 0.8 mmol, 1.05 equiv), tris(dibenzylideneacetone)dipalladium (21 mg, 0.03 mmol, 3 mol%), 2-(di-tert-butylphosphino)biphenyl (14 mg, 0.06 mmol, 6 mol%), and sodium tert-butoxide (146 mg, 1.5 mmol, 2.0 equiv). Toluene (5 mL) was added. The reaction was allowed to react at 85°C for 3 hours, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 271 mg of a white solid (50% yield). This was used directly in subsequent reactions.

[0078] Synthesis of Ligand L-162: To a reaction flask, add LNH-162 (271 mg, 0.29 mmol, 1.0 equivalent), followed by ammonium hexafluorophosphate (94 mg, 0.58 mmol, 2.0 equivalent), and triethyl orthoformate (5 mL). After reacting at 80°C for 2 hours, the reaction was stopped, cooled to room temperature, concentrated, and purified by silica gel column chromatography to afford 197 mg of a white solid (63% yield). 1H NMR (500MHz, DMSO) δ1.31 (s, 9H), 1.36 (s, 9H), 1.43 (s, 9H), 6.81 (t, J = 2.0Hz, 1H), 6. 95(t,J=1.5Hz,1H),7.11–7.16(m,10H),7.24(dd,J=8.5,2.5Hz,1H),7.44–7.58(m,8H ),7.72–7.75(m,4H),7.83(d,J=1.5Hz,1H),8.15(d,J=8.5Hz,1H),8.25(d,J=7.5Hz,1 H),8.35(d,J=8.0Hz,1H),8.46(d,J=8.5Hz,1H),8.58(d,J=5.5Hz,1H),10.24(s,1H).

[0079] Synthesis of Pt162: To a reaction flask, add L-162 (153 mg, 0.15 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (55 mg, 0.16 mmol, 1.05 equiv), and sodium acetate (37 mg, 0.45 mmol, 3.0 equiv). Add diethylene glycol dimethyl ether (10 mL). React at 120°C for 72 hours, cool to room temperature, concentrate, and purify by silica gel column chromatography to afford 138 mg of a light yellow solid (78% yield). 1 H NMR (500MHz, CDCl3) δ1.13(s,9H),1.47(s,9H),1.53(s,9H),6.22(t,J=7.5Hz,2H),6.37(dd,J=6.0,1.5Hz,1H),6.48 (t,J=2.5Hz,1H),6.69(d,J=6.5Hz,2H),6.94(d,J=7.0Hz,1H),7.07–7.02(m,1H),7.12(d,J=1.5Hz,1H),7.21–7.25(m ,2H),7.28–7.32(m,2H),7.35–7.39(m,2H),7.44–7.51(m,4H),7.54(d,J=1.5Hz,1H),7.61(d,J=7.5Hz,2H),7.70(s, 1H),7.86(d,J=8.0Hz,1H),7.99(d,J=8.5Hz,1H),8.06(d,J=8.0Hz,1H),8.12(d,J=8.0Hz,2H),9.04(d,J=6.0Hz,1H).

[0080] Example 4: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt6

[0081] The synthetic route is as follows:

[0082] Pt6 was synthesized using the same synthesis steps and reaction conditions as Pt162. The target product, LNH-6, was obtained as a light green foamy solid (680 mg) in a 59% yield. The target product, L-6, was obtained as a light green foamy solid (377 mg) in a 58% yield. Molecular weight [M] + :883.4. The target product Pt6 was synthesized as a yellow solid (180 mg) with a yield of 60%. Molecular weight [M+H] + :1076.3.

[0083] Example 5: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt13

[0084] The synthetic route is as follows:

[0085] Pt13 was synthesized using the same synthesis steps and reaction conditions as Pt162. The target product, LNH-13, was obtained as a light green foamy solid (900 g) in a 64% yield. The target product, L-13, was obtained as a light green foamy solid (423 mg) in a 58% yield. Molecular weight [M] + :827.3. The target product Pt13 was synthesized as a yellow solid (30 mg) with a yield of 26%. Molecular weight [M+H] + :1020.33.

[0086] Example 6: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt14

[0087] The synthetic route is as follows:

[0088] Pt14 was synthesized using the same synthesis steps and reaction conditions as Pt162. The target product, LNH-14, was obtained as a light green foamy solid (1.5 g) with a yield of 70%. The target product, L-14, was obtained as a light green foamy solid (800 mg) with a yield of 62%. Molecular weight [M] + :883.4. The target product Pt14 was synthesized as a yellow solid (346 mg) with a yield of 59%. Molecular weight [M+H] + :1076.3.

[0089] Example 7: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt-154

[0090] The synthetic route is as follows:

[0091] Pt154 was synthesized using the same synthesis steps and reaction conditions as Pt162. The target product, LNH-154, was obtained as a light green foamy solid (1.1 g) in a 60% yield. The target product, L-154, was obtained as a light green foamy solid (504 mg) in a 63% yield. Molecular weight [M] + : 939.5. The target product Pt154 was synthesized as a yellow solid (178 mg). Yield: 78%. Molecular weight [M+H] + :1132.4.

[0092] Example 8: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt197

[0093] The synthetic route is as follows:

[0094] Pt197 was synthesized using the same synthesis steps and reaction conditions as Pt162. The target product, LNH-197, was obtained as a light green foamy solid (2.4 g) with a yield of 50%. The target product, L-197, was obtained as a light green foamy solid (1 g) with a yield of 60%. Molecular weight [M] + :843.3. The target product Pt197 was synthesized as a yellow solid (210 mg) with a yield of 23%. Molecular weight [M+H] + :1036.3.

[0095] Example 9: Synthesis of Pt26

[0096] Pt26 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product Pt26 was obtained as a yellow solid (530 mg) with a yield of 58%. Molecular weight [M+H] + :1215.5.

[0097] Example 10: Synthesis of Pt63

[0098] Pt63 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product Pt63 was obtained as a yellow solid (432 mg) with a yield of 70%. Molecular weight [M+H] + :1264.5.

[0099] Example 11: Synthesis of Pt76

[0100] Pt76 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (801 mg) with a yield of 65%. Molecular weight [M+H] + :1474.7.

[0101] Example 12: Synthesis of Pt230

[0102] Pt230 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt-162. The target product Pt230 was obtained as a yellow solid (56 mg) with a yield of 40%. Molecular weight [M+H] + :1510.7.

[0103] Example 13: Synthesis of Pt237

[0104] Pt237 was synthesized using the same synthesis steps and reaction conditions as Pt162. The target product was obtained as a yellow solid (730 mg) with a yield of 43%. Molecular weight [M+H] + :1342.5.

[0105] Example 14: Synthesis of Pt244

[0106] Pt244 was synthesized using the same synthesis steps and reaction conditions as Pt162. The target product was obtained as a yellow solid (530 mg) with a yield of 52%. Molecular weight [M+H] + :1490.6.

[0107] Example 15: Synthesis of Pt252

[0108] Pt252 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product Pt252 was obtained as a yellow solid (121 mg) with a yield of 61%. Molecular weight [M+H] + :1399.6.

[0109] Example 16: Synthesis of Pt257

[0110] Pt257 was synthesized using the same synthesis steps and reaction conditions as Pt162. The target product, Pt257, was obtained as a yellow solid (158 mg) in a 30% yield. Molecular weight [M+H] + :1260.4.

[0111] Example 17: Synthesis of Pt258

[0112] Pt258 was synthesized using the same synthesis steps and reaction conditions as Pt162. The target product, Pt258, was obtained as a yellow solid (188 mg) in a 60% yield. Molecular weight [M+H] + :1343.5.

[0113] Example 18: Synthesis of Pt263

[0114] Pt263 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. 472 mg of the target product was obtained as a yellow solid with a yield of 50%. Molecular weight [M+H] + :1461.5.

[0115] Example 19: Synthesis of Pt264

[0116] Pt264 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (545 mg) with a yield of 49%. Molecular weight [M+H] + :1461.5.

[0117] Example 20: Synthesis of Pt328

[0118] Pt328 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (571 mg) with a yield of 45%. Molecular weight [M+H] + :1378.5.

[0119] Example 21: Synthesis of Pt333

[0120] Pt333 was synthesized using the same synthesis steps and reaction conditions as Pt162. The target product was obtained as a yellow solid (418 mg) with a yield of 47%. Molecular weight [M+H] + :1126.3.

[0121] Example 22: Synthesis of Pt362

[0122] Pt362 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (590 mg) with a yield of 63%. Molecular weight [M+H] + :1414.7.

[0123] Example 23: Synthesis of Pt364

[0124] Pt364 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (518 mg) with a yield of 53%. Molecular weight [M+H] + :1490.7.

[0125] Example 24: Synthesis of Pt365

[0126] Pt365 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (459 mg) with a yield of 61%. Molecular weight [M+H] + :1283.4.

[0127] Example 25: Synthesis of Pt372

[0128] Pt372 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (480 mg) with a yield of 63%. Molecular weight [M+H] +:1413.6.

[0129] Example 26: Synthesis of Pt378

[0130] Pt378 was synthesized using the same synthesis steps and reaction conditions as Pt162. The target product was obtained as a yellow solid (556 mg) with a yield of 52%. Molecular weight [M+H] + :1307.4.

[0131] Example 27: Synthesis of Pt383

[0132] Pt383 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt162. The target product was obtained as a yellow solid (458 mg) with a yield of 47%. Molecular weight [M+H] + :1471.7.

[0133] Theoretical calculation instructions

[0134] 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.

[0135] Table 1. Electrons and holes in the T1 excited state of some metal complexes of the present invention

[0136] As can be seen from Table 1, the present invention introduces cyclization at different positions of carbazole, expands the conjugated system and increases the distribution of local excited states, making the emission shoulder peak lower and the half-peak width narrower, with higher color purity, which can meet the requirements of blue light materials.

[0137] Photophysical properties:

[0138] Table 2. Photophysical properties of some complexes in dichloromethane solution

[0139] Figures 1-3 show the room-temperature emission spectra of Pt150, Pt162, Pt166, and R1 in dichloromethane solutions, respectively. Comparing the room-temperature emission spectra of these platinum complexes in dichloromethane solutions, Figures 1-3 and Table 2 demonstrate that the introduction of cyclization at different positions of the carbazole expands the conjugated system and increases the distribution of localized excited states, resulting in a lower emission shoulder, a narrower half-width (FWHM), and higher color purity. The maximum emission wavelength of the platinum complex Pt166 is 462.2 nm, with a FWHM of 18.6 nm.

[0140] Fabrication of OLED devices:

[0141] As a reference preparation method for a device embodiment, the present invention deposits a p-type dopant material on 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.

[0142] 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) (Pt150:HTH-85:ETH-45 mass ratio is 10:60:30) / ETH-5 (5 nm) / ET-14 (40 nm) / LiQ (1 nm) / Al (100 nm).

[0143] Device Examples 2-27 and Comparative Example 1 were prepared using structures similar to those of Device Example 1, with the only difference being that Pt150 in Device Example 1 was replaced with Pt166, Pt162, Pt6, Pt13, Pt14, Pt154, Pt197, Pt26, Pt63, Pt76, Pt230, Pt237, Pt63, Pt76, Pt244, Pt313, Pt327, Pt333, Pt338, Pt362, Pt364, Pt365, Pt367, Pt372, Pt378, Pt380, and R1, respectively. The luminescence characteristics of the comparative examples and device examples prepared above were tested using standard methods and are shown in Table 2. The device structures involved are as follows: wherein P-4 is HATCN and ET-14 is BPyTP.

[0144] Table 3. Device luminescence characteristics data table

[0145] As can be seen from Table 3, compared with Comparative Example 1, Device Examples 1 to 27 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, and the CIEy values ​​are all less than 0.19.

[0146] In a preferred specific embodiment, the structure of device example 28 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) (Pt150:BN1-8:HTH-85:ETH-45 mass ratio is 10:1:59:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0147] Device Examples 29-34 were prepared using structures similar to those of Device Example 28, differing only in that the platinum (II) complex and the boron-containing compound in Device Example 29 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.

[0148] Table 4. Device structure and luminescence characteristics data

[0149] 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.

[0150] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A tetradentate metal platinum (II) complex of cyclic carbazole, characterized in that: The complex has a general structure as shown in formula (I) to formula (V): In formula (I) to formula (V), X is selected from C, 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 deuterated alkyl, C1-C30 haloalkyl, C1-C30 cycloalkyl, C1-C30 heterocycloalkyl, C6-C60 aryl or condensed aromatic hydrocarbon group, C6-C60 heteroaryl or condensed heteroaromatic hydrocarbon group, C6-C60 aromatic amine group and combinations thereof; when containing heteroatoms, the heteroatoms are selected from N and O.

2. The tetradentate metal platinum (II) complex of cyclic carbazole according to claim 1, characterized in that: R 1 , R 6 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, 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 and combinations thereof.

3. The tetradentate metal platinum (II) complex of cyclic carbazole according to claim 1, characterized in that: R 1 , R 6 -R 9 Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, and combinations thereof.

4. The tetradentate metal platinum (II) complex of cyclic carbazole according to claim 1, characterized in that: R 2 -R 5 Each is independently selected from the group consisting of hydrogen, deuterium, CD3, F, CF3, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, naphthyl, pyridyl, quinolyl, cyclopentane, cyclohexane, a five-membered heterocycle, diphenylamine, and combinations thereof.

5. The tetradentate metal platinum (II) complex of cyclic carbazole according to claim 1, characterized in that: The complex is selected from any one of the following chemical structures, wherein "D" represents deuterium:

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 8, 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.

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