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

Abstract

The present invention belongs to the field of organic electroluminescence, and specifically relates to a fluorine-containing tetradentate ring metal platinum (II) complex, an electronic device and its application. The provided tetradentate ring metal platinum (II) complex has a structure as shown in formula (I) or formula (II): #imgabs0# In formula (I) or formula (II), F n It indicates that there are one or more F substitutions on the benzene ring, wherein n is a positive integer from 1 to 5. The compound provided by the present invention has good chemical stability, can improve and balance the transport of holes and electrons, and make the energy transfer between the host and the guest more efficient, which is specifically manifested in the improvement of the current efficiency and life of the compound or composition of the present invention as an organic electroluminescent device, and has great application prospects in the field of OLED display and lighting.

Description

Technical Field

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

[0002] Organic light-emitting diodes (OLEDs) are a new generation of full-color display and lighting technology. Compared with liquid crystal displays, which have the disadvantages of 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-saving; 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 also 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 is the design and development of luminescent materials. In the currently used OLED devices, the luminescent layer almost all uses the host-guest luminescent system mechanism, that is, the guest luminescent material is doped in the host material. The energy system of the host material is generally greater than that of the guest luminescent material. The energy is transferred from the host material to the guest material, so that the guest material is excited and emits light. Commonly used organic phosphorescent guest materials are generally heavy metal atoms such as iridium (III), platinum (II), Pd (II), etc. Commonly used phosphorescent organic materials mCBP (3,3′-bis (9-carbazolyl) -biphenyl) and 2,6-mCPy (2,6-bis (9-carbazolyl) -pyridine) have high efficiency and high triplet energy levels. When used as organic materials, the triplet energy can be effectively transferred from the luminescent organic material to the guest phosphorescent luminescent material. However, due to the characteristics of mCBP that holes are easy to transport and electrons are difficult to flow, and 2,6-mCPy has poor hole transport, the charge of the luminescent layer is unbalanced, resulting in a reduction in the current efficiency of the device. In addition, the number of heavy metal phosphorescent organic complex molecules and cyclometallated iridium (III) complex molecules currently used 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 that of PtCl2 used to prepare phosphorescent materials of platinum (II) complexes. In addition, the preparation of phosphorescent materials of iridium (III) complexes involves four steps: iridium (III) dimer, iridium (III) intermediate ligand exchange, synthesis of mer-iridium (III) complexes, and conversion of mer- to fac-iridium (III) complex isomers, which greatly reduces the total yield and the cost of raw material IrCl3 . The 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 involves the metallization of the ligand in the last step, which is the reaction of designing platinum salts. The utilization rate of platinum elements is high, which 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, there are still some technical difficulties in the development of platinum complex materials and devices. How to improve the efficiency and life of the device is a relatively important research issue. Therefore, it is urgent to develop new phosphorescent metal platinum (II) complexes. Summary of the invention

[0004] In view of this, the object of the present invention is to provide a fluorine-containing tetradentate ring metal platinum (II) complex, an electronic device and its application. The fluorine-containing tetradentate ring metal platinum (II) complex of the present invention can be used as a guest phosphorescent material of the light-emitting layer to make the device have excellent performance. Furthermore, combining it with a specific host material can improve the current efficiency of electronic devices, especially organic electroluminescent devices, improve the device life, and also reduce the operating voltage of the components.

[0005] The present invention provides a fluorine-containing tetradentate ring metal platinum (II) complex, wherein the complex has a structure as shown in formula (I) or formula (II):

[0006]

[0007] In formula (I) or formula (II), F n Indicates that the benzene ring is substituted with one or more F, wherein n is a positive integer from 1 to 5;

[0008] R a It represents mono-, di-, tri-, tetra- or unsubstituted; R a is selected from H or C1-C30 alkyl;

[0009] R1, R2, and R3 are each independently selected from the group consisting of hydrogen, F, N, O, S, CN, C1-C30 alkyl, C1-C30 cycloalkyl, C1-C30 cycloheteroalkyl, C1-C30 haloalkyl, C6-C60 aryl, and C6-C60 heteroaryl.

[0010] Preferably, at least one hydrogen in R1, R2, and R3 can be replaced by deuterium or F.

[0011] Preferably, R1 and R3 are each independently selected from hydrogen or a C1-C30 alkyl group.

[0012] Further preferably, R2 is selected from hydrogen, deuterium, CN, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C1-C30 cycloalkyl, substituted or unsubstituted C1-C30 cycloheteroalkyl, substituted or unsubstituted C1-C30 haloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 heteroaryl; wherein the heteroatoms on the heteroalkyl, cycloheteroalkyl or heteroaryl are selected from one or more of O, S and / or N.

[0013] Further preferably, the tetradentate cyclometal platinum (II) complex is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027] Furthermore, the present invention also provides the use of the tetradentate metal platinum (II) complex having a structure shown in formula (I) or formula (II) in electronic devices.

[0028] 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).

[0029] In another aspect, the present invention further provides an organic electroluminescent device, which comprises the tetradentate metal platinum (II) complex having a structure represented by formula (I) or formula (II) as described above.

[0030] Furthermore, the organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises the tetradentate metal platinum (II) complex having a structure represented by formula (I) or formula (II) as described above.

[0031] Preferably, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the tetradentate metal platinum (II) complex having a structure represented by formula (I) or formula (II) as described above.

[0032] Furthermore, the light-emitting layer further comprises a fluorescent doping material; the fluorescent doping material is selected from any one or more of the compounds represented by formula (BN1) to formula (BN5):

[0033]

[0034] Wherein, X is O, S, Se or NR 300 ;

[0035] X 1 , X 2 , X 3 , X 4 Each independently represents O, S, Se or N;

[0036] R b -R e Each independently represents mono-, di-, tri-, tetra- or unsubstituted; R b -R e Each is independently selected from the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, and C6-C60 aryl; 11 Each independently represents the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, and C6-C60 aryl.

[0037] Preferably, R4, R5, R6, and R9 are each independently selected from a substituted or unsubstituted diphenylamine group, a substituted or unsubstituted carbazole group; the substitution may be multiple substitutions, and when containing substituents, the substituents are selected from deuterium, C1-C30 alkyl groups, and C6-C30 aryl groups.

[0038] Preferably, the R7-R8, R 10 -R 11 Each is independently selected from the group consisting of hydrogen, C1-C30 alkyl, and C6-C60 aryl.

[0039] Further preferably, the R4-R 11 At least one hydrogen in may be replaced by deuterium.

[0040] Further, the fluorescent doping material is selected from any one of the chemical structures shown below, wherein Ph represents a phenyl group, and D4 and D5 mean substituted by 4 and 5 deuterium atoms, respectively:

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049] In another aspect, the present invention further provides an organic photoelectric device, which comprises: a substrate layer; a first electrode, the first electrode being on the substrate; an organic light-emitting functional layer, the organic light-emitting functional layer being on the first electrode; a second electrode, the second electrode being on the organic light-emitting functional layer; wherein the organic light-emitting functional layer comprises a tetradentate metal platinum (II) complex having a structure shown in formula (I) or formula (II) as above. For example, the platinum (II) complex can be included in the organic light-emitting functional layer as a light-emitting material.

[0050] Furthermore, the organic light-emitting functional layer further comprises any one or more fluorescent doping materials of the compounds represented by formula (BN1) to formula (BN5) as above.

[0051] The present invention also provides a composition, which comprises a tetradentate metal platinum (II) complex having a structure as shown in formula (I) or formula (II). Preferably, the composition further comprises any one or more fluorescent doping materials of the compounds represented by formula (BN1) to formula (BN5).

[0052] The present invention also provides a preparation, the preparation comprising a tetradentate metal platinum (II) complex having a structure shown in formula (I) or formula (II) as above or a composition as described above and at least one solvent. The solvent is not particularly limited, and can be used, for example, unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, methylene chloride, ethylene dichloride, butyl chloride, butyl bromide, pentyl chloride, pentyl bromide, hexyl chloride, hexyl bromide, chlorocyclohexane, bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, ether solvents such as tetrahydrofuran, tetrahydropyran, ester solvents such as alkyl benzoate, etc., which are well known to those skilled in the art.

[0053] Preferably, the composition further comprises any one or more fluorescent doping materials of the compounds represented by formula (BN1) to formula (BN5) as above.

[0054] The present invention also provides a display or lighting device, which comprises one or more of the organic photoelectric devices described above.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] The present invention provides a phosphorescent material of a tetradentate ring metal platinum (II) complex. The charge distribution of the excited state is improved by introducing fluorine atoms at appropriate positions of the ligands, so that the excited state of the material has more metal to pyridocarbene charge transfer states ( 3 MLCT), which is beneficial to improve its radiation rate and thus improve the life of the device. The materials involved in the present invention have good chemical stability and thermal stability, and are easy to prepare vapor-deposited OLED devices. After being combined with fluorescent doping materials, the transmission of holes and electrons can be balanced, making the energy transfer between the host and the guest more efficient. The organic electroluminescent device made using the compound of the present invention as the light-emitting layer has a significant improvement in current efficiency and life, and significantly reduces the lighting voltage. In particular, the light color purity of the device can be improved when used together with phosphorescence-sensitized boron-containing compounds. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 This is the room temperature emission spectrum of the prepared platinum complex Pt1-Pt6 in dichloromethane solution. DETAILED DESCRIPTION

[0058] The contents of the present invention will be described in detail below. The description of the constituent elements 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.

[0059] The term "substituted" used in the present invention is intended to include all allowed substituents of organic compounds. In a wide aspect, allowed 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, allowed substituents can be one or more, the same or different. For the purpose of the present invention, heteroatoms (such as nitrogen) can have hydrogen substituents and / or any allowed substituents of organic compounds described in the present invention, which satisfy the valence of the heteroatoms. The present invention is not intended to impose any restrictions in any way with the allowed substituents of organic compounds. Similarly, the term "substituted" or "substituted with" contains implicit conditions that this substitution conforms to the allowed valence of the substituted atom and the substituent, and the substitution leads to a stable compound (for example, a compound that will not spontaneously undergo transformation (for example, by rearrangement, cyclization, elimination, etc.)). It is also contemplated that, in certain aspects, unless explicitly stated to the contrary, individual substituents can be further optionally substituted (ie, further substituted or unsubstituted).

[0060] In defining various terms, “R1”-“R 11 " are used as general symbols in the present invention to indicate 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 may be limited to some other substituents in other cases.

[0061] The "R1", "R2", "R3" ... "R n "" (wherein n is an integer) may independently have one or more of the groups listed above. For example, if R 1 For straight chain alkyl, one hydrogen atom of alkyl can be optionally substituted with hydroxyl, alkoxy, alkyl, halogen etc. Depending on the selected group, the first group can be combined in the second group, or alternatively, the first group can be suspended and connected to the second group. For example, for the phrase "alkyl containing amino", the amino group can be combined in the main chain of alkyl. Alternatively, the amino group can be connected to the main chain of alkyl. The nature of the selected group will determine whether the first group is embedded in or connected to the second group.

[0062] The term "alkyl" used in the present invention is a saturated hydrocarbon group of 1 to 60 carbon atoms that 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, sulphur-oxo or sulfhydryl groups of the present invention.

[0063] 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 the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, sulfo-oxo or thiol groups described herein.

[0064] The term "amine" or "amino group" as used herein refers to an amino group of the formula -NR 1 R 2 Indicates that R 1 and R 2 The radicals may be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl.

[0065] Compounds of the present invention may contain "optionally substituted" parts. Typically, the term "substituted" (whether or not the term "optionally" is present in the front) means that one or more hydrogens of the indicated part are replaced by suitable substituents. Unless otherwise specified, "optionally substituted" groups may have suitable substituents at each substitutable position of the group, and when more than one position may be substituted with more than one substituent selected from a specified group in any given structure, the substituents at each position may be the same or different. The substituent combinations envisioned by the present invention are preferably those that form stable or chemically feasible compounds. In some respects, unless clearly indicated to the contrary, it is also contemplated that each substituent may be further optionally substituted (that is, further substituted or unsubstituted).

[0066] The structure of the compound can be represented by the following formula:

[0067]

[0068] It is understood to be equivalent to the following formula:

[0069]

[0070] Where n is usually an integer. That is, R n is understood to mean five individual substituents R a(1) , R a(2) , R a(3) , R a(4) , R a (5) "Individual substituent" means that each R substituent can be defined independently. For example, if in one case R a(m) is a halogen, then in this case R a(n) Not necessarily halogen.

[0071] 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.

[0072] The compounds of the present invention may be prepared using a variety of methods, including but not limited to those described in the examples provided herein.

[0073] It should be noted that the above general description and the following detailed description are exemplary and explanatory only and are not restrictive.

[0074] The present application may be understood more readily by reference to the following detailed description and the Examples included therein.

[0075] 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 this can of course vary. It should also be understood that the terms used in the present invention are only used 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 in the present invention can be used in the practice or test, exemplary methods and materials are described below. Synthesis Examples All raw materials and solvents are commercially available unless otherwise specified, and solvents are used directly without further treatment.

[0076] The substrate of the present invention can be any substrate used in typical organic optoelectronic devices. It can be a glass or transparent plastic substrate, or a substrate of an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance. Depending on the properties of the substrate, the use direction is different. As the material for the hole injection layer, the hole transport layer, and the electron injection layer, any material can be selected from the known related materials for OLED devices, and the present invention does not make specific restrictions thereon.

[0077] Synthesis Example

[0078] The following examples of compound synthesis, composition, device or method are only to provide a general method for the industry, and are not intended to limit the scope of protection of the patent. The data (quantity, temperature, etc.) mentioned in the patent are as accurate as possible, but there may be some errors. Unless otherwise specified, weighing is separate weighing, temperature is ℃, or room temperature, and pressure is close to normal pressure.

[0079] The following examples provide methods for preparing new compounds, but the preparation of such compounds is not limited to this method. In this professional and technical field, since the protected compounds in the present invention are easy to modify and prepare, their preparation can adopt the following methods or other methods. The following examples are only examples and are not intended to limit the scope of protection of this patent. Temperature, catalyst, concentration, reactants and reaction process can all be changed to select different conditions for preparing the compounds for different reactants.

[0080] 1 H NMR (500MHz), 1 H NMR (400MHz), 13 C NMR (126 MHz) spectra were measured on an ANANCE III (500M) NMR spectrometer. Unless otherwise specified, DMSO-d6 or CDCl3 containing 0.1% TMS was used as the solvent for NMR. 1When CDCl3 is used as the solvent, TMS (δ=0.00 ppm) is used as the internal standard for H NMR spectra. When DMSO-d6 is used as the solvent, TMS (δ=0.00 ppm) or the residual DMSO peak (δ=2.50 ppm) or the residual water peak (δ=3.33 ppm) is used as the internal standard. 13 In the C NMR spectrum, 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 spectrum was 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.

[0081] Synthesis of intermediate 1

[0082] The synthetic route of intermediate 1 is as follows:

[0083]

[0084] (1) A (256 mg, 1.0 mmol, 1.0 equivalent), B (210 mg, 1.5 mmol, 1.5 equivalent), tetrakis(triphenylphosphine)palladium (29 mg, 0.025 mmol, 0.025 equivalent), tripotassium phosphate (425 mg, 2.0 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried. The nitrogen was replaced three times. Dioxane (8 mL) and water (2 mL) were added under nitrogen protection. The mixture was stirred in an oil bath at 60 ° C for 12 hours, cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 2:1, and product C was obtained, a red liquid of 183 mg, with a yield of 88%. It was used directly in the next step.

[0085] (2) C (180 mg, 0.71 mmol, 1.0 equivalent), D (130 mg, 0.65 mmol, 1.1 equivalent), tris(dibenzylidene-BASE acetone)dipalladium (6 mg, 0.065 mmol, 0.01 equivalent), 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (16 mg, 0.026 mmol, 0.04 equivalent), cesium carbonate (263 mg, 0.81 mmol, 1.25 equivalent) were added to a sealed tube with a magnetic rotor and dried. The nitrogen was replaced three times, and toluene (5 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 120°C for 12 hours, cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 10:1, to obtain product E, a yellow solid 981 mg, yield 84%. It was used directly in the next step.

[0086] (3) E (6.52 g, 17.4 mmol, 1.0 equivalent) and stannous chloride dihydrate (16 g, 69.6 mmol, 4.0 equivalent) were added to a sealed tube with a magnetic rotor and dried, and nitrogen was replaced three times. Ethanol (60 mL) and ethyl acetate (60 mL) were added under nitrogen protection, and the mixture was stirred in an oil bath at 78 ° C for 9 hours, cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 5:1, to obtain intermediate 1, 5.7 g of purple solid, yield 90%.

[0087] Synthesis of intermediate 1-Cl

[0088] The synthetic route of intermediate 1-Cl is as follows:

[0089]

[0090] (1) F (10 g, 50.7 mmol, 1.0 equivalent), G (13 g, 60.8 mmol, 1.2 equivalent), tris(dibenzylidene-BASE acetone)dipalladium (464 mg, 0.5 mmol, 0.01 equivalent), 2-(di-tert-butylphosphino)biphenyl (303 mg, 1.0 mmol, 0.02 equivalent), sodium tert-butoxide (9.7 g, 101 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried. The nitrogen was replaced three times, and toluene (80 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 110° C. for 12 hours, cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 30:1, to obtain product H, 15 g of yellow oily liquid, with a yield of 91%.

[0091] (2) H (28 g, 84.7 mmol, 1.0 equivalent) and hydrobromic acid (69 g, 0.847 mmol, 10.0 equivalent) were added sequentially to a sealed tube with a magnetic rotor, and the mixture was stirred in an oil bath at 120° C. for 12 hours, cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The crude product was slurried and filtered to obtain product I, 26 g of a white solid, with a yield of 97%.

[0092] (3) I (5 g, 15.8 mmol, 1.0 equivalent), J (3.3 g, 17.4 mmol, 1.1 equivalent), cuprous iodide (300 mg, 1.58 mmol, 0.1 equivalent), 2-picolinic acid (389 mg, 3.16 mmol, 0.2 equivalent), tripotassium phosphate (6.7 g, 31.6 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried. The nitrogen was replaced three times, and dimethyl sulfoxide (50 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 100 ° C. for 12 hours, cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 20:1, to obtain the product intermediate 1-Cl. 5.3 g of white solid, yield 79%.

[0093] It should be noted that the above is only a feasible preparation scheme for one of the intermediates of the present invention. The intermediates required for each embodiment can be prepared with reference to the synthesis process of intermediate 1 and intermediate 1-Cl. The preparation of such intermediate compounds is not limited to this method. The preparation can be carried out by the methods listed above or by other methods known in the art. It is not intended to limit the scope of protection of the present invention.

[0094] Example 1: Synthesis of Pt1

[0095] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt1 is as follows:

[0096]

[0097] Synthesis of intermediate (1-NH): 1 (363 mg, 1.0 mmol, 1.0 equivalent), 1-Cl (470 mg, 1.1 mmol, 1.1 equivalent), tris (dibenzylidene-BASE acetone) dipalladium (27 mg, 0.03 mmol, 0.03 equivalent), 2- (di-tert-butylphosphine) biphenyl (18 mg, 0.06 mmol, 0.06 equivalent), sodium tert-butoxide (192 mg, 2.0 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried. The nitrogen was replaced three times, and toluene (5 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 100 ° C for 12 hours, cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 30:1, and the product 1-NH was obtained, a light green foamy solid 580 mg, a yield of 77%. It was used directly in the next step.

[0098] Synthesis of ligand L1: 1-NH (580 mg, 0.77 mmol, 1.0 equivalent) and ammonium hexafluorophosphonate (251 mg, 1.54 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried, and nitrogen was replaced three times. Triethyl orthoformate (10 mL) was added under nitrogen protection, and the mixture was stirred in an oil bath at 80 ° C for 10 hours, cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated and purified by silica gel chromatography, eluent: dichloromethane, to obtain product L1, 483 mg of light green foamy solid, yield 69%. 1 H NMR (500MHz, DMSO-d6): δ1.09(d,J=7.0Hz,6H),1.19(d,J=7.0Hz,6H),1.32(s,9H),2.36-2.42 (m,2H),7.24(dd,J=8.5,6.0Hz,1H),7.33–7.40(m,3H),7.45–7.51(m,3H),7.55(d,J=2.5Hz,1H ),7.62(d,J=8.0Hz,1H),7.69–7.76(m,5H),7.79(q,J=3.0Hz,4H),7.88–7.93(m,2H),8.01(d,J =8.0Hz, 1H), 8.26 (d, J = 8.0Hz, 1H), 8.35 (d, J = 8.5Hz, 1H), 8.60 (d, J = 5.5Hz, 1H), 10.62 (s, 1H).

[0099] Synthesis of Pt1: L1 (483 mg, 0.53 mmol, 1.0 equivalent), (1,5-cyclooctadiene) platinum dichloride (198 mg, 0.53 mmol, 1.0 equivalent) and sodium acetate (216 mg, 1.59 mmol, 3.0 equivalent) were added to a sealed tube with a magnetic rotor and dried, nitrogen was replaced three times, diethylene glycol dimethyl ether (30 mL) was added under nitrogen protection, nitrogen was bubbled for 30 minutes, and the sealed tube was wrapped with tin foil to avoid light, and the mixture was stirred in an oil bath at 120 ° C for 3 days, cooled to room temperature, added deionized water and stirred for 5-10 minutes to quench, added dichloromethane to extract, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by reduced pressure distillation. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 2:1, and the product Pt1 was obtained as a yellow solid 162 mg, with a yield of 32%. 1 H NMR (500MHz, DMSO-d6): δ0.97(s,9H),1.14(d,J=6.5Hz,6H),1.17(d,J=6.5Hz,6H),2.84–2.92(m,2H),6 .36(dd,J=6.5,4.5Hz,1H),6.78(d,J=1.0Hz,1H),7.14(d,J=8.0Hz,1H),7.27(d,J=8.0Hz,1H),7.30(d, J=7.5Hz,2H),7.37-7.41(m,5H),7.46-7.52(m,2H),7.54(s,1H),7.86(d,J=8.0Hz,2H),7.89(d,J=8.5H z, 1H), 7.97 (dd, J = 9.0, 5.5Hz, 2H), 8.14 (d, J = 7.0Hz, 1H), 8.27 (d, J = 8.5Hz, 1H), 8.65 (d, J = 6.0Hz, 1H).

[0100] Example 2: Synthesis of Pt2

[0101] The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material Pt2 is as follows:

[0102]

[0103] Synthesis of intermediate (2-NH): 1 (363 mg, 1.0 mmol, 1.0 equivalent), 2-Cl (531 mg, 1.1 mmol, 1.1 equivalent), tris (dibenzylidene-BASE acetone) dipalladium (27 mg, 0.03 mmol, 0.03 equivalent), 2- (di-tert-butylphosphine) biphenyl (18 mg, 0.06 mmol, 0.06 equivalent), sodium tert-butoxide (192 mg, 2.0 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried. The nitrogen was replaced three times, and toluene (5 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 100 ° C for 12 hours, cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 30:1, and the product 2-NH was obtained, a light green foamy solid 530 mg, a yield of 87%. It was used directly in the next step.

[0104] Synthesis of ligand L2: 2-NH (702 mg, 0.64 mmol, 1.0 equivalent) and ammonium hexafluorophosphonate (203 mg, 1.84 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried, and nitrogen was replaced three times. Triethyl orthoformate (10 mL) was added under nitrogen protection, and the mixture was stirred in an oil bath at 80 ° C for 10 hours, cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated and purified by silica gel chromatography, eluent: dichloromethane, to obtain product L2, 600 mg of light green foamy solid, yield 72%. 1 H NMR (500MHz, DMSO): δ1.15(d,J=5.0Hz,6H),1.24(d,J=5.0Hz,6H),1.37(s,9H),1.43(s,9H),2.39–2.48(m ,2H),7.29(dd,J=8.0,6.0Hz,1H),7.37–7.47(m,3H),7.49–7.58(m,3H),7.58(t,J=2.5Hz,1H),7.59(d,J= 2.5Hz,1H),7.69(d,J=8.0Hz,1H),7.74(q,J=2.0Hz,2H),7.77-7.82(m,3H),7.84(s,2H),7.94-7.98(m,2H ), 8.02 (d, J = 8.0Hz, 1H), 8.30 (d, J = 8.0Hz, 1H), 8.39 (d, J = 8.5Hz, 1H), 8.64 (d, J = 5.0Hz, 1H), 10.70 (s, 1H).

[0105] Synthesis of Pt2: L2 (600 mg, 0.62 mmol, 1.0 equivalent), (1,5-cyclooctadiene) platinum dichloride (221 mg, 0.59 mmol, 1.0 equivalent) and sodium acetate (153 mg, 1.87 mmol, 3.0 equivalent) were added to a sealed tube with a magnetic rotor and dried, nitrogen was replaced three times, diethylene glycol dimethyl ether (30 mL) was added under nitrogen protection, nitrogen was bubbled for 30 minutes, and the sealed tube was wrapped with tin foil to avoid light, and the mixture was stirred in an oil bath at 120 ° C for 3 days, cooled to room temperature, added deionized water and stirred for 5-10 minutes to quench, added dichloromethane to extract, the organic phase was combined, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 2: 1, and the product Pt2 was obtained, a yellow solid of 100 mg, with a yield of 84%. 1 H NMR (500MHz, DMSO-d6): δ0.94–1.29(m,21H),1.49(s,9H),2.70-3.01(m,2H),6.34(dd,J=6.0,4.0Hz, 1H),7.06(d,J=1.5Hz,1H),7.14(d,J=8.5Hz,1H),7.26(d,J=8.5Hz,1H),7.35–7.45(m,5H),7.49(t,J =6.0Hz,1H),7.59(t,J=8.5Hz,1H),7.66(s,1H),7.73(d,J=1.5Hz,1H),7.84(d,J=8.5Hz,2H),7.87(d ,J=8.5Hz,1H),7.93–8.01(m,2H),8.13(d,J=8.0Hz,1H),8.36(d,J=8.5Hz,1H),8.59(d,J=6.5Hz,1H).

[0106] Example 3: Synthesis of Pt3

[0107] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt3 is as follows:

[0108]

[0109] Synthesis of intermediate (3-NH): 1 (363 mg, 1.0 mmol, 1.0 equivalent), 3-Cl (646 mg, 1.1 mmol, 1.1 equivalent), tris (dibenzylidene-BASE acetone) dipalladium (27 mg, 0.03 mmol, 0.03 equivalent), 2- (di-tert-butylphosphine) biphenyl (18 mg, 0.06 mmol, 0.06 equivalent), sodium tert-butoxide (192 mg, 2.0 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried. The nitrogen was replaced three times, and toluene (5 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 100 ° C for 12 hours, cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 30:1, and the product 3-NH was obtained, a light green foamy solid 730 mg, a yield of 80%. It was used directly in the next step.

[0110] Synthesis of ligand L3: 3-NH (730 mg, 0.64 mmol, 1.0 equivalent) and ammonium hexafluorophosphonate (261 mg, 1.60 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried, and nitrogen was replaced three times. Triethyl orthoformate (10 mL) was added under nitrogen protection, and the mixture was stirred in an oil bath at 80 ° C for 10 hours, cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated and purified by silica gel chromatography, eluent: dichloromethane, to obtain product L3, 633 mg of light green foamy solid, yield 74%. 1 H NMR (500MHz, DMSO-d6): δ0.93(d,J=4.5Hz,6H),1.10(t,J=6.5Hz,12H),1.20(d,J=6.5Hz,6H),1.34(s,9H),2.39-2.45(m,2H),2 .58-2.64(m,2H),7.09(dd,J=2.0,1.0Hz,1H),7.22(d,J=7.5Hz,2H),7.28(dd,J=8.5,6.0Hz,1H),7.33–7.40(m,4H),7.46–7.53 (m,3H),7.57(d,J=2.5Hz,1H),7.66(d,J=8.5Hz,1H),7.71–7.79(m,3H),7.80(s,2H),7.83(t,J=8.5Hz,1H),7.87(t,J=2.5Hz,1 H),7.89–7.93(m,2H),8.02(d,J=8.0Hz,1H),8.26(d,J=7.5Hz,1H),8.36(d,J=8.5Hz,1H),8.60(d,J=5.5Hz,1H),10.65(s,1H).

[0111] Synthesis of Pt3: L3 (633 mg, 0.59 mmol, 1.0 equivalent), (1,5-cyclooctadiene) platinum dichloride (222 mg, 0.59 mmol, 1.0 equivalent) and sodium acetate (241 mg, 1.78 mmol, 3.0 equivalent) were added to a sealed tube with a magnetic rotor and dried, and nitrogen was replaced three times. Diethylene glycol dimethyl ether (30 mL) was added under nitrogen protection, and nitrogen was bubbled for 30 minutes. The sealed tube was wrapped with tin foil to avoid light, and the mixture was stirred in an oil bath at 120 ° C for 3 days, cooled to room temperature, and deionized water was added and stirred for 5-10 minutes to quench, and dichloromethane was added to extract, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 2:1, and the product Pt3 was obtained as a yellow solid 476 mg, with a yield of 72%. 1 H NMR (500MHz, DMSO-d6): δ0.70–1.64(m,33H),2.77–3.21(m,4H),6.34(dd,J=6.0,4.0Hz,1H),7.06(d,J=8.0Hz,1H),7.13(d,J=8.0Hz,1H),7.26(d,J =8.0Hz,1H),7.31–7.79(m,11H),7.80–7.91(m,4H),7.97(dd,J=5.5,3.0H z, 2H), 8.13 (d, J = 6.5Hz, 1H), 8.45 (d, J = 8.0Hz, 1H), 8.61 (d, J = 5.0Hz, 1H).

[0112] Example 4: Synthesis of Pt4

[0113] The synthesis route of the tetradentate metal platinum (II) complex phosphorescent material Pt4 is as follows:

[0114]

[0115] Synthesis of intermediate 4-NH: 2 (413 mg, 1.0 mmol, 1.0 equivalent), 2-Cl (531 mg, 1.1 mmol, 1.1 equivalent), tris (dibenzylidene-BASE acetone) dipalladium (27 mg, 0.03 mmol, 0.03 equivalent), 2- (di-tert-butylphosphine) biphenyl (18 mg, 0.06 mmol, 0.06 equivalent), sodium tert-butoxide (192 mg, 2.0 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried. The nitrogen was replaced three times, and toluene (5 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 100 ° C for 12 hours, cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 30:1 to obtain the product 4-NH, a light green foamy solid 661 mg, a yield of 77%. Since it is easily oxidized and not stable enough, it is directly used in the next reaction.

[0116] Synthesis of ligand L4: 4-NH (661 mg, 0.77 mmol, 1.0 equivalent) and ammonium hexafluorophosphonate (251 mg, 1.54 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried, and nitrogen was replaced three times. Triethyl orthoformate (10 mL) was added under nitrogen protection, and the mixture was stirred in an oil bath at 80 ° C for 10 hours, cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated and purified by silica gel chromatography, eluent: dichloromethane, to obtain product L4, 500 mg of light green foamy solid, yield 64%. 1 H NMR (500MHz, DMSO-d6): δ1.10(d,J=7.0Hz,6H),1.19(d,J=6.5Hz,6H),1.30(s,9H),1.36(s,9H),2.36-2 .43(m,2H),7.24(dd,J=8.5,6.5Hz,1H),7.34(t,J=8.0Hz,1H),7.45–7.54(m,5H),7.65(d,J=7.5Hz,1H) ,7.66–7.69(m,2H),7.72–7.78(m,3H),7.87(s,2H),7.89(d,J=8.5Hz,2H),7.96(dd,J=8.0,6.5Hz,1H), 8.07(d,J=8.0Hz,2H), 8.24(d,J=7.5Hz,1H), 8.33(d,J=8.5Hz,1H), 8.58(d,J=5.5Hz,1H), 10.65(s,1H).

[0117] Synthesis of Pt4: L4 (500 mg, 0.49 mmol, 1.0 equivalent), (1,5-cyclooctadiene) platinum dichloride (184 mg, 0.49 mmol, 1.0 equivalent) and sodium acetate (201 mg, 1.48 mmol, 3.0 equivalent) were added to a sealed tube with a magnetic rotor and dried, nitrogen was replaced three times, diethylene glycol dimethyl ether (30 mL) was added under nitrogen protection, nitrogen was bubbled for 30 minutes, and the sealed tube was wrapped with tin foil to avoid light, and the mixture was stirred in an oil bath at 120 ° C for 3 days, cooled to room temperature, added deionized water and stirred for 5-10 minutes to quench, added dichloromethane to extract, the organic phase was combined, dried over anhydrous sodium sulfate, and the solvent was removed by reduced pressure distillation. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 2:1, and the product Pt4 was obtained, a yellow solid 466 mg, and a yield of 89%. 1 H NMR (500MHz, DMSO-d6): δ0.92-1.25(m,21H),1.48(s,9H),2.9-3.15(m,2H),6.34(dd,J=4.0,2.0Hz,1H) ,7.06(d,J=1.5Hz,1H),7.15(d,J=8.5Hz,1H),7.25(d,J=8.5Hz,1H),7.36(t,J=7.5Hz,1H),7.43(t,J=7 .5Hz,1H),7.44–7.51(m,1H),7.59(t,J=7.5Hz,1H),7.67–7.84(m,5H),7.87(d,J=8.5Hz,1H),7.90(d,J =8.0Hz, 2H), 8.11 (d, J = 7.5Hz, 1H), 8.15 (d, J = 8.5Hz, 2H), 8.36 (d, J = 8.0Hz, 1H), 8.57 (d, J = 6.5Hz, 1H).

[0118] Example 5: Synthesis of Pt5

[0119] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt5 is as follows:

[0120]

[0121] Synthesis of intermediate 5-NH: 1 (363 mg, 1.0 mmol, 1.0 equivalent), 4-Cl (545 mg, 1.1 mmol, 1.1 equivalent), tris (dibenzylidene-BASE acetone) dipalladium (27 mg, 0.03 mmol, 0.03 equivalent), 2- (di-tert-butylphosphine) biphenyl (18 mg, 0.06 mmol, 0.06 equivalent), sodium tert-butoxide (192 mg, 2.0 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried. The nitrogen was replaced three times, and toluene (5 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 100 ° C for 12 hours, cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 30:1, and the product 5-NH was obtained, a light green foamy solid 525 mg, a yield of 64%. It was directly used for the next step reaction.

[0122] Synthesis of ligand L5: 5-NH (525 mg, 0.64 mmol, 1.0 equivalent) and ammonium hexafluorophosphonate (208 mg, 1.28 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried, and nitrogen was replaced three times. Triethyl orthoformate (10 mL) was added under nitrogen protection, and the mixture was stirred in an oil bath at 80 ° C for 10 hours, cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated and purified by silica gel chromatography, eluent: dichloromethane, to obtain product L5, 325 mg of light green foamy solid, yield 52%. 1 H NMR (500MHz, DMSO-d6): δ1.08(d,J=6.5Hz,6H),1.18(d,J=7.0Hz,6H),1.33(s,9H),2.40-2.46(m,2H),7.31(dd,J=8.0, 6.0Hz,1H),7.36(dd,J=5.0,3.0Hz,1H),7.39(d,J=2.0Hz,2H),7.47–7.50(m,1H),7.52(dd,J=5.5,4.0Hz,1H),7.64(t,J =3.5Hz,2H),7.72(d,J=8.5Hz,2H),7.74–7.79(m,2H),7.80(s,2H),7.83(s,1H),7.88–7.95(m,2H),8.03(d,J=8.5Hz,1H ), 8.07 (t, J = 2.0Hz, 1H), 8.19 (s, 1H), 8.28 (d, J = 8.0Hz, 1H), 8.39 (d, J = 8.5Hz, 1H), 8.61 (d, J = 5.0Hz, 1H), 10.64 (s, 1H).

[0123] Synthesis of Pt5: L5 (325 mg, 0.33 mmol, 1.0 equivalent), (1,5-cyclooctadiene) platinum dichloride (124 mg, 0.33 mmol, 1.0 equivalent) and sodium acetate (136 mg, 1.0 mmol, 3.0 equivalent) were added to a sealed tube with a magnetic rotor and dried, and nitrogen was replaced three times. Diethylene glycol dimethyl ether (30 mL) was added under nitrogen protection, and nitrogen was bubbled for 30 minutes. The sealed tube was wrapped with tin foil to avoid light, and the mixture was stirred in an oil bath at 120 ° C for 3 days, cooled to room temperature, and deionized water was added and stirred for 5-10 minutes to quench, and dichloromethane was added to extract, the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed by reduced pressure distillation. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 2: 1, and the product Pt5 was obtained, a yellow solid 205 mg, and a yield of 60%. 1 H NMR (500MHz, DMSO-d6): δ0.96-1.27(m,21H),2.81-3.01(m,2H),6.37(dd,J=6.0,2.0Hz,1H) ,7.17(d,J=8.5Hz,1H),7.29(d,J=8.5Hz,1H),7.33–7.41(m,6H),7.46(t,J=7.5Hz,1H),7.51 (td,J=8.5,7.0Hz,1H),7.59(td,J=7.0,6.0Hz,1H),7.86(d,J=2.0Hz,1H),7.88(d,J=8.0Hz ,2H),7.95–7.99(m,3H),8.15(d,J=6.5Hz,1H),8.42(d,J=8.5Hz,1H),8.59(d,J=6.0Hz,1H).

[0124] Example 6: Synthesis of Pt6

[0125] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt6 is as follows:

[0126]

[0127] Synthesis of intermediate 6-NH: 3 (380 mg, 1.0 mmol, 1.0 equivalent), 2-Cl (531 mg, 1.1 mmol, 1.1 equivalent), tris (dibenzylidene-BASE acetone) dipalladium (27 mg, 0.03 mmol, 0.03 equivalent), 2- (di-tert-butylphosphine) biphenyl (18 mg, 0.06 mmol, 0.06 equivalent), sodium tert-butoxide (192 mg, 2.0 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried. The nitrogen was replaced three times, and toluene (5 mL) was added under nitrogen protection. The mixture was stirred in an oil bath at 100 ° C for 12 hours, cooled to room temperature, and the solvent was removed by distillation under reduced pressure. The crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 30:1, and the product 6-NH was obtained, a light green foamy solid 604 mg, a yield of 73%. It was directly used for the next step reaction.

[0128] Synthesis of ligand L6: 6-NH (604 mg, 0.73 mmol, 1.0 equivalent) and ammonium hexafluorophosphonate (238 mg, 1.46 mmol, 2.0 equivalent) were added to a sealed tube with a magnetic rotor and dried, and nitrogen was replaced three times. Triethyl orthoformate (10 mL) was added under nitrogen protection, and the mixture was stirred in an oil bath at 80 ° C for 10 hours, cooled to room temperature, and the solvent was removed by vacuum distillation. The crude product was separated and purified by silica gel chromatography, eluent: dichloromethane, to obtain product L6, 538 mg of light green foamy solid, yield 75%. 1 H NMR (500MHz, DMSO-d6): δ1.09(d,J=6.5Hz,6H),1.18(d,J=7.0Hz,6H),1.30(s,9H),1.36(s,9H),2. 35-2.40(m,2H),7.23(dd,J=8.5,6.0Hz,1H),7.31-7.37(m,2H),7.44-7.49(m,3H),7.52(t,J=2.0Hz ,1H),7.53(d,J=2.5Hz,1H),7.61(d,J=8.0Hz,1H),7.66–7.79(m,7H),7.89(s,2H),7.96(dd,J=8.0, 6.5Hz, 1H), 8.24 (dd, J = 7.5, 7.0Hz, 1H), 8.33 (d, J = 8.5Hz, 1H), 8.58 (d, J = 5.5Hz, 1H), 10.64 (s, 1H).

[0129] Synthesis of Pt6: L6 (538 mg, 0.55 mmol, 1.0 equivalent), (1,5-cyclooctadiene) platinum dichloride (206 mg, 0.55 mmol, 1.0 equivalent) and sodium acetate (223 mg, 1.64 mmol, 3.0 equivalent) were added to a sealed tube with a magnetic rotor and dried, nitrogen was replaced three times, diethylene glycol dimethyl ether (30 mL) was added under nitrogen protection, nitrogen was bubbled for 30 minutes, and the sealed tube was wrapped with tin foil to avoid light, and the mixture was stirred in an oil bath at 120 ° C for 3 days, cooled to room temperature, added deionized water and stirred for 5-10 minutes to quench, added dichloromethane to extract, the organic phase was combined, dried over anhydrous sodium sulfate, and the solvent was removed by reduced pressure distillation. The obtained crude product was separated and purified by silica gel chromatography, eluent: petroleum ether / dichloromethane = 2:1, and the product Pt6 was obtained as a yellow solid 463 mg, with a yield of 82%. 1 H NMR (500MHz, DMSO-d6): δ0.96-1.3(m,21H),1.47(s,9H),3.9-4.20(m,2H),6.34(dd,J=6.5, 6.0Hz,1H),7.04(d,J=2.0Hz,1H),7.11(d,J=8.5Hz,1H),7.24(d,J=8.5Hz,1H),7.28–7.33( m,1H),7.36(t,J=7.5Hz,1H),7.43(t,J=7.5Hz,1H),7.47(t,J=7.5Hz,1H),7.58(t,J=8.0Hz ,1H),7.68–7.88(m,8H),8.10(d,J=8.0Hz,1H),8.34(d,J=8.5Hz,1H),8.53(d,J=6.5Hz,1H).

[0130] The prepared platinum complexes Pt1, Pt4-Pt6 were subjected to spectral testing experiments. Figure 1 This is the room temperature emission spectrum of the prepared platinum complexes Pt1, Pt4-Pt6 in dichloromethane solution. Figure 1 It can be seen that Pt1, Pt4-Pt6 all emit deep blue light with high color purity. The maximum emission peak of Pt1 is 454nm, which is deep blue emission with a half-peak width of 19nm. It can be seen that the present invention improves the charge distribution of the excited state by introducing fluorine atoms at appropriate positions of the ligand, so that the excited state of the material has more metal to pyridocarbene charge transfer states ( 3 MLCT) is beneficial to improve its radiation rate and thus improve the device life. It provides an effective way to design platinum (II) complexes for high-quality blue light phosphorescent materials.

[0131] Example 7: Synthesis of Pt225

[0132] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt225 is as follows:

[0133]

[0134] Pt225 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product 225-NH was synthesized, 804 mg of light green foamy solid, with a yield of 77%. The target product L225 was obtained, 705 mg of light green foamy solid, with a yield of 63%. Molecular weight [M] + :721.6. The target product Pt225 was obtained as a yellow solid (606 mg) with a yield of 82%. Molecular weight [M+H] + :767.7.

[0135] Example 8: Synthesis of Pt16

[0136] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt16 is as follows:

[0137]

[0138] Pt16 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product 16-NH was synthesized as a light green foamy solid of 804 mg with a yield of 77%. The target product L16 was obtained as a light green foamy solid of 705 mg with a yield of 63%. Molecular weight [M] + :876.4. The target product Pt16 was obtained as a yellow solid (606 mg) with a yield of 82%. Molecular weight [M+H] + :1068.4.

[0139] Example 9: Synthesis of Pt19

[0140] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt19 is as follows:

[0141]

[0142] Pt19 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product 19-NH was synthesized, 906 mg of light green foamy solid, with a yield of 79%. The target product L19 was synthesized, 509 mg of light green foamy solid, with a yield of 59%. Molecular weight [M] + :888.5. The target product Pt19 was obtained as a yellow solid of 203 mg with a yield of 48%. Molecular weight [M+H] + :1080.2.

[0143] Example 10: Synthesis of Pt21

[0144] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt21 is as follows:

[0145]

[0146] Pt21 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product 21-NH was obtained, 1.56 g of light green foamy solid, with a yield of 61%. The target product L21 was synthesized, 705 mg of light green foamy solid, with a yield of 70%. Molecular weight [M] + :942.4. The target product Pt21 was obtained as a yellow solid 432 mg with a yield of 55%. Molecular weight [M+H] + :1134.5.

[0147] Example 11: Synthesis of Pt24

[0148] The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt24 is as follows:

[0149]

[0150] Pt24 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product 24-NH was obtained as a light green foamy solid of 1.02 g, with a yield of 75%. The target product L24 was obtained as a light green foamy solid of 708 mg, with a yield of 63%. Molecular weight [M] + :756.4. The target product Pt24 was obtained as a yellow solid 201 mg with a yield of 50%. Molecular weight [M+H] + :948.3.

[0151] Example 12: Synthesis of Pt37

[0152] Pt37 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid of 562 mg with a yield of 70%. Molecular weight [M+H] + :1065.1.

[0153] Example 13: Synthesis of Pt39

[0154] Pt39 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (624 mg) with a yield of 56%. Molecular weight [M+H] + :1067.1.

[0155] Example 14: Synthesis of Pt65

[0156] Pt65 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (661 mg) with a yield of 82%. Molecular weight [M+H]+ :996.1.

[0157] Example 15: Synthesis of Pt81

[0158] Pt81 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (484 mg) with a yield of 67%. Molecular weight [M+H] + :939.0.

[0159] Example 16: Synthesis of Pt82

[0160] Pt82 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (455 mg) with a yield of 60%. Molecular weight [M+H] + :981.0.

[0161] Example 17: Synthesis of Pt86

[0162] Pt86 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (410 mg) with a yield of 66%. Molecular weight [M+H] + :1019.1.

[0163] Example 18: Synthesis of Pt111

[0164] Pt111 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (369 mg) with a yield of 58%. Molecular weight [M+H] + :1080.2.

[0165] Example 19: Synthesis of Pt112

[0166] Pt112 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (492 mg) with a yield of 82%. Molecular weight [M+H] + :1096.2.

[0167] Example 20: Synthesis of Pt210

[0168] Pt210 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (471 mg) with a yield of 80%. Molecular weight [M+H] + :1089.2.

[0169] Example 21: Synthesis of Pt233

[0170] Pt233 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid of 596 mg with a yield of 74%. Molecular weight [M+H]+ :835.9.

[0171] Example 22: Synthesis of Pt311

[0172] Pt311 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid (615 mg) with a yield of 68%. Molecular weight [M+H] + :931.9.

[0173] Example 23: Synthesis of Pt318

[0174] Pt318 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt1. The target product was obtained as a yellow solid of 582 mg with a yield of 66%. Molecular weight [M+H] + :881.8.

[0175] Theoretical calculation instructions

[0176] Density functional theory (DFT) was used to optimize the molecular geometry in the ground state (S0). 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.

[0177] Table 1. Frontier orbital energy levels of some metal complexes

[0178]

[0179]

[0180]

[0181] It can be seen from the calculated data shown in Table 1 that the compound materials provided by the present invention all have a large energy gap (>3.20 eV), which can meet the needs of blue light materials. In addition, it can be seen that the frontier orbital energy levels (HOMO and LUMO) of the platinum (II) complex can be adjusted by regulating the ligand structure. Most of the LUMO of the pyridocarbene platinum (II) complex is in the pyridocarbene part. The present invention introduces fluorine atoms at appropriate positions of its ligands to improve the charge distribution of its excited state, so that the excited state of the material has more metal to pyridocarbene charge transfer states ( 3 MLCT) component; and because there is both a coordination bond and a feedback π bond between carbene and platinum (II), its stability is higher than the coordination bond between pyridine and platinum (II); the above results are conducive to improving its radiation rate and thus improving the life of the device.

[0182] Fabrication of OLED devices:

[0183] As a reference preparation method for a device embodiment, the present invention deposits a p-doped material on the surface of an ITO glass or an anode with a light-emitting area of ​​2mm×2mm, or co-evaporates the p-doped material with a hole injection material at a concentration of 1% to 50% to form a 5-100nm hole injection layer (HIL), a 5-200nm hole transport layer (HTL), and then forms a 10-100nm light-emitting layer (EML) (which may contain the compound described in the present invention) on the hole transport layer, forms an electron transport layer (ETL) of 20-200nm and a cathode of 50-200nm; if necessary, an electron blocking layer (EBL) is added between the HTL and EML layers, and an electron injection layer (EIL) is added between the ETL and the cathode to manufacture an OLED device. The OLED is tested by a standard method. The device materials involved in the present invention can be obtained by known synthesis methods unless otherwise specified.

[0184] In a preferred specific embodiment, the structure of device example 1 provided by the present invention is: ITO / P-4 (10nm) / NPD (60nm) / HTH-85 (5nm) / platinum (II) complex: HTH-85:ETH-45 (25nm) (Pt-1:HTH-85:ETH-45 mass ratio is 10:60:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0185] Device Examples 2 to 22 and Comparative Example 1 were prepared using structures similar to those of Device Example 1, except that Pt-2, Pt-3, Pt-4, Pt-5, Pt-225, Pt-16, Pt-19, Pt-21, Pt-24, Pt-37, Pt-39, Pt-65, Pt-81, Pt-82, Pt-86, Pt-111, Pt-112, Pt-210, Pt-233, Pt-311, Pt-318, and R1 were used to replace Pt-1 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 2. The device structures involved are as follows: wherein P-4 is HATCN and ET-14 is BPyTP.

[0186]

[0187]

[0188] Table 2. Device luminescence characteristics data table

[0189]

[0190] As can be seen from Table 2, compared with Comparative Example 1, the device examples 1 to 22 prepared in the present application all show good device performance in terms of driving voltage, current efficiency and device life. The improvement in the performance of each device example is based on the specific compound material of the present invention having better electron transport capability. It can be seen that when it is used as a light-emitting layer material to prepare an electronic device, it has higher current efficiency and device life while reducing the driving voltage. It shows that the compound provided by the present invention has certain commercial application value.

[0191] In a preferred specific embodiment, the structure of device example 23 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) (the mass ratio of Pt1:BN1-8:HTH-85:ETH-45 is 10:1:59:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0192] Device Examples 24 to 30 were prepared using structures similar to that of Device Example 23, except that the platinum (II) complex and the boron-containing compound in Device Example 23 were replaced by the compounds listed in Table 3. The device structures and luminescence characteristic data are shown in Table 3.

[0193] Table 3. Device structure and luminescence characteristics data table

[0194]

[0195] As shown in Table 3, when the compounds of the present invention are used as sensitizing materials and the boron-containing compounds are used as luminescent materials in devices, the performance of each device is significantly improved, which further indicates that the compounds provided by the present invention have certain commercial application value.

[0196] In addition, the devices prepared by the present invention are all deep blue light devices, and the CIEy values ​​are all less than 0.20. After adding the boron-containing compound to sensitize the device structure, the CIEy value can be further reduced, thereby improving the purity of the device luminescent color.

[0197] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope 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 shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A fluorine-containing tetradentate ring metal platinum (II) complex, characterized in that: The complex has a structure as shown in formula (I) or formula (II): In formula (I) or formula (II), F n Indicates that the benzene ring is substituted with one or more F, wherein n is a positive integer from 1 to 3; R a It represents mono-, di-, tri-, tetra- or unsubstituted; R a Selected from H or methyl; The R1 and R3 are independently selected from one or more of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, and heptyl; R2 is independently selected from hydrogen, F, CN, C1-C30 alkyl, C1-C30 cycloalkyl, substituted or unsubstituted phenyl, and C6-C60 heteroaryl; the substituent is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, and the heteroatoms on the heteroaryl are selected from one or more of O, S and / or N.

2. The tetradentate ring metal platinum (II) complex according to claim 1, characterized in that At least one hydrogen atom in R1, R2, or R3 may be replaced by deuterium or F.

3. A tetradentate ring metal platinum (II) complex, characterized in that: The tetradentate metal platinum (II) complex is selected from any one of the chemical structures shown below, wherein "D" represents deuterium:

4. Use of the tetradentate ring metal platinum (II) complex according to any one of claims 1 to 3 in electronic devices.

5. The use according to claim 4, characterized in that: The electronic devices include organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quenching devices, light emitting electrochemical cells and organic laser diodes.

6. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the tetradentate metal platinum (II) complex according to any one of claims 1 to 3.

7. The organic electroluminescent device according to claim 6, characterized in that: The light-emitting layer further comprises a fluorescent doping material; the fluorescent doping material is selected from any one or more of the compounds represented by formula (BN1) to formula (BN5): Wherein, X is O, S, Se; X 1 , X 2 , X 3 , X 4 Each independently represents O, S, Se or N; R b -R e Each independently represents mono-, di-, tri-, tetra- or unsubstituted; R b -R e Each is independently selected from the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, and C6-C60 aryl; 11 Each independently represents the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, and C6-C60 aryl.

8. The organic electroluminescent device according to claim 7, characterized in that: The R4-R6 and R9 are each independently selected from substituted or unsubstituted diphenylamine groups, substituted or unsubstituted carbazole groups; the substitution may be multiple substitutions, and when containing substituents, the substituents are selected from deuterium, C1-C30 alkyl groups, and C6-C30 aryl groups.

9. The organic electroluminescent device according to claim 7, characterized in that: R7-R8, R 10 -R 11 Each is independently selected from the group consisting of hydrogen, C1-C30 alkyl, and C6-C60 aryl.

10. The organic electroluminescent device according to claim 7, characterized in that: The fluorescent doping material is selected from any one of the chemical structures shown below, wherein Ph represents a phenyl group, and D4 and D5 mean substitution by 4 and 5 deuterium atoms, respectively:

11. 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 according to any one of claims 1 to 3.

12. The organic optoelectronic device according to claim 11, characterized in that: The organic light-emitting functional layer further comprises a fluorescent doping material; the fluorescent doping material is selected from any one or more of the compounds represented by formula (BN1) to formula (BN5): Wherein, X is O, S, Se; X 1 , X 2 , X 3 , X 4 Each independently represents O, S, Se or N; R b -R e Each independently represents mono-, di-, tri-, tetra- or unsubstituted; R b -R e Each is independently selected from the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, and C6-C60 aryl; 11 Each independently represents the group consisting of hydrogen, deuterium, N, C1-C30 alkyl, and C6-C60 aryl.

13. A composition, characterized in that The composition comprises the fluorine-containing tetradentate platinum (II) complex according to any one of claims 1 to 3.

14. A preparation, characterized in that The preparation comprises the fluorine-containing tetradentate platinum (II) complex according to any one of claims 1 to 3.

15. A display or lighting device, characterized in that: The device comprises one or more of the organic electroluminescent devices according to claim 6.

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