Pyridinocarbene-based tetradentate cyclometalated platinum (II) complex and use thereof

Abstract

The present invention belongs to the field of organic electroluminescence, and specifically relates to a pyridinocarbene-based tetradentate cyclometalated platinum (II) complex, and a use thereof. Compared with a benzocarbene platinum (II) complex, pyridinocarbene has a stronger electron-withdrawing ability, so that an excited state has more metal-to-pyridinocarbene charge transfer (3MLCT) states, which helps to improve a radiation rate thereof, and thus extend device service life. The material provided by the present invention has good chemical stability and thermal stability, and is easy to prepare in a vapor-deposited OLED device. An organic electroluminescent device made using the compound of the present invention as a light-emitting layer has significant improvements in current efficiency and service life, and significantly reduces lighting voltage. When combined with a fluorescent doping material (a boron-containing compound), it can balance hole and electron transport, make energy transfer between a host and a guest more efficient, and improve the light color purity of the device.

Description

A tetradentate ring metal platinum (II) complex based on pyridocarbene and its application Technical Field

[0001] The present invention belongs to the field of organic electroluminescence, and in particular relates to a pyridocarbene-based tetradentate ring metal platinum (II) complex and its application. Background Art

[0002] Organic light-emitting diodes (OLEDs) are a new generation of full-color display and lighting technology. As an autonomous light-emitting device, it does not require a backlight, has a low driving voltage, a fast response speed, high resolution and contrast, a wide viewing angle, and excellent 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. The core of OLED development is the design and development of luminescent materials. Organic red and green OLEDs have basically reached the standards for commercial applications. However, due to the long lifetime of triplet excitons and the wide band gap of blue light materials, triplet exciton accumulation and breakage of organic molecular chemical bonds are prone to occur in blue OLEDs devices at high brightness, which seriously affects the stability of the device. This has greatly restricted the development and application of blue OLEDs.

[0003] Research on organic blue OLED materials, both domestically and internationally, is developing along multiple pathways. Currently, the emitting layers in OLED devices almost exclusively utilize a host-guest luminescence mechanism. This involves doping a guest luminescent material within a host material. The host material's energy system is generally greater than that of the guest luminescent material, and energy is transferred from the host material to the guest material, exciting the guest material to emit light. Commonly used organic phosphorescent guest materials are heavy metal atoms such as iridium(III), platinum(II), and palladium(II). Currently, the available heavy metal phosphorescent organic complexes are limited to cyclometallated iridium(III) complexes. In contrast, the preparation of platinum(II) complex phosphorescent materials boasts a high platinum utilization rate, further reducing the cost of preparing them. The cost of preparing platinum(II) complex phosphorescent materials is significantly lower than that of iridium(III) complex phosphorescent materials. However, the development of platinum complex materials and devices still faces several technical challenges, and improving device efficiency and lifetime is a key research topic. Therefore, the development of novel phosphorescent metal platinum(II) complexes is crucial.

[0004] Summary of the Invention

[0005] In view of this, the present invention aims to provide a pyridocarbene-based tetradentate platinum(II) complex and its application. The pyridocarbene-based tetradentate platinum(II) complex of the present invention, when used as a light-emitting layer in an organic electroluminescent device, can provide excellent device performance. This can improve the current efficiency and device life of the organic electroluminescent device, while also reducing the device's operating voltage.

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

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

[0008] In formula (I), R 1 -R 5 Each independently represents a single substitution to the maximum number of substitutions, or no substitution; R 1 -R 5 Each is independently selected from the group consisting of hydrogen, deuterium, C1-C30 alkyl, C1-C30 deuterated alkyl, C6-C60 aryl, C6-C30 arylsilane, and combinations thereof; R is selected from the group consisting of hydrogen, deuterium, C1-C30 alkyl, C1-C30 cycloalkyl, C1-C30 deuterated alkyl, C6-C60 aryl, C6-C30 fused ring aryl, and combinations thereof.

[0009] Furthermore, R 1 -R 5 Each is independently selected from hydrogen, deuterium, 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, n-decyl, isodecyl, sec-decyl, tert-decyl, phenyl, triphenylsilane, and combinations thereof.

[0010] Further, R is selected from adamantaneamine, tert-butyl, tert-butylphenyl or a group having the following structural formula;

[0011] The R 6 represents single substitution to the maximum amount of substitution, or no substitution; R 6 Selected from hydrogen, C1-C20 alkyl, C1-C20 deuterated alkyl;

[0012] R a and R b are identical or independently represented by a C3-C30 alkyl group, a C1-C20 deuterated alkyl group, or a C5-C30 cycloalkyl group.

[0013] Furthermore, R 6 is selected from hydrogen, methyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, D, CD3; said R a 、R b The same or each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, phenyl.

[0014] Furthermore, the tetradentate metal platinum (II) complex of the pyridocarbene may be selected from any one of the chemical structures shown below, wherein "D" represents deuterium and Ph represents a phenyl group:

[0015] Furthermore, the present invention also provides the use of the tetradentate ring metal platinum (II) complex having the structure shown in formula (I) in electronic devices.

[0016] 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).

[0017] In another aspect, the present invention further provides an organic electroluminescent device, which comprises the tetradentate ring metal platinum (II) complex having a structure represented by formula (I) as described above.

[0018] Furthermore, the organic electroluminescent device comprises a cathode, an anode and an organic functional layer therebetween; the organic functional layer comprises the tetradentate ring metal platinum (II) complex having the structure shown in formula (I) as described above.

[0019] Preferably, the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises the tetradentate ring metal platinum (II) complex having the structure represented by formula (I) as described above.

[0020] 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.

[0021] 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 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.

[0022] 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.

[0023] 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.

[0024] The present invention also provides a composition comprising a tetradentate ring metal platinum (II) complex having a structure represented by formula (I). Preferably, the composition further comprises a fluorescent dopant material, preferably a fluorescent boron-containing organic molecule luminescent material. The compound of the present invention can phosphoresce the boron-containing compound.

[0025] The present invention also provides a preparation comprising the tetradentate ring metal platinum (II) complex having a structure represented by formula (I) or the composition described above and at least one solvent.

[0026] 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.

[0027] The present invention also provides a display or lighting device, which comprises one or more of the organic photoelectric devices described above.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] The present invention provides a pyridocarbene-based tetradentate metal platinum (II) complex phosphorescent material. Compared with benzocarbene platinum (II) complexes, pyridocarbene has a stronger electron-withdrawing ability, resulting in more metal-to-pyridocarbene charge transfer states in the excited state ( 3 The materials provided by the present invention all have excellent chemical and thermal stability, making them easy to prepare vapor-deposited OLED devices. Organic electroluminescent devices fabricated using the compounds of the present invention as the light-emitting layer exhibit significant improvements in current efficiency and lifespan, while significantly reducing the turn-on voltage. Combining them with fluorescent doping materials (boron-containing organic molecular luminescent materials) can balance the transport of holes and electrons, making energy transfer between the host and guest more efficient and improving the light color purity of the device. DETAILED DESCRIPTION

[0030] 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.

[0031] 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).

[0032] In defining various terms, “R 1 ”-“R 6 ”, “R a ”, “R b " 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.

[0033] The term "alkyl" as used herein refers to a saturated hydrocarbon group of 1 to 24 carbon atoms, 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. A "lower alkyl" group is an alkyl group containing 1 to 6 (e.g., 1 to 4) carbon atoms.

[0034] Throughout this specification, "alkyl" is generally used to refer to both unsubstituted and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituents on the alkyl group. For example, the term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl group substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, as described below, etc. When "alkyl" is used in one context and a specific term such as "alkyl alcohol" is used in another context, it is not meant to imply that the term "alkyl" does not also refer to the specific term such as "alkyl alcohol", etc.

[0035] The term "cycloalkyl" as used herein is a non-aromatic carbon-based ring consisting of at least three carbon atoms. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and the like.

[0036] As used herein, the term "aryl" refers to a group containing any carbon-based aromatic group, including but not limited to phenyl, naphthyl, phenyl, biphenyl, phenoxyphenyl, anthracenyl, phenanthrenyl, and the like. The term "aryl" also includes "heteroaryl," which is defined as a group containing an aromatic group having at least one heteroatom introduced into the ring of the aromatic group. Examples of heteroatoms include but are not limited to nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term "non-heteroaryl" (which is also included in the term "aryl") defines a group containing an aromatic group that does not contain heteroatoms. An aryl group may be substituted or unsubstituted. An 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, sulfanyl-oxo, or mercapto groups as described herein. The term "biaryl" is a specific type of aryl group and is included in the definition of "aryl." A biaryl group refers to two aryl groups bound together by a fused ring structure, as in naphthalene, or linked by one or more carbon-carbon bonds, as in biphenyl.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] Synthesis Example

[0043] The following examples of compound syntheses, compositions, devices, or methods are intended only to provide a general approach to the industry and are not intended to limit the scope of protection of this patent. While the data (quantities, temperatures, etc.) mentioned in the patent are as accurate as possible, some errors may exist. Unless otherwise noted, all weighings are separate, temperatures are in °C or at room temperature, and pressures are near atmospheric pressure.

[0044] The following examples provide methods for preparing new compounds, but the preparation of such compounds is not limited to these methods. In this field of expertise, since the compounds protected in this patent are easily modified and prepared, they can be prepared using the methods listed below or other methods. The following examples are merely examples and are not intended to limit the scope of protection of this patent. The temperature, catalyst, concentration, reactants, and reaction process can all be varied to select different conditions for preparing the compounds for different reactants.

[0045] 1 H NMR (500 MHz), 1 H NMR (400 MHz), 13 C NMR (126 MHz) spectra were measured on an ANANCE III (500M) nuclear magnetic resonance spectrometer. Unless otherwise specified, DMSO-d6 or CDCl3 containing 0.1% TMS was used as the solvent for NMR. 1 When CDCl3 was used as the solvent, TMS (δ = 0.00 ppm) was used as the internal standard for H NMR spectra. When DMSO-d6 was used as the solvent, TMS (δ = 0.00 ppm), the residual DMSO peak (δ = 2.50 ppm), or the residual water peak (δ = 3.33 ppm) was used as the internal standard. 13In C NMR spectra, CDCl3 (δ = 77.00 ppm) or DMSO-d6 (δ = 39.52 ppm) was used as the internal standard. HPLC-MS was measured on an Agilent 6210 TOF LC / MS mass spectrometer; HRMS spectra were measured on an Agilent 6210 TOF LC / MS liquid chromatography-time-of-flight mass spectrometer. 1 In H NMR spectrum data: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad.

[0046] Synthesis route

[0047] Example 1: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt51

[0048] The synthetic route is as follows:

[0049] Synthesis of intermediate (NH1): DiPr-NH2 (623 mg, 2.2 mmol, 1.3 equiv), DiPr-Cl (1.0 g, 1.7 mmol, 1.0 equiv), trisdibenzylideneacetone dipalladium (47 mg, 0.05 mmol, 3 mol%), 2-dicyclohexylphosphino-3,6-dimethoxy-2',4',6'-triisopropyldiphenyl (BrettPhos) (55 mg, 0.1 mmol, 6 mol%), and sodium tert-butoxide (408 mg, 4.2 mmol, 2.5 equiv) were added to a Schlenk tube equipped with a magnetic stirrer. The nitrogen atmosphere was purged three times, and toluene (8 mL) was added under nitrogen. The mixture was reacted in an oil bath at 100°C for 10 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the crude product was separated by silica gel chromatography using petroleum ether / ethyl acetate (40:1-20:1) as the eluent to obtain 1.03 g of a solid in a 73% yield. The product was not structurally characterized and was used directly in the next step.

[0050] Synthesis of Ligand L1: NH1 (1.03 g, 1.2 mmol, 1.0 equiv) and ammonium hexafluorophosphate (391 mg, 2.4 mmol, 2.0 equiv) were added to a Schlenk tube equipped with a magnetic stirrer. The nitrogen atmosphere was purged three times, and triethyl formate (5 mL) was added under nitrogen. The mixture was reacted in an oil bath at 75°C for 6 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the product was separated by silica gel chromatography using an eluent of dichloromethane / ethyl acetate (100:1-50:1) to obtain 900 mg of a solid in a 78% yield. NMR(500MHz,DMSO-d6)δ0.89(d,J=6.5Hz,6H),0.99(d,J=6.5Hz,6H),1.09(d,J=6.5Hz,6H),1.14(d,J=6.5Hz,6H),1. 33(s,9H),2.42(m,J=7.0Hz,2H),2.57(m,J=6.5Hz,2H),2.61(s,3H),7.03(q,J=1.0Hz,1H),7.21(d,J=8.0Hz,2H),7. 25(dd,J=8.5,2.5Hz,1H),7.30–7.37(m,2H),7.44–7.57(m,6H),7.67–7.75(m,3H),7.78(d,J=8.5Hz,1H),7.85(t,J= 2.0Hz,1H),8.25(d,J=8.0Hz,1H),8.34(d,J=8.5Hz,1H),8.47(d,J=9.0Hz,1H),8.58(d,J=5.0Hz,1H),10.75(s,1H).

[0051] Synthesis of Pt51: To a sealed tube with a magnetic stirrer, L1 (900 mg, 0.9 mmol, 1.0 equiv), (1,5-cyclooctadiene) platinum dichloride (337 mg, 0.9 mmol, 1.0 equiv) and sodium acetate (221 mg, 2.7 mmol, 3.0 equiv) were added. The nitrogen atmosphere was purged three times, and tetrahydrofuran (8 mL) was added under nitrogen protection. Nitrogen was bubbled through the tube for 30 min to deoxygenate. The mixture was reacted in an oil bath at 120°C for 44 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel chromatography using petroleum ether / dichloromethane (4:1-1:1) as eluent to obtain 304 mg of a yellow solid in a 32% yield. 1H NMR(500MHz, CDCl3-d)δ0.77–1.42(m,33H),2.49(s,3H),3.01(s,4H),6.10(dd, J=6.5,2.0Hz,1H),7.01(d,J=1.5Hz,1H),7.13(d,J=8.5Hz,1H),7.26(s,3H),7. 27–7.31(m,3H),7.32–7.44(m,5H),7.79(dd,J=8.5,4.0Hz,2H),7.97(d,J=2.0H z,1H),8.02(dd,J=8.0,1.5Hz,1H),8.13(d,J=8.5Hz,1H),8.64(d,J=6.0Hz,1H).

[0052] Example 2: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt52

[0053] The synthetic route is as follows:

[0054] Synthesis of the intermediate tBu-NO2: To a Schlenk tube equipped with a magnetic stirrer, add Cl-NO2 (1.0 g, 5.8 mmol, 1.0 equiv) and tBu-NH1 (1.3 g, 8.68 mmol, 1.5 equiv). The nitrogen atmosphere was purged three times, and N,N-dimethylformamide (3 mL) was added under nitrogen. The mixture was reacted in an oil bath at 65°C for 17 hours, then cooled to room temperature. The mixture was extracted with water and ethyl acetate. The organic phase was collected and the solvent was removed by vacuum distillation. The crude product was separated by silica gel chromatography using a 40:1-20:1 ratio of petroleum ether to ethyl acetate to afford 1.15 g of a solid in a 95% yield. The product was used directly in the next step without structural characterization.

[0055] Synthesis of the intermediate tBu-NH2: To a three-necked flask with a magnetic stirrer were added tBu-NO2 (1.15 g, 5.55 mmol, 1.0 equivalent), palladium on carbon (113 mg, 0.11 mmol, 2.0 mmol%), and then ethanol (15 mL) and ethyl acetate (10 mL). The mixture was reacted under a hydrogen atmosphere for 16 hours, filtered through celite, and the solvent was removed by distillation under reduced pressure to obtain 978 mg of a solid in a 99% yield. The product was used directly in the next step without structural characterization.

[0056] Synthesis of intermediate NH2: To a Schlenk tube equipped with a magnetic stirrer, tBu-NH2 (500 mg, 2.8 mmol, 1.3 equiv), H-Br (1.01 g, 2.14 mmol, 1.0 equiv), trisdibenzylideneacetone dipalladium (59 mg, 0.064 mmol, 3 mol%), 2-dicyclohexylphosphino-3,6-dimethoxy-2',4',6'-triisopropyldiphenyl (BrettPhos) (69 mg, 0.13 mmol, 6 mol%), and sodium tert-butoxide (514 mg, 5.35 mmol, 2.5 equiv) were added. The atmosphere was purged with nitrogen three times, and toluene (6 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 100°C for 12 hours, then cooled to room temperature and extracted with water and ethyl acetate. The organic phase was collected and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel chromatography with an eluent of petroleum ether / ethyl acetate = 30:1-10:1 to obtain 978 mg of a brown solid in an 82% yield.

[0057] Synthesis of Ligand L2: To a Schlenk tube equipped with a magnetic stirrer, NH2 (978 mg, 1.7 mmol, 1.0 equiv) and ammonium hexafluorophosphate (554 mg, 3.4 mmol, 2.0 equiv) were added. The nitrogen atmosphere was purged three times, and triethyl formate (5 mL) was added under nitrogen. The mixture was reacted in an oil bath at 75°C for 6 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the mixture was separated by silica gel chromatography using a solvent ratio of dichloromethane to ethyl acetate (30:1-10:1) to afford 968 mg of a solid (79% yield). 1 H NMR (500MHz, DMSO-d6) δ1.31(s,9H),1.87(s,9H),2.72(s,3H),7.18(dd,J=8.5,2.0Hz,1H),7.34(ddd,J=7.5,7.0,1.0Hz,1H),7.38– 7.42(m,1H),7.44–7.51(m,3H),7.58–7.65(m,3H),7.68–7.76(m,3H),8.23–8.27(m,2H),8.32(d,J=8.5Hz,1H),8.59(dd,J=5.5,0.5 Hz,1H),10.04(s,1H).

[0058] Synthesis of Pt52: L2 (600 mg, 1.05 mmol, 1.0 equivalent), (1,5-cyclooctadiene) platinum dichloride (393 mg, 1.05 mmol, 1.0 equivalent) and sodium acetate (258 mg, 3.15 mmol, 3.0 equivalent) were added to a sealed tube with a magnetic stirrer. The nitrogen atmosphere was evacuated three times. Tetrahydrofuran (5 mL) was added under nitrogen protection and nitrogen was bubbled for deoxygenation for 30 min. The reaction was carried out in a 120°C oil bath for 44 hours. After the reaction was cooled to room temperature, the solvent was distilled off under reduced pressure. The crude product was separated by silica gel chromatography with an eluent of petroleum ether / dichloromethane = 4:1-1:1 to obtain 92 mg of a yellow solid with a yield of 10%. 1 H NMR (500MHz, CDCl3-d) δ1.33(s,9H),2.01(s,9H),2.68(s,3H),6.94(dd,J=6.0,2.0Hz,1H),7.08(dd,J=8.5,1.0Hz,1H),7.19(d,J=8.5Hz,1H),7.2 9(d,J=8.0Hz,1H),7.33–7.51(m,4H),7.89(d,J=8.5Hz,1H),7.91(d,J=7. 5Hz,1H),8.02–8.13(m,2H),8.27(d,J=8.0Hz,1H),9.21(d,J=6.5Hz,1H).

[0059] Example 3: The synthesis route of the tetradentate ring metal platinum (II) complex phosphorescent material Pt46 is as follows:

[0060] Synthesis of intermediate iPr-NO2: Cl-NO2 (10 g, 57.95 mmol, 1.0 equivalent) and iPr-NH1 (15.41 g, 86.92 mmol, 1.5 equivalent) were added to a three-necked flask. Nitrogen was replaced three times and ethylene glycol (15 mL) was added. After reacting at 140 ° C for 20 hours, it was cooled to room temperature, quenched with water, neutralized with NaHCO3, extracted with EA, and the organic phase was collected. After the solvent was removed by distillation under reduced pressure, the crude product was separated by silica gel chromatography, eluent: petroleum ether / ethyl acetate = 100: 1-30: 1, to obtain 19 g of crude product. The structure was not characterized and it was used directly in the next step.

[0061] Synthesis of the intermediate iPr-NH2: To a single-necked flask equipped with a magnetic stirrer, iPr-NO2 (19 g, 71 mmol, 1.0 equiv) and palladium on carbon (2.5 g, 1.18 mmol, 1.0 mmol%) were added, followed by ethanol (30 mL) and ethyl acetate (100 mL). The mixture was reacted under a hydrogen atmosphere for 20 hours, filtered through celite, and the solvent was removed by vacuum distillation. Separation was performed on a silica gel chromatography column using petroleum ether / ethyl acetate in a ratio of 10:1 to 1:1 as eluent to afford 10.63 g of a solid, yielding 99% for both steps. The product was used directly in the next step without structural characterization.

[0062] Synthesis of intermediate NH3: iPr-NH2 (355 mg, 1.25 mmol, 1.1 equiv), tBu-Br (600 mg, 1.14 mmol, 1.0 equiv), trisdibenzylideneacetone dipalladium (31 mg, 0.034 mmol, 3 mol%), 2-dicyclohexylphosphino-3,6-dimethoxy-2',4',6'-triisopropyldiphenyl (BrettPhos) (37 mg, 0.068 mmol, 6 mol%), and sodium tert-butoxide (274 mg, 2.85 mmol, 2.5 equiv) were added to a Schlenk tube equipped with a magnetic stirrer. The atmosphere was purged with nitrogen three times, and toluene (6 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 100°C for 14 hours, then cooled to room temperature and extracted with water and ethyl acetate. The organic phase was collected and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel chromatography with an eluent of petroleum ether / ethyl acetate in a ratio of 20:1 to 10:1 to obtain 720 mg of a brown solid in a yield of 87%.

[0063] Synthesis of Ligand L3: To a Schlenk tube equipped with a magnetic stirrer, NH2 (720 mg, 0.99 mmol, 1.0 equiv) and ammonium hexafluorophosphate (323 mg, 1.98 mmol, 2.0 equiv) were added. The nitrogen atmosphere was purged three times, and triethyl formate (3 mL) was added under nitrogen. The mixture was reacted in an oil bath at 75°C for 9 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the mixture was separated by silica gel chromatography using petroleum ether / ethyl acetate in a ratio of 3:1 to 1:1 as eluent to afford 794 mg of a solid in an 86% yield. NMR(500MHz,DMSO-d6)δ0.99(d,J=7.0Hz,6H),1.13(d,J=7.0Hz,6H),1.31(s,9H),1. 36(s,9H),2.35–2.41(m,2H),2.60(s,3H),7.22(dd,J=8.0,2.0Hz,1H),7.35(td,J=7 .5,1.0Hz,1H),7.45–7.56(m,7H),7.64–7.76(m,5H),8.25(dt,J=7.5,1.0Hz,1H),8. 33(d,J=8.5Hz,1H),8.45(d,J=8.5Hz,1H),8.58(dd,J=5.5,0.5Hz,1H),10.76(s,1H).

[0064] Synthesis of Pt46: To a sealed tube with a magnetic stirrer, L2 (670 mg, 0.76 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum dichloride (283 mg, 0.76 mmol, 1.0 equiv), and sodium acetate (186 mg, 2.27 mmol, 3.0 equiv) were added. The nitrogen atmosphere was purged three times, and tetrahydrofuran (5 mL) was added under nitrogen protection. Nitrogen was bubbled through the mixture for 30 min to deoxygenate. The mixture was reacted in a 120°C oil bath for 72 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel chromatography using petroleum ether / dichloromethane (2:1-1:1) as eluent to obtain 250 mg of a yellow solid in a 35% yield. 1 H NMR(500MHz, CDCl3-d)δ1.26(s,22H),1.49(s,9H),2.52(s,3H),3.07(s,2H),6.07(dd,J=6.5,2.0Hz,1H),7.15–7.25(m,3H),7.29–7.44(m,4 H),7.56(d,J=1.5Hz,1H),7.76–7.79(m,2H),7.94(d,J=2.0Hz,1H),8.01(dd,J=7.5,1.5Hz,1H),8.26(d,J=8.0Hz,1H),8.58(d,J=6.5Hz,1H).

[0065] Example 4: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt47

[0066] The synthetic route is as follows:

[0067] Pt47 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt46. The target product was obtained as a yellow solid (3 g) with a yield of 20%. 1 H NMR(500MHz, CDCl3-d)δ0.84–1.27(m,22H),2.51(s,3H),3.04(s,2H),6.08(dd,J=6.5,2.0Hz,1H),7.08–7.25(m,3H),7.29–7.46(m,5H),7.52(dd ,J=7.5,1.0Hz,1H),7.78(dd,J=8.0,2.5Hz,2H),7.94(d,J=2.0Hz,1H),8.01(dd,J=7.5,1.0Hz,1H),8.28(d,J=8.0Hz,1H),8.59(d,J=7.0Hz,1H).

[0068] Example 5: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt48

[0069] The synthetic route is as follows:

[0070] Synthesis of the intermediate (dBr-NO2): F-NO2 (500 mg, 3.52 mmol, 1.0 equiv) was added to a Schlenk tube equipped with a magnetic stirrer. The nitrogen atmosphere was purged three times, and N,N-dimethylformamide (10 mL) was added under nitrogen. The mixture was cooled to -20°C and sodium hydroxide was added, followed by dBr-NH2 (1.15 g, 4.57 mmol, 1.3 equiv). The reaction was allowed to proceed at room temperature for 26 hours, followed by extraction with water and ethyl acetate. The organic phase was collected and the solvent removed by distillation under reduced pressure. The organic phase was then separated by silica gel chromatography using a 20:1 ratio of petroleum ether to ethyl acetate as the eluent to afford 946 mg of a yellow solid in a 72% yield. The product was used directly in the next step without structural characterization.

[0071] Synthesis of the intermediate (dPh-NO2): To a Schlenk tube equipped with a magnetic stirrer were added dBr-NO2 (500 mg, 1.34 mmol, 1.0 equiv), boron hydride (489 mg, 4.01 mmol, 3.0 equiv), tetrakistriphenylphosphine palladium (46 mg, 0.04 mmol, 3.0 mmol%), and potassium carbonate (463 mg, 3.35 mmol, 2.5 equiv). The atmosphere was purged with nitrogen three times, and 1,4-dioxane (4 mL) and water (1 mL) were added. The reaction was incubated at 90°C for 24 hours, cooled to room temperature, and extracted with water and ethyl acetate. The organic phase was collected and the solvent was removed by distillation under reduced pressure. The organic phase was separated by silica gel chromatography using petroleum ether / ethyl acetate (20:1-10:1) as eluent to afford 380 mg of a yellow solid in a 77% yield. The product was used directly in the next step without structural characterization.

[0072] Synthesis of the intermediate (dPh-NH2): To a single-necked flask equipped with a magnetic stirrer, dPh-NO2 (380 mg, 1.03 mmol, 1.0 equivalent) and palladium on carbon (33 mg, 0.031 mmol, 3.0 mmol%) were added, followed by ethanol (10 mL) and ethyl acetate (2 mL). The mixture was reacted under a hydrogen atmosphere for 15 hours, filtered through celite, and the solvent was removed by vacuum distillation. Separation was performed on a silica gel column using petroleum ether / ethyl acetate (10:1-5:1) as the eluent to afford 330 mg of a brown solid in a 95% yield. The product was used directly in the next step without structural characterization.

[0073] Synthesis of intermediate (NH5): To a Schlenk tube equipped with a magnetic stirrer, dPh-NH2 (330 mg, 0.98 mmol, 1.0 equiv), H-Cl (418 mg, 0.98 mmol, 1.0 equiv), trisdibenzylideneacetone dipalladium (27 mg, 0.03 mmol, 3 mol%), 2-dicyclohexylphosphino-3,6-dimethoxy-2',4',6'-triisopropyldiphenyl (BrettPhos) (32 mg, 0.06 mmol, 6 mol%), and sodium tert-butoxide (188 mg, 1.96 mmol, 2.0 equiv) were added. The atmosphere was purged with nitrogen three times, and toluene (4 mL) was added under nitrogen protection. The reaction mixture was reacted in an oil bath at 110°C for 30 hours, then cooled to room temperature and extracted with water and ethyl acetate. The organic phase was collected and the solvent was removed by distillation under reduced pressure. The mixture was separated by silica gel chromatography with an eluent of petroleum ether / ethyl acetate = 20:1-10:1 to obtain 490 mg of a brown solid in a yield of 68%.

[0074] Synthesis of Ligand L5: NH5 (490 mg, 0.67 mmol, 1.0 equiv) and ammonium hexafluorophosphate (219 mg, 1.35 mmol, 2.0 equiv) were added to a Schlenk tube equipped with a magnetic stirrer. The nitrogen atmosphere was purged three times, and triethyl formate (4 mL) was added under nitrogen. The mixture was reacted in an oil bath at 75°C for 10 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the mixture was separated by silica gel chromatography using dichloromethane / ethyl acetate (50:1-10:1) as the eluent to afford 473 mg of a brown solid in an 81% yield. NMR(500MHz,DMSO-d6)δ1.29(s,9H),7.11–7.14(m,10H),7.17(dd,J=8.5,2.0Hz,1H), 7.21(ddd,J=8.0,2.2,0.9Hz,1H),7.34–7.38(m,1H),7.40(ddd,J=8.5,2.5,0.5Hz,1H ),7.46–7.51(m,3H),7.67–7.77(m,6H),7.94(t,J=7.5Hz,1H),8.28(dt,J=7.5,1.0Hz ,1H),8.34–8.40(m,2H),8.57–8.62(m,1H),8.67(dd,J=5.0,1.5Hz,1H),10.65(s,1H).

[0075] Synthesis of Pt48: To a sealed tube with a magnetic stirrer, L5 (473 mg, 0.54 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum dichloride (200 mg, 0.54 mmol, 1.0 equiv), and sodium acetate (133 mg, 1.62 mmol, 3.0 equiv) were added. The nitrogen atmosphere was purged three times, and tetrahydrofuran (5 mL) was added under nitrogen protection. Nitrogen was bubbled through the mixture for 30 min to deoxygenate. The mixture was reacted in an oil bath at 125°C for 80 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel chromatography using petroleum ether / dichloromethane (2:1-1:1) as eluent to obtain 50 mg of a yellow solid in a 10% yield. 1 H NMR(500MHz, CDCl3-d)δ1.31(s,9H),6.23(dd,J=6.5,2.0Hz,1H),6.59–7.25(m,12H),7.30–7.45(m,5H),7.48–7.56(m,3H) ,7.77(d,J=8.0Hz,1H),8.08–8.12(m,3H),8.17(dd,J=5.0,1.5Hz,1H),8.20(dd,J=8.0,1.0Hz,1H),8.98(d,J=6.0Hz,1H).

[0076] Example 6: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt49

[0077] The synthetic route is as follows:

[0078] Synthesis of intermediate (N1-NO2): To a three-necked flask, add Cl-NO2 (1.0 g, 5.79 mmol, 1.0 equiv) and N1-NH2 (1.24 g, 8.69 mmol, 1.5 equiv). The nitrogen atmosphere was purged three times, and N,N-dimethylformamide (3 mL) was added. After reacting at 100°C for 12 hours, the mixture was cooled to room temperature and extracted with water and EA. The organic phase was collected and evaporated under reduced pressure. The crude product was separated by silica gel chromatography using petroleum ether / ethyl acetate (20:1-10:1) as eluent to obtain 1.12 g of a yellow solid in a 69% yield. The product was used directly in the next step without structural characterization.

[0079] Synthesis of intermediate N1N-NH2: To a single-necked flask equipped with a magnetic stirrer was added N1-NO2 (1.12 g, 4.01 mmol, 1.0 equivalent), palladium on carbon (128 mg, 0.12 mmol, 3.0 mmol%), ethanol (10 mL), and ethyl acetate (3 mL). The reaction was carried out under a hydrogen atmosphere for 13 hours, followed by filtration through celite, vacuum distillation, and separation through silica gel chromatography using a 10:1 to 5:1 ratio of petroleum ether to ethyl acetate to afford 990 mg of a gray solid in a 99% yield. The product was used directly in the next step without structural characterization.

[0080] Synthesis of intermediate (NH6): To a Schlenk tube equipped with a magnetic stirrer, N1N-NH2 (321 mg, 1.29 mmol, 1.1 equiv), H-Cl (500 mg, 1.17 mmol, 1.0 equiv), trisdibenzylideneacetone dipalladium (32 mg, 0.035 mmol, 3 mol%), 2-dicyclohexylphosphino-3,6-dimethoxy-2',4',6'-triisopropyldiphenyl (BrettPhos) (38 mg, 0.07 mmol, 6 mol%), and sodium tert-butoxide (225 mg, 2.34 mmol, 2.0 equiv) were added. The nitrogen atmosphere was purged three times, and toluene (4 mL) was added under nitrogen protection. The reaction was carried out in an oil bath at 100°C for 24 hours, then cooled to room temperature and extracted with water and ethyl acetate. The organic phase was collected and distilled under reduced pressure. The mixture was separated by silica gel chromatography using petroleum ether / ethyl acetate = 20:1-10:1 as eluent to obtain 723 mg of a brown solid in a yield of 97%.

[0081] Synthesis of Ligand L6: NH6 (723 mg, 1.13 mmol, 1.0 equiv) and ammonium hexafluorophosphate (368 mg, 2.26 mmol, 2.0 equiv) were added to a Schlenk tube equipped with a magnetic stirrer. The nitrogen atmosphere was purged three times, and triethyl formate (4 mL) was added under nitrogen. The mixture was reacted in an oil bath at 75°C for 10 hours, then cooled to room temperature. The solvent was removed by distillation under reduced pressure, and the mixture was separated by silica gel chromatography using a dichloromethane / ethyl acetate ratio of 50:1 to 20:1 as the eluent to afford 740 mg of a brown solid in an 82% yield. NMR(500MHz,DMSO-d6)δ1.30(s,9H),2.53(s,3H),7.22(dd,J=8.0,2.0Hz,1H),7.34(t,J=7.5Hz,1 H),7.46–7.48(m,2H),7.52(d,J=2.0Hz,1H),7.59(ddd,J=8.0,7.0,1.0Hz,1H),7.65(t,J=2.5Hz,1 H),7.67–7.75(m,7H),7.79–7.83(m,2H),7.97(dd,J=7.5,2.0Hz,1H),8.19(d,J=8.0Hz,1H),8.24( d,J=7.5Hz,1H),8.33(d,J=8.5Hz,2H),8.46(d,J=8.5Hz,1H),8.59(d,J=5.0Hz,1H),10.73(s,1H).

[0082] Synthesis of Pt49: To a sealed tube with a magnetic stirrer, L6 (500 mg, 0.63 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum dichloride (214 mg, 0.57 mmol, 1.0 equiv), and sodium acetate (140 mg, 1.71 mmol, 3.0 equiv) were added. The nitrogen atmosphere was purged three times, and tetrahydrofuran (5 mL) was added under nitrogen protection. Nitrogen was bubbled through the mixture for 30 min to deoxygenate. The mixture was reacted in a 125°C oil bath for 80 hours. After cooling to room temperature, the reaction mixture was evaporated under reduced pressure and separated by silica gel chromatography using petroleum ether / dichloromethane (1:1-1:3) as the eluent to obtain 101 mg of a yellow solid in a 22% yield. 1 H NMR(500MHz, CDCl3-d)δ1.10(s,9H),2.52(s,3H),7.18(dd,J=8.0,1.0Hz,1H),7.28(s,1H),7.29–7.36(m,3H),7.36–7.44( m,3H),7.52(d,J=8.0Hz,2H),7.64(br,2H),7.72–7.87(m,5H),8.00(d,J=7.5Hz,2H),8.26(br,1H),8.33(d,J=8.5Hz,1H).

[0083] Example 7: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt50

[0084] The synthetic route is as follows:

[0085] Pt50 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt49 to obtain 120 mg of the target product as a yellow solid with a yield of 25%. 1 H NMR(500MHz, CDCl3-d)δ0.75(s,9H),2.67(s,3H),5.63(s,1H),7.22(dd,J=8.0,1.0Hz,1H),7.28–7.54(m,9H),7.68(d, J=8.0Hz,2H),7.81(d,J=8.0Hz,1H),7.86(d,J=8.5Hz,1H),7.89–8.09(m,3H),8.28(d,J=8.0Hz,1H),8.37–8.40(m,2H).

[0086] Example 8: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt171

[0087] The synthetic route is as follows:

[0088] Pt171 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt46. The target product was obtained as a yellow solid (84 mg) with a yield of 32%. 1 H NMR(500MHz, CDCl3-d)δ1.21–1.52(m,36H),6.15(dd,J=6.5,2.0Hz,1H),7.25(d,J=1.5Hz,1H),7.34–7.49(m,8H),7.62(d,J=1.5Hz,1H),7.78(dd,J=7. 5,1.5Hz,1H),7.88(d,J=8.5Hz,2H),7.94–7.97(m,2H),8.05–8.08(m,1H),8.11–8.14(m,2H),8.50(d,J=8.5Hz,1H),8.75(d,J=6.5Hz,1H).

[0089] Example 9: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt53

[0090] The synthetic route is as follows:

[0091] Pt53 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt49. 94 mg of the target product was obtained as a yellow solid with a yield of 11%. Molecular weight [M+H] + :851.2.

[0092] Example 10: Tetradentate Ring Metal Platinum (II) Complex Phosphorescent Material Pt54

[0093] The synthetic route is as follows:

[0094] Pt54 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt49 to obtain 87 mg of the target product as a yellow solid with a yield of 18%. 1 H NMR (500MHz, CDCl3-d) δ1.07(s,9H),1.27(s,9H),2.64(s,3H),6.15(dd,J=6. 5,2.0Hz,1H),7.18(dd,J=8.0,1.0Hz,1H),7.24(s,1H),7.27–7.42(m,6H),7.4 5(d,J=8.5Hz,1H),7.69(d,J=8.0Hz,1H),7.75(d,J=2.0Hz,1H),7.84–7.88(m, 3H), 8.06 (dd, J=7.5, 1.5Hz, 1H), 8.24 (d, J=8.0Hz, 1H), 8.59 (d, J=6.5Hz, 1H).

[0095] Example 11: Synthesis of Pt3

[0096] Pt3 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt51. The target product was obtained as a yellow solid (75 mg) with a yield of 26%. Molecular weight [M+H] + :919.4.

[0097] Example 12: Synthesis of Pt6

[0098] Pt6 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt51. The target product was obtained as a yellow solid (72 mg) with a yield of 16%. Molecular weight [M+H] + :1051.4.

[0099] Example 13: Synthesis of Pt20

[0100] Pt20 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt51. The target product was obtained as a yellow solid (63 mg) with a yield of 22%. Molecular weight [M+H] + :933.4.

[0101] Example 14: Synthesis of Pt41

[0102] Pt41 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt51. The target product was obtained as a yellow solid (67 mg) with a yield of 32%. Molecular weight [M+H] + :905.4.

[0103] Example 15: Synthesis of Pt71

[0104] Pt71 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt51. The target product was obtained as a yellow solid (52 mg) with a yield of 28%. Molecular weight [M+H] + :1107.5.

[0105] Example 16: Synthesis of Pt72

[0106] Pt72 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt51. The target product was obtained as a yellow solid (58 mg) with a yield of 38%. Molecular weight [M+H] + :1135.6.

[0107] Example 17: Synthesis of Pt76

[0108] Pt76 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt51. The target product was obtained as a yellow solid (60 mg) with a yield of 39%. Molecular weight [M+H] + :993.5.

[0109] Example 18: Synthesis of Pt80

[0110] Pt80 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt51. The target product was obtained as a yellow solid (53 mg) with a yield of 27%. Molecular weight [M+H] + :1063.5.

[0111] Example 19: Synthesis of Pt81

[0112] Pt81 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt51. The target product was obtained as a yellow solid (42 mg) with a yield of 28%. Molecular weight [M+H] + :1205.5.

[0113] Example 20: Synthesis of Pt102

[0114] Pt102 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt51. The target product was obtained as a yellow solid (37 mg) with a yield of 22%. Molecular weight [M+H] + :970.5.

[0115] Example 21: Synthesis of Pt111

[0116] Pt111 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt51. The target product was obtained as a yellow solid (34 mg) with a yield of 24%. Molecular weight [M+H] + :909.4.

[0117] Example 22: Synthesis of Pt174

[0118] Pt174 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt51. The target product was obtained as a yellow solid (39 mg) with a yield of 31%. Molecular weight [M+H] + :1127.5.

[0119] Example 23: Synthesis of Pt183

[0120] Pt183 was synthesized by referring to the synthesis steps and reaction conditions of compound Pt51. The target product was obtained as a yellow solid (38 mg) with a yield of 27%. Molecular weight [M+H] + :1131.5.

[0121] Theoretical calculation instructions

[0122] 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.

[0123] Table 1. Frontier orbital energy levels of some metal complexes

[0124] As can be seen from the calculated data shown in Table 1, the materials provided by the present invention all have a large energy gap (>3.10 eV), which can meet the requirements of blue light materials; and the frontier orbital energy levels (HOMO and LUMO) of the platinum (II) complex can be adjusted by regulating the ligand structure.

[0125] Photophysical properties:

[0126] Table 2. Photophysical properties of some metal complexes in dichloromethane solution

[0127] Table 3. Photophysical properties of some metal complexes in dichloromethane solution at 77K

[0128] As shown in Tables 2 and 3, the room temperature emission wavelength of the material provided by the present invention in dichloromethane solution is between 465 and 487 nm, and the emission wavelength of the emission spectrum at 77K is between 459 and 490 nm, achieving deep blue light to blue light emission.

[0129] Fabrication of OLED devices:

[0130] As a reference preparation method for a device embodiment, the present invention deposits a p-type dopant material onto the surface of an ITO glass or anode with a luminescent area of ​​2mm×2mm, or co-evaporates the p-type dopant material with a hole injection material at a concentration of 1% to 50% to form a 5-100nm hole injection layer (HIL) and a 5-200nm hole transport layer (HTL). Subsequently, a 10-100nm light-emitting layer (EML) (which may contain the compound described herein) is formed on the hole transport layer, followed by a 20-200nm electron transport layer (ETL) and a 50-200nm cathode. If necessary, an electron blocking layer (EBL) is added between the HTL and EML layers, and an electron injection layer (EIL) is added between the ETL and cathode to produce an OLED device. The OLED device is then tested using standard methods. Unless otherwise specified, the device materials involved in this invention can be obtained by known synthesis methods.

[0131] 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) (Pt51:HTH-85:ETH-45 mass ratio is 10:60:30) / ETH-5 (5 nm) / ET-14 (40 nm) / LiQ (1 nm) / Al (100 nm).

[0132] Device Examples 2-23 and Comparative Example 1 were prepared using structures similar to those of Device Example 1, with the only difference being that Pt52, Pt46, Pt47, Pt48, Pt49, Pt50, Pt171, Pt53, Pt54, Pt3, Pt6, Pt20, Pt41, Pt71, Pt72, Pt76, Pt80, Pt81, Pt102, Pt111, Pt174, Pt183, and R1 were used to replace Pt51 in Device Example 1. The luminescence properties of the comparative examples and device examples prepared above were tested using standard methods, and the data are shown in Table 4. The device structures involved are as follows: where P-4 is HATCN and ET-14 is BPyTP.

[0133] Table 4. Device luminescence characteristics data table

[0134] As can be seen from Table 4, compared with Comparative Example 1, Device Examples 1 to 23 prepared in the present application all showed 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 better electron transport capability of the specific compound material of the present invention. It can be seen that when it is used as a light-emitting layer material to prepare an electronic device, the current efficiency and device life of the device are improved while reducing the driving voltage. In addition, the devices prepared by the present invention are all deep blue light devices, and the CIEy values ​​are all less than 0.19. This shows that the compound provided by the present invention has certain commercial application value.

[0135] In a preferred specific embodiment, the structure of device example 24 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) (Pt51:BN1-8:HTH-85:ETH-45 mass ratio is 10:1:59:30) / ETH-5 (5nm) / ET-14 (40nm) / LiQ (1nm) / Al (100nm).

[0136] Device Examples 25 to 30 were prepared using structures similar to Device Example 24, with the only difference being that the platinum (II) complex and the boron-containing compound in Device Example 24 were replaced with the compounds listed in Table 5. The device structures and luminescence characteristics are shown in Table 5.

[0137] Table 5. Device structure and luminescence characteristics data

[0138] As shown in Table 5, the compounds of the present invention, when used as sensitizing materials in conjunction with boron-containing compounds as luminescent materials, significantly improve the performance of each device. This further demonstrates that the compounds provided by the present invention have considerable commercial application value. Furthermore, the addition of boron-containing compounds to sensitize the device structure can further reduce the CIEy value, thereby further improving the color purity of the device emission.

[0139] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. A tetradentate metal platinum (II) complex of a pyridocarbene, characterized in that: It has the general structure shown in formula (I): In formula (I), R 1 -R 5 Each independently represents a single substitution to the maximum amount of substitution, or no substitution; R 1 -R 5 Each is independently selected from the group consisting of hydrogen, deuterium, C1-C30 alkyl, C1-C30 deuterated alkyl, C6-C60 aryl, C6-C30 arylsilane and combinations thereof; R is selected from the group consisting of hydrogen, deuterium, C1-C30 alkyl, C1-C30 cycloalkyl, C1-C30 deuterated alkyl, C6-C60 aryl, C6-C30 fused ring aryl and combinations thereof.

2. The tetradentate ring metal platinum (II) complex according to claim 1, characterized in that R 1 -R 5 Each is independently selected from hydrogen, deuterium, 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, n-decyl, isodecyl, sec-decyl, tert-decyl, phenyl, triphenylsilane and combinations thereof.

3. The tetradentate ring metal platinum (II) complex according to claim 1, characterized in that R is selected from adamantaneamine, tert-butyl, tert-butylphenyl or a group of the structural formula shown below; The R 6 represents single substitution to the maximum amount of substitution, or no substitution; R 6 is selected from hydrogen, C1-C20 alkyl, C1-C20 deuterated alkyl; R a and R b and are identical or independently selected from C3-C30 alkyl, C1-C20 deuterated alkyl, C5-C30 cycloalkyl, C6-C30 aryl, and combinations thereof.

4. The tetradentate ring metal platinum (II) complex according to claim 3, characterized in that R 6 is selected from hydrogen, methyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, D, CD3; said R a , R b The same or each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, phenyl and combinations thereof.

5. The tetradentate ring metal platinum (II) complex according to any one of claims 1 to 3 and 4, characterized in that Select any one of the chemical structures shown below, wherein "D" represents deuterium and Ph represents phenyl:

6. Use of the tetradentate metal platinum (II) complex according to any one of claims 1 to 3, 4, and 5 in electronic devices, wherein the electronic devices include one or more of 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, or organic laser diodes.

7. 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 the tetradentate metal platinum (II) complex according to any one of claims 1-3, 4 and 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 according to any one of claims 1 to 3, 4 and 5.

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

10. An organic optoelectronic device, characterized in that: The organic photoelectric device comprises: a substrate layer; a first electrode, which is on the substrate; an organic light-emitting functional layer, which is on the first electrode; and a second electrode, which is on the organic light-emitting functional layer; wherein the organic light-emitting functional layer contains the tetradentate metal platinum (II) complex according to any one of claims 1 to 3, 4, and 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 organic molecular light-emitting material.

12. A composition, characterized in that The composition comprises the tetradentate platinum (II) complex according to any one of claims 1-3, 4 and 5.

13. A preparation, characterized in that The preparation comprises the tetradentate platinum (II) complex according to any one of claims 1-3, 4 and 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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