Multi-emission tetradentate metal platinum (II) complex and application thereof in organic light-emitting device

Abstract

The invention belongs to the field of preparation of organic electroluminescent materials, and particularly relates to a multi-emission tetradentate metal platinum (II) complex and application thereof in an organic light-emitting device. According to the tetradentate cyclometalated platinum (II) complex phosphorescent material based on the diaza-carbazole structure, the interaction among molecules can be increased, and single emission and multi-emission can be realized. The compound has good chemical stability and thermal stability, hole and electron transmission is balanced, and an evaporation type OLED device is easy to prepare. When the compound disclosed by the invention is used as a luminescent layer material for manufacturing an organic electroluminescent device, the current efficiency and the service life are greatly improved, and the lighting voltage is reduced. The organic light emitting diode has a great application prospect in the field of OLED display and illumination.

Description

Technical Field

[0001] The present invention belongs to the field of preparation of organic electroluminescent materials, and particularly relates to a multi-emission tetradentate platinum(II) complex and its application in organic light-emitting devices. Background Art

[0002] White organic light-emitting materials have extensive applications in practice and have received continuous attention in the academic community. So far, research reports mainly rely on the combination of multiple components to cover the entire visible light range in terms of emission color. Compared with combined emitters, single-molecule white light emitters have advantages such as no phase separation, no color attenuation, good stability and reproducibility, and simple device preparation process, creating new possibilities for the development of low-cost and high-efficiency devices. Single-component multi-emission organic light-emitting materials have advantages such as simple structure and multiple emissions, and have broad application prospects in sensing, bioimaging, and white organic light-emitting diodes, etc. Generally, organic light-emitting materials with multi-emission characteristics are composed of different light-emitting groups connected by covalent or non-covalent methods, and the emission wavelength is adjusted by different chromophores, and the intensity of multi-emission is regulated by the content of different chromophores. However, the synthesis repeatability and luminescence stability of such materials are poor. For small-molecule organic materials, the above preparation methods are not feasible.

[0003] According to Kasha's rule, luminescence must come from the lowest excited state of the molecule. It is very difficult to achieve incomplete energy transfer between different chromophores. Therefore, in most cases, only one chromophore can emit light directly, and it is a huge challenge to achieve multi-emission in organic small-molecule light-emitting materials.

[0004] In addition, it is also a great challenge to enable the same material to achieve single emission and multi-emission. Almost all the light-emitting layers in currently applied OLED single-emission devices use the host-guest light-emitting system mechanism, that is, a low-concentration guest light-emitting material is doped in the host material, and its luminescence can exhibit single emission or multi-emission with the change of doping concentration. The energy level of the host material is generally greater than that of the guest light-emitting material, and the energy is transferred from the host material to the guest material to excite the guest material to emit light. The commonly used phosphorescent organic material CBP (4,4′-bis(9-carbazolyl)-biphenyl) has high efficiency and high triplet energy level. When it is used as an organic material, the triplet energy can effectively transfer from the light-emitting organic material to the guest phosphorescent light-emitting material. However, due to the characteristics of CBP that holes are easy to transport and electrons are difficult to flow, the charge imbalance in the light-emitting layer is caused, resulting in a reduction in the current efficiency of the device. Summary of the Invention

[0005] The object of the present invention is to provide a multi-emissive tetradentate platinum(II) metal complex and its application in organic light-emitting devices. Preparing an organic electroluminescent device with the compound of the present invention as a doping material can improve the current efficiency of the organic electroluminescent device, improve the device lifetime, and also reduce the operating voltage of the device components.

[0006] The multi-emissive tetradentate platinum(II) metal complex provided by the present invention has the structure shown in the following formula Pt-(I);

[0007]

[0008] Wherein: in formula Pt-(I), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represents a single substituent to the maximum possible number of substitutions or no substitution; R 1 , R 2 each independently represents any one of hydrogen, deuterium, halogen, cyano, C1–C30 alkyl, C1–C30 haloalkyl, C1–C30 deuterated alkyl, C6–C60 aryl, and C6–C60 arylsilane; R 3 , R 4 , R 5 and R 6 each independently represents hydrogen, deuterium, C1–C10 alkyl; R a and R b each independently represents C3–C30 alkyl.

[0009] Preferably, in formula Pt-(I), the said R 1 is selected from one or more of hydrogen, deuterium, methyl, ethyl, tert-butyl, and deuterated tert-butyl; R 2 is selected from one or more of hydrogen, deuterium, CN, CF3, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, phenyl, and triarylsilane.

[0010] In formula Pt-(I), the said R 3 , R 4 , R 5 and R 6 each independently represents one or more of hydrogen, deuterium, methyl, ethyl, propyl, butyl, and tert-butyl.

[0011] Furthermore, the platinum(II) metal complex is selected from any one of the following chemical structures, where "D" represents deuterium:

[0012]

[0013]

[0014]

[0015] Furthermore, the present invention also provides an application of a tetradentate cyclometalated platinum(II) complex having the structure shown in the above formula Pt-(I) in the preparation of electronic devices.

[0016] Furthermore, the electronic devices include organic photovoltaic devices, organic optoelectronic devices, organic light-emitting diodes (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), 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). The multi-emission tetradentate metal platinum(II) complex is used as a luminescent doping material in electronic devices.

[0017] According to one or more embodiments, the present invention also provides an organic light-emitting device, which includes a cathode, an anode, and at least one organic functional layer therebetween; the organic functional layer contains a tetradentate cyclometalated platinum(II) complex having the structure shown in the above formula Pt-(I).

[0018] Furthermore, the organic functional layer includes a light-emitting material layer, and the light-emitting material layer contains a tetradentate cyclometalated platinum(II) complex having the structure shown in the above formula Pt-(I). The mass percentage of the complex is 0.1%-50%.

[0019] On the other hand, the present invention also provides an organic optoelectronic device, which includes:

[0020] A substrate layer;

[0021] A first electrode;

[0022] A second electrode facing the first electrode;

[0023] And a light-emitting material layer disposed between the first electrode and the second electrode; the light-emitting material layer contains a host material and a doping material; the tetradentate cyclometalated platinum(II) complex having the structure shown in the above formula Pt-(I) can be included as a doping material in the light-emitting material layer.

[0024] Further, the host material includes an electron-transporting host material and a hole-transporting host material.

[0025] Further, the usage ratio of the host material is greater than that of the doping material.

[0026] More preferably, the doping material further comprises a fluorescent doping material, which is preferably a boron-containing organic molecular luminescent material. The compound of the present invention can phosphorescently sensitize boron-containing compounds.

[0027] The present invention also provides a composition comprising a tetradentate cyclometalated platinum(II) complex having the structure shown by the above formula Pt-(I).

[0028] The present invention also provides a preparation comprising a tetradentate cyclometalated platinum(II) complex having the structure shown by the above formula Pt-(I) or the composition as described above and at least one solvent. There is no particular limitation on the solvent, and unsaturated hydrocarbon solvents well known to those skilled in the art such as toluene, xylene, mesitylene, tetralin, decalin, dicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, etc., halogenated saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, etc., halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, etc., ether solvents such as tetrahydrofuran, tetrahydropyran, etc., and ester solvents such as alkyl benzoates can be used.

[0029] The present invention also provides a display or lighting device comprising one or more of the above-described organic optoelectronic devices.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0031] Compared with conventional tetradentate platinum(II) complexes, the phosphorescent material of the tetradentate cyclometalated platinum(II) complex based on the diazabenzocarbazole structure of the present invention can increase the intermolecular interaction, and can achieve single emission or multi-emission. The complex can be used as a single-molecule blue light material at low concentrations, and excimer aggregates are generated at high concentrations to achieve white light emission, and the white light color can be regulated according to the excitation wavelength. In addition, the luminescent materials involved in the present invention all have good chemical stability and thermal stability. Introducing an alkyl group at the ortho position of diazabenzocarbazole will significantly improve the thermal stability of the platinum(II) complex; the introduction of a bulky alkyl group or a substituted aryl group on the benzene ring at the lower left of the molecule will also contribute to the improvement of thermal stability. It balances the transport of holes and electrons and is easy to prepare vapor-deposited OLED devices. Using the compound of the present invention as the luminescent layer material to fabricate an organic electroluminescent device can greatly improve the current efficiency and lifetime and reduce the turn-on voltage. Further adopting a phosphorescent sensitization boron-containing compound system can improve the color purity of the device. The emission peaks of the luminescent materials involved in the present invention cover the three primary color bands of red, green, and blue, and can be used as blue light or single-doped white light OLEDs, and have great application prospects in the fields of OLED display and lighting. Description of the Drawings

[0032] To more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings, where:

[0033] Figure 1 is the emission spectrum of Pt1 at low concentration and the emission spectra at different excitation wavelengths at high concentration in toluene solution;

[0034] Figure 2 is the high-resolution mass spectrometry data of Pt1;

[0035] Figure 3 is the comparison of the theoretical calculation data between Pt1 and R1. Detailed implementation manners

[0036] The term "optional" or "optionally" used in the present invention means that the subsequent described event or situation may or may not occur, and this description includes the situation where the event or situation occurs and the situation where it does not occur.

[0037] Disclosed are the components that can be used to prepare the compositions described in the present invention, as well as the compositions themselves to be used in the methods disclosed in the present invention. These and other substances are disclosed in the present invention, and it should be understood that when combinations, subsets, interactions, groups, etc. of these substances are disclosed, and without specifically disclosing the specific references of each various individual and total combinations and permutations of these compounds, each is specifically anticipated and described in the present invention. For example, if a specific compound is disclosed and discussed, and many modifications that can be made to many molecules containing the compound are discussed, then specifically anticipated are various and each combination and permutation of the compound, and the said modifications can be made, unless specifically stated to the contrary otherwise. Therefore, if a class of molecules A, B, and C and a class of molecules D, E, and F are disclosed, and an example of the combined molecule A-D is disclosed, then even if each is not individually recorded, each individually and totally anticipated meaning combination, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F is considered disclosed. Similarly, any subset or combination of these is also disclosed. Therefore, for example, the sub-groups A-E, B-F, and C-E should be considered disclosed. These concepts apply to all aspects of the present invention, including but not limited to the steps of the methods for preparing and using the compositions. Therefore, if there are various additional steps that can be carried out, it should be understood that each of these additional steps can be carried out in a specific embodiment of the method or a combination of embodiments.

[0038] The linking atoms used in the present invention are capable of linking two groups, e.g., N and C groups. The linking atom can optionally (if valence bonds permit) have other attached chemical moieties. For example, in one aspect, oxygen will not have any other chemical groups attached because once bonded to two atoms (e.g., N or C), the valence bonds are satisfied. In contrast, when carbon is the linking atom, two additional chemical moieties can be attached to the carbon atom. Suitable chemical moieties include, but are not limited to, hydrogen, hydroxy, alkyl, alkoxy, ═O, halogen, nitro, amine, amide, mercapto, aryl, heteroaryl, cycloalkyl, and heterocycloalkyl.

[0039] In defining the various terms, "R 1 ", "R 2 ", "R 3 ", and "R 4 " are used in the present invention as general symbols to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed in the present invention, and when they are defined as certain substituents in one instance, they can be defined as some other substituents in other instances.

[0040] The term "alkyl" as used in the present invention is 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 can be cyclic or acyclic. The alkyl can be branched or unbranched. The alkyl can also be substituted or unsubstituted. For example, the alkyl can be substituted with one or more groups including, but not limited to, optionally substituted alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxy, nitro, silyl, sulfo-oxo, or mercapto as described in the present invention. A "lower alkyl" group is an alkyl group containing 1 to 6 (e.g., 1 to 4) carbon atoms.

[0041] Throughout the specification, "alkyl" is generally used to refer to both unsubstituted alkyl and substituted alkyl simultaneously; however, substituted alkyl is also specifically referred to in the present invention by identifying the specific substituents on the alkyl. For example, the term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "alkoxyalkyl" specifically refers to an alkyl substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl substituted with one or more amino groups, as described below, etc. When "alkyl" is used in one instance and a specific term such as "alkyl alcohol" is used in another instance, it is not meant to imply that the term "alkyl" does not simultaneously refer to specific terms such as "alkyl alcohol", etc.

[0042] This practice is also used for other groups described in the present invention. That is, when terms such as "cycloalkyl" refer to both unsubstituted and substituted cycloalkyl moieties, the substituted moiety can be further specifically determined in the present invention; for example, a specifically substituted cycloalkyl can be referred to as, for example, "alkylcycloalkyl". Similarly, a substituted alkoxy can be specifically referred to as, for example, "halogenated alkoxy", and a specific substituted alkenyl can be, for example, "enol", etc. Likewise, the practice of using a general term such as "cycloalkyl" and a specific term such as "alkylcycloalkyl" is not intended to imply that the general term does not simultaneously include the specific term.

[0043] The term "aryl" used in the present invention is a group containing any carbon-based aromatic group, and the carbon-based aromatic group includes, but is not limited to, phenyl, naphthyl, phenyl group, biphenyl, phenoxyphenyl, anthryl, phenanthryl, etc. The term "aryl" also includes "heteroaryl", which is defined as a group containing an aromatic group having at least one heteroatom within the ring introducing 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. The aryl can be substituted or unsubstituted. The aryl can be substituted with one or more groups, and the groups include, but are not limited to, the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde group, amino group, carboxyl group, ester group, halogen, hydroxyl group, carbonyl group, azide group, nitro group, silyl group, sulfo-oxo or mercapto group described in the present invention. The term "biaryl" is a specific type of aryl and is included in the definition of "aryl". Biaryl refers to two aryl groups joined together by a fused ring structure, as in naphthalene, or two aryl groups connected by one or more carbon-carbon bonds, as in biphenyl.

[0044] The term "halogen" used in the present invention refers to the halogens fluorine, chlorine, bromine, and iodine.

[0045] The term "nitrile" used in the present invention is represented by the formula -CN.

[0046] "R 1 ", "R 2 ", "R 3 ", "R n " (where n is an integer) can independently have one or more of the groups listed above. For example, if R 1If it is a straight-chain alkyl group, then one hydrogen atom of the alkyl group can be optionally substituted with a hydroxyl group, an alkoxy group, an alkyl group, a halogen, etc. Depending on the selected group, the first group can be incorporated within the second group, or alternatively, the first group can be pendant, i.e., attached to the second group. For example, for the phrase "alkyl group containing an amino group", the amino group can be incorporated within the main chain of the alkyl group. Alternatively, the amino group can be attached to the main chain of the alkyl group. The nature of the selected group will determine whether the first group is embedded or attached to the second group.

[0047] For various reasons, the use of organic materials in optoelectronic devices has become increasingly urgent. Many of the materials used to fabricate such devices are relatively inexpensive, so organic optoelectronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, can make them very suitable for special applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials may have performance advantages over conventional materials. For example, the wavelength of light emitted by the organic light-emitting layer can usually be tuned with appropriate dopants.

[0048] Excitons decay from the singlet excited state to the ground state to produce prompt luminescence, which is fluorescence. If excitons decay from the triplet excited state to the ground state to produce luminescence, this is phosphorescence. Due to the strong spin-orbit coupling of heavy metal atoms between the singlet and triplet excited states, effectively enhancing intersystem crossing (ISC), phosphorescent metal complexes (such as platinum complexes) have shown their potential to utilize both singlet and triplet excitons simultaneously, achieving 100% internal quantum efficiency. Therefore, phosphorescent metal complexes are a good choice for dopants in the emissive layer of organic light-emitting diodes (OLEDs) and have received great attention in both academic and industrial fields. In the past decade, many achievements have been made, leading to profitable applications of this technology. For example, OLEDs have been used in advanced displays for smartphones, TVs, and digital cameras.

[0049] However, to date, blue electroluminescent devices are still the most challenging area in this technology, and the stability of blue devices is a major problem. It has been demonstrated that the choice of host material is very important for the stability of blue devices. However, the lowest energy of the triplet excited state (T1) of blue luminescent materials is very high, which means that the lowest energy of the triplet excited state (T1) of the host material for blue devices should be even higher. This has increased the difficulty in developing host materials for blue devices.

[0050] The metal complexes of the present invention can be customized or tuned for specific applications that are desired to have specific emission or absorption characteristics. The optical properties of the metal complexes disclosed in the present invention can be adjusted by changing the structure of the ligands surrounding the metal center or by changing the structure of the fluorophores on the ligands. For example, in the emission and absorption spectra, metal complexes with ligands having electron-donating substituents or electron-withdrawing substituents can generally exhibit different optical properties. The color of the metal complexes can be adjusted by modifying the fluorophores and the conjugated groups on the ligands.

[0051] The emission of the complexes of the present invention can be adjusted, for example, by changing the ligand or fluorophore structure, for example, from ultraviolet to near-infrared. A fluorophore is a group of atoms in an organic molecule that can absorb energy to produce a singlet excited state, and the singlet exciton rapidly decays to produce immediate luminescence. On the one hand, the complexes of the present invention can provide emission in most of the visible spectrum. In a specific example, the complexes of the present invention can emit light in the wavelength range of visible light or near-infrared light. On the other hand, the complexes of the present invention have improved stability and efficiency compared to traditional emission complexes. In addition, the complexes of the present invention can be used as luminescent labels for, for example, biological applications, anticancer agents, emitters in organic light-emitting diodes (OLEDs), or combinations thereof. In another aspect, the complexes of the present invention can be used in light-emitting devices, such as compact fluorescent lamps (CFLs), light-emitting diodes (LEDs), incandescent lamps, and combinations thereof.

[0052] Compounds or complex complexes containing platinum are disclosed herein. The terms compound or complex can be used interchangeably in the present invention. In addition, the compounds disclosed herein have a neutral charge.

[0053] The compounds disclosed herein can exhibit desired properties and have emission and / or absorption spectra that can be adjusted by selecting appropriate ligands. In another aspect, the present invention can exclude any one or more of the compounds, structures, or portions thereof specifically recited herein.

[0054] The compounds disclosed herein can be used in various applications. As a luminescent material, the compound can be used in organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting devices.

[0055] In addition, compared to traditional materials, the compounds in the present invention used in light-emitting devices (such as OLEDs) can improve the luminescence efficiency and the operating time of the devices.

[0056] 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.

[0057] The compounds disclosed herein can be delayed fluorescence and / or phosphorescence emitters. In one aspect, the compounds disclosed herein can be delayed fluorescence emitters. In one aspect, the compounds disclosed herein can be phosphorescence emitters. In another aspect, the compounds disclosed herein can be both delayed fluorescence emitters and phosphorescence emitters.

[0058] The compounds disclosed in the embodiments of the present invention are applicable to a variety of optical and electro-optical devices, including but not limited to light absorption devices such as solar and photosensitive sensors, organic light-emitting diodes (OLEDs), light-emitting devices or devices with both light absorption and light-emitting capabilities, and markers for biological applications.

[0059] The compounds provided in the embodiments of the present invention can be used in a light-emitting device such as an OLED. The device includes at least one cathode, at least one anode, and at least one light-emitting layer, and at least one of the light-emitting layers includes the tetradentate cyclometalated platinum(II) complex having the structure shown by Pt-(I) above. Specifically, the light-emitting device can include an anode, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode formed by sequential deposition. Among them, the hole transport layer, the light-emitting layer, and the electron transport layer are all organic layers, and the anode and the cathode are electrically connected. The light-emitting device can be selected from known or unknown materials, and the present invention does not make specific limitations on them.

[0060] It should be noted that the above general description and the following detailed description are only exemplary and explanatory, and are not restrictive.

[0061] The present disclosure can be more easily understood by referring to the following specific embodiments and the examples included therein.

[0062] 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 synthesis methods (otherwise indicated), or specific reagents (otherwise indicated), because 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 in the present invention can be used in this practice or test, exemplary methods and materials are described below. Unless otherwise stated, all commercial reagents involved in the following tests are used directly after purchase.

[0063] Synthesis Examples

[0064] The following examples regarding compound synthesis, composition, devices, or methods are only to provide a general method to the industry field and are not used to limit the protection scope of the patent. For the data (quantity, temperature, etc.) mentioned in the patent, every effort is made to ensure accuracy, but there may still be some errors. Unless otherwise specified, weighing is done separately, the temperature is in °C, or at room temperature, and the pressure is close to atmospheric pressure.

[0065] The following examples provide methods for preparing new compounds, but the preparation of such compounds is not limited to these methods. In this technical field, since the compounds protected in this patent are easy to modify and prepare, their preparation can adopt the methods listed below or other methods. The following examples are only for illustration and do not limit the scope of protection of this patent. The temperature, catalyst, concentration, reactants, and reaction process can all be changed to select different conditions for preparing the compounds for different reactants.

[0066] 1 H NMR (500 MHz), 1 H NMR (400 MHz), 13 The 1H NMR (500 MHz), 13C NMR (126 MHz) spectra were measured on a Bruker AVANCE III (500 M) nuclear magnetic resonance spectrometer; unless otherwise specified, NMR was performed using DMSO-d6 or CDCl3 containing 0.1% TMS as the solvent, where 1 For 1H NMR spectra, when CDCl3 was used as the solvent, TMS (δ = 0.00 ppm) was used as the internal standard; when DMSO-d6 was 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) was used as the internal standard. 13 In the 13C NMR spectra, CDCl3 (δ = 77.00 ppm) or DMSO-d6 (δ = 39.52 ppm) was used as the internal standard. The HPLC-MS was measured on an Agilent 6210TOF LC / MS mass spectrometer; the HRMS spectra were measured on an Agilent 6210TOF LC / MS liquid chromatography-time of flight mass spectrometer. 1 In the 1H NMR spectral data: s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, m = multiplet, br = broad.

[0067] Example 1: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt1

[0068] The synthetic route is as follows:

[0069]

[0070] Synthesis of Intermediate 3: Add 1 (746 mg, 3.67 mmol, 1.0 equiv), 2 (880 mg, 3.67 mmol, 1.0 equiv), Pd(dppf)Cl2 (269 mg, 0.37 mmol, 10 mol%), and sodium carbonate (779 mg, 7.35 mmol, 2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Then evacuate and refill with nitrogen three times, and add diglyme (13 mL) and water (2 mL) under nitrogen protection. After reacting in an oil bath at 90 °C for 26 h, cool to room temperature. After removing the solvent by distillation under reduced pressure, the crude product is separated by silica gel column chromatography. Eluent: ethyl acetate / methanol = 1:0 - 100:1, obtaining 483 mg of a gray solid with a yield of 56%. It was not structurally characterized and was directly used for the next step.

[0071] Synthesis of Intermediate 4: Add 3 (380 mg, 1.61 mmol, 1.0 equiv), PyBr (380 mg, 1.78 mmol, 1.1 equiv), tris(dibenzylideneacetone)dipalladium(0) (74 mg, 0.08 mmol, 5 mol%), SPhos (66 mg, 0.16 mmol, 10 mol%), and sodium tert-butoxide (465 mg, 4.84 mmol, 3.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Evacuate and refill with nitrogen three times, and add toluene (5 mL) under nitrogen protection. After reacting in an oil bath at 100 °C for 17 h, cool to room temperature. After removing the solvent by distillation under reduced pressure, the crude product is separated by silica gel column chromatography. Eluent: ethyl acetate / methanol = 1:0 - 50:1, obtaining 304 mg of a yellow solid with a yield of 57%. 1 1H NMR (400 MHz, DMSO-d6) δ 1.39 (s, 9H), 3.91 (s, 3H), 7.58 (dd, J = 5.6, 1.6 Hz, 1H), 7.71 (d, J = 2.6 Hz, 1H), 7.77 (dd, J = 5.8, 1.0 Hz, 1H), 7.81 (d, J = 1.7 Hz, 1H), 8.41 (d, J = 2.5 Hz, 1H), 8.57 (d, J = 5.8 Hz, 1H), 8.66 (d, J = 5.3 Hz, 1H), 9.38 (s, 1H).

[0072] Synthesis of Intermediate 6: 4 (368 mg, 1.11 mmol, 1.0 equiv), hydrobromic acid (15 mL), and acetic acid (1 mL) were added to a three-necked flask equipped with a magnetic stir bar. After reacting in an oil bath at 120 °C for 43 h, it was cooled to room temperature, neutralized with sodium bicarbonate, extracted with ethyl acetate, dried over sodium sulfate, and concentrated to obtain Compound 5, which was directly used in the next step. Take 5 in a three-necked flask, add m-chlorobromobenzene (601 mg, 3.14 mmol, 2.0 equiv), CuI (149 mg, 0.79 mmol, 0.5 equiv), 2-pyridinecarboxylic acid (97 mg, 0.79 mmol, 0.5 equiv), and potassium phosphate (833 mg, 3.93 mmol, 2.5 equiv). The nitrogen was evacuated and replaced three times, and dimethyl sulfoxide (4 mL) was added under nitrogen protection. After reacting in an oil bath at 110 °C for 72 h, it was cooled to room temperature, quenched with water, extracted with ethyl acetate, washed with water, dried over sodium sulfate, and the solvent was removed by distillation under reduced pressure. The obtained crude product was separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 2:1 - 1:1 and then ethyl acetate / methanol = 1:0 - 100:1, to obtain 350 mg of solid, with a yield of 74%. 1 H NMR (500 MHz, DMSO-d6) δ 1.32 (s, 9H), 7.15 (ddd, J = 8.5, 2.5, 1.0 Hz, 1H), 7.27 (ddd, J = 8.0, 2.0, 1.0 Hz, 1H), 7.29 (t, J = 2.0 Hz, 1H), 7.44 (t, J = 8.0 Hz, 1H), 7.54 (dd, J = 5.5, 1.5 Hz, 1H), 7.73 (dd, J = 1.5, 0.5 Hz, 1H), 7.77 (d, J = 2.5 Hz, 1H), 7.85 (d, J = 5.5 Hz, 1H), 8.57 (d, J = 2.5 Hz, 1H), 8.60 (dd, J = 5.5, 0.5 Hz, 1H), 8.65 (s, 1H), 9.48 (s, 1H).

[0073] Synthesis of Intermediate 7: 6 (350 mg, 0.82 mmol, 1.0 equiv), NH2 (365 mg, 1.23 mmol, 1.5 equiv), tris(dibenzylideneacetone)dipalladium(0) (75 mg, 0.082 mmol, 10 mol%), SPhos (67 mg, 0.16 mmol, 20 mol%), and sodium tert-butoxide (158 mg, 1.64 mmol, 2.0 equiv) were added to a three-necked flask equipped with a magnetic stir bar. The nitrogen was evacuated and replaced three times, and toluene (3 mL) was added under nitrogen protection. After reacting in an oil bath at 95 °C for 23 h, it was cooled to room temperature, filtered, and the solvent was removed by distillation under reduced pressure. The crude product was separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 10:1 - 1:1, to obtain 428 mg of brown solid, with a yield of 76%. It was not structurally characterized and was directly used in the next step.

[0074] Synthesis of ligand L1: Add 7 (428 mg, 0.62 mmol, 1.0 equiv), ammonium hexafluorophosphate (203 mg, 1.24 mmol, 2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Evacuate and refill with nitrogen three times, and then add triethyl orthoformate (3 mL) under nitrogen protection. React in an oil bath at 75 °C for 5 h, then cool to room temperature. Remove the solvent by rotary evaporation under reduced pressure, and separate by silica gel column chromatography. Eluent: dichloromethane / ethyl acetate = 100:1 - 20:1, obtaining 483 mg of a brown solid with a yield of 92%. 1 1H NMR (500 MHz, DMSO-d6) δ 1.32 (s, 9H), 1.36 (s, 18H), 7.54–7.59 (m, 2H), 7.65 (d, J = 1.5 Hz, 2H), 7.71–7.76 (m, 3H), 7.77–7.80 (m, 3H), 7.82–7.86 (m, 2H), 7.88–7.91 (m, 1H), 7.96–8.00 (m, 1H), 8.03 (d, J = 2.5 Hz, 1H), 8.61 (d, J = 5.5 Hz, 1H), 8.66 (d, J = 6.0 Hz, 1H), 8.68 (d, J = 2.5 Hz, 1H), 9.49 (d, J = 1.0 Hz, 1H), 10.51 (s, 1H).

[0075] Synthesis of Pt1: Add L1 (200 mg, 0.24 mmol, 1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (89 mg, 0.24 mmol, 1.0 equiv) and sodium acetate (79 mg, 0.96 mmol, 4.0 equiv) into a sealed tube equipped with a magnetic stir bar. Evacuate and refill with nitrogen three times, and then add diglyme (15 mL) under nitrogen protection. Bubble nitrogen through the solution for 30 min to remove oxygen. React in an oil bath at 135 °C for 48 h. After cooling to room temperature, remove the solvent by rotary evaporation under reduced pressure. Separate the crude product by silica gel column chromatography. Eluent: petroleum ether / dichloromethane = 2:1 - 1:1, obtaining 30 mg of a yellow solid with a yield of 14%. 11H NMR (500 MHz, DMSO-d6) δ 1.39 (s, 18H), 1.42 (s, 9H), 7.03 (d, J = 8.5 Hz, 1H), 7.12 (d, J = 8.5 Hz, 1H), 7.35 (t, J = 8.0 Hz, 1H), 7.41–7.45 (m, 3H), 7.53 (t, J = 8.0 Hz, 1H), 7.65 (dd, J = 7.5, 2.0 Hz, 2H), 7.81 (d, J = 6.0 Hz, 1H), 7.85 (d, J = 5.5 Hz, 2H), 8.38 (s, 1H), 8.46 (d, J = 8.5 Hz, 1H), 8.64 (d, J = 6.0 Hz, 1H), 8.70 (d, J = 5.5 Hz, 1H), 9.43 (s, 1H).

[0076] Example 2: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt2

[0077] The synthesis route is as follows:

[0078]

[0079]

[0080] Synthesis of intermediate 2-6: Add 5 (1.0 equivalent) to a three-necked flask equipped with a magnetic stir bar, then add 1-bromo-3-tert-butyl-5-chlorobenzene (2.0 equivalents), CuI (0.5 equivalent), 2-pyridinecarboxylic acid (0.5 equivalent), and potassium phosphate (2.5 equivalents). Evacuate and refill with nitrogen three times, add dimethyl sulfoxide (5 mL) under nitrogen protection, react in an oil bath at 110 °C for 72 hours, then cool to room temperature. Quench with water, extract with ethyl acetate, wash with water, dry over sodium sulfate, and remove the solvent by rotary evaporation under reduced pressure. The obtained crude product is separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 2:1 - 1:1, then ethyl acetate / methanol = 1:0 - 100:1, to obtain 300 mg of solid, with a yield of 64%.

[0081] Synthesis of intermediate 2-7: Add 2-6 (1.0 equivalent), NH2 (1.5 equivalents), tris(dibenzylideneacetone)dipalladium(0) (10 mol%), SPhos (20 mol%), and sodium tert-butoxide (2.0 equivalents) to a three-necked flask equipped with a magnetic stir bar. Evacuate and refill with nitrogen three times, add toluene (5 mL) under nitrogen protection. React in an oil bath at 95 °C for 20 hours, then cool to room temperature, filter, and remove the solvent by rotary evaporation under reduced pressure. The crude product is separated by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 10:1 - 1:1, to obtain 310 mg of brown solid, with a yield of 70%. Without structural characterization, it is directly used for the next step.

[0082] Synthesis of Ligand L2: Add 2-7 (1.0 equiv), ammonium hexafluorophosphate (2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Evacuate and backfill with nitrogen three times, and then add triethyl orthoformate (3 mL) under nitrogen protection. React in an oil bath at 75 °C for 5 h, then cool to room temperature. Remove the solvent by rotary evaporation under reduced pressure, and separate by silica gel column chromatography. Eluent: dichloromethane / ethyl acetate = 100:1 - 20:1, obtaining 295 mg of brown solid with a yield of 83%. MS: m / z 755.44 (M) + 。

[0083] Synthesis of Pt2: Add L2 (1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (1.0 equiv) and sodium acetate (4.0 equiv) into a sealed tube equipped with a magnetic stir bar. Evacuate and backfill with nitrogen three times, and then add diglyme (15 mL) under nitrogen protection. Bubble nitrogen through the solution for 30 min to remove oxygen. React in an oil bath at 135 °C for 48 h, then cool to room temperature. Remove the solvent by rotary evaporation under reduced pressure, and separate the crude product by silica gel column chromatography. Eluent: petroleum ether / dichloromethane = 2:1 - 1:1, obtaining 43 mg of yellow solid with a yield of 21%. MS: m / z 948.39 (M + H) + 。

[0084] Example 3: Tetradentate Cyclometalated Platinum(II) Complex Phosphorescent Luminescent Material Pt3

[0085] The synthesis route is as follows:

[0086]

[0087]

[0088] Synthesis of Intermediate 3-6: Add 5 (1.0 equiv) into a three-necked flask equipped with a magnetic stir bar, then add 1-bromo-3-tert-butyl-5-chlorobenzene (2.0 equiv), CuI (0.5 equiv), 2-pyridinecarboxylic acid (0.5 equiv) and potassium phosphate (2.5 equiv). Evacuate and backfill with nitrogen three times, and then add dimethyl sulfoxide (5 mL) under nitrogen protection. React in an oil bath at 110 °C for 72 h, then cool to room temperature. Quench with water, extract with ethyl acetate, wash with water and dry over sodium sulfate. Remove the solvent by rotary evaporation under reduced pressure, and separate the crude product by silica gel column chromatography. Eluent: petroleum ether / ethyl acetate = 2:1 - 1:1 then ethyl acetate / methanol = 1:0 - 100:1, obtaining 321 mg of solid with a yield of 61%.

[0089] Synthesis of Intermediate 3-7: Add 3-6 (1.0 equiv), NH2 (1.5 equiv), tris(dibenzylideneacetone)dipalladium (10 mol%), SPhos (20 mol%) and sodium tert-butoxide (2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Flush with nitrogen three times, and then add toluene (5 mL) under nitrogen protection. React in an oil bath at 95 °C for 20 h, then cool to room temperature. Filter, remove the solvent by rotary evaporation under reduced pressure, and separate the crude product by silica gel column chromatography. Eluent: petroleum ether / ethyl acetate = 10:1 - 1:1, to obtain 387 mg of a brown solid with a yield of 75%. Without structural characterization, it was directly used for the next step.

[0090] Synthesis of Ligand L3: Add 3-7 (1.0 equiv) and ammonium hexafluorophosphate (2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Flush with nitrogen three times, and then add triethyl orthoformate (3 mL) under nitrogen protection. React in an oil bath at 75 °C for 5 h, then cool to room temperature. Remove the solvent by rotary evaporation under reduced pressure, and separate by silica gel column chromatography. Eluent: dichloromethane / ethyl acetate = 100:1 - 20:1, to obtain 303 mg of a brown solid with a yield of 81%. MS: m / z 859.51 (M) + 。

[0091] Synthesis of Pt3: Add L3 (1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (1.0 equiv) and sodium acetate (4.0 equiv) into a sealed tube equipped with a magnetic stir bar. Flush with nitrogen three times, and then add diethylene glycol dimethyl ether (15 mL) under nitrogen protection. Bubble nitrogen to remove oxygen for 30 min. React in an oil bath at 135 °C for 48 h. After the reaction is cooled to room temperature, remove the solvent by rotary evaporation under reduced pressure, and separate the crude product by silica gel column chromatography. Eluent: petroleum ether / dichloromethane = 2:1 - 1:1, to obtain 36 mg of a yellow solid with a yield of 17%. MS: m / z 1052.46 (M+H) + 。

[0092] Example 4: Tetradentate Cyclometalated Platinum(II) Complex Phosphorescent Luminescent Material Pt4

[0093] The synthesis route is as follows:

[0094]

[0095]

[0096] Synthesis of Intermediate 4-7: Add 3-6 (1.0 equiv), dMNH2 (1.5 equiv), tris(dibenzylideneacetone)dipalladium (10 mol%), SPhos (20 mol%), and sodium tert-butoxide (2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Flush with nitrogen three times, and then add toluene (5 mL) under nitrogen protection. React in an oil bath at 95 °C for 20 h, then cool to room temperature. Filter, remove the solvent by rotary evaporation under reduced pressure, and separate the crude product by silica gel column chromatography. Eluent: petroleum ether / ethyl acetate = 10:1 - 1:1 to obtain 335 mg of a brown solid with a yield of 71%.

[0097] Synthesis of Ligand L4: Add 4-7 (1.0 equiv) and ammonium hexafluorophosphate (2.0 equiv) into a three-necked flask equipped with a magnetic stir bar. Flush with nitrogen three times, and then add triethyl orthoformate (3 mL) under nitrogen protection. React in an oil bath at 75 °C for 5 h, then cool to room temperature. Remove the solvent by rotary evaporation under reduced pressure, and separate by silica gel column chromatography. Eluent: dichloromethane / ethyl acetate = 100:1 - 20:1 to obtain 254 mg of a brown solid with a yield of 73%. MS: m / z 887.54 (M) + 。

[0098] Synthesis of Pt4: Add L4 (1.0 equiv), (1,5-cyclooctadiene)platinum(II) dichloride (1.0 equiv), and sodium acetate (4.0 equiv) into a sealed tube equipped with a magnetic stir bar. Flush with nitrogen three times, and then add diglyme (15 mL) under nitrogen protection. Bubble nitrogen through the solution for 30 min to remove oxygen. React in an oil bath at 135 °C for 48 h. After the reaction mixture is cooled to room temperature, remove the solvent by rotary evaporation under reduced pressure. Separate the crude product by silica gel column chromatography. Eluent: petroleum ether / dichloromethane = 2:1 - 1:1 to obtain 31 mg of a yellow solid with a yield of 12%. MS: m / z 1080.49 (M + H) + 。

[0099] Example 5: Tetradentate Cyclometalated Platinum(II) Complex Phosphorescent Luminescent Material Pt7

[0100] The synthesis route is as follows:

[0101]

[0102] Synthesis of Intermediate 7-7: Add 3-6 (1.0 equivalent), DNH2 (1.5 equivalents), tris(dibenzylideneacetone)dipalladium(0) (10 mol%), SPhos (20 mol%), and sodium tert-butoxide (2.0 equivalents) into a three-necked flask equipped with a magnetic stir bar. Flush and replace with nitrogen three times, and then add toluene (5 mL) under nitrogen protection. After reacting in an oil bath at 95 °C for 20 h, cool to room temperature, filter, and remove the solvent by rotary evaporation under reduced pressure. The crude product is separated by silica gel column chromatography with an eluent of petroleum ether / ethyl acetate = 10:1 - 1:1 to obtain 421 mg of a brown solid with a yield of 73%.

[0103] Synthesis of Ligand L7: Add 7-7 (1.0 equivalent) and ammonium hexafluorophosphate (2.0 equivalents) into a three-necked flask equipped with a magnetic stir bar. Flush and replace with nitrogen three times, and then add triethyl orthoformate (3 mL) under nitrogen protection. After reacting in an oil bath at 75 °C for 5 h, cool to room temperature, remove the solvent by rotary evaporation under reduced pressure, and separate by silica gel column chromatography with an eluent of dichloromethane / ethyl acetate = 100:1 - 20:1 to obtain 311 mg of a brown solid with a yield of 77%. MS: m / z 703.41 (M) + 。

[0104] Synthesis of Pt7: Add L7 (1.0 equivalent), (1,5-cyclooctadiene)platinum(II) chloride (1.0 equivalent), and sodium acetate (4.0 equivalents) into a sealed tube equipped with a magnetic stir bar. Flush and replace with nitrogen three times, and then add diglyme (15 mL) under nitrogen protection. Bubble nitrogen through the solution to remove oxygen for 30 min. React in an oil bath at 135 °C for 48 h. After cooling to room temperature, remove the solvent by rotary evaporation under reduced pressure. The crude product is separated by silica gel column chromatography with an eluent of petroleum ether / dichloromethane = 2:1 - 1:1 to obtain 15 mg of a yellow solid with a yield of 14%. MS: m / z 896.35 (M + H) + 。

[0105] Example 6: Tetradentate Cyclometalated Platinum(II) Complex Phosphorescent Luminescent Material Pt8

[0106] The synthesis route is as follows:

[0107]

[0108] Synthesize Pt8 according to the synthesis steps and reaction conditions of reference compound Pt1. Obtain 19 mg of a yellow solid with a yield of 15%. MS: m / z 952.42 (M + H) + 。

[0109] Example 7: Tetradentate Cyclometalated Platinum(II) Complex Phosphorescent Luminescent Material Pt78

[0110] The synthesis route is as follows:

[0111]

[0112] Synthesize Pt78 according to the synthesis steps and reaction conditions of reference compound Pt1. Obtain 11 mg of yellow solid with a yield of 10%. MS: m / z 968.35 (M+H) + 。

[0113] Example 8: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt5

[0114] Synthesize compound Pt5 according to the synthesis steps and reaction conditions of reference compound Pt1. Obtain a yellow solid. MS: m / z 1150.43 (M+H) + 。

[0115] Example 9: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt11

[0116] Synthesize compound Pt11 according to the synthesis steps and reaction conditions of reference compound Pt1. Obtain a yellow solid. MS: m / z 909.36 (M+H) + 。

[0117] Example 10: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt13

[0118] Synthesize compound Pt13 according to the synthesis steps and reaction conditions of reference compound Pt1. Obtain a yellow solid. MS: m / z 1069.48 (M+H) + 。

[0119] Example 11: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt17

[0120] Synthesize compound Pt17 according to the synthesis steps and reaction conditions of reference compound Pt1, yellow solid, MS: m / z 994.47 (M+H) + 。

[0121] Example 12: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt21

[0122] Synthesize compound Pt21 according to the synthesis steps and reaction conditions of reference compound Pt1, yellow solid. MS: m / z 912.38 (M+H) + 。

[0123] Example 13: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt26

[0124] Synthesize compound Pt26 according to the synthesis steps and reaction conditions of reference compound Pt1. Obtain a yellow solid. MS: m / z 906.34 (M+H) + 。

[0125] Example 14: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt28

[0126] Compound Pt28 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1. A yellow solid was obtained. MS: m / z 1164.43 (M+H) + 。

[0127] Example 15: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt29

[0128] Compound Pt29 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, a yellow solid. MS: m / z 1065.45 (M+H) + 。

[0129] Example 16: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt31

[0130] Compound Pt31 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, a yellow solid. MS: m / z 948.39 (M+H) + 。

[0131] Example 17: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt34

[0132] Compound P34 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, a yellow solid. MS: m / z 1108.51 (M+H) + 。

[0133] Example 18: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt45

[0134] Compound Pt45 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, a yellow solid. MS: m / z 1104.55 (M+H) + 。

[0135] Example 19: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt47

[0136] Compound Pt47 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, a yellow solid. MS: m / z 962.40 (M+H) + 。

[0137] Example 20: Tetradentate cyclometalated platinum(II) complex phosphorescent material Pt49

[0138] Compound Pt49 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, a yellow solid. MS: m / z 1094.50 (M+H) + 。

[0139] Example 21: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt51

[0140] Compound Pt51 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, yellow solid. MS: m / z 920.36 (M+H) + 。

[0141] Example 22: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt52

[0142] Compound Pt52 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, yellow solid. MS: m / z 976.43 (M+H) + 。

[0143] Example 23: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt56

[0144] Compound Pt56 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, yellow solid. MS: m / z 934.38 (M+H) + 。

[0145] Example 24: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt61

[0146] Compound Pt61 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, yellow solid. MS: m / z 976.42 (M+H) + 。

[0147] Example 25: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material Pt66

[0148] Compound Pt66 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, yellow solid. MS: m / z 938.41 (M+H) + 。

[0149] Example 26: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material P76

[0150] Compound Pt76 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, yellow solid. MS: m / z 917.33 (M+H) + 。

[0151] Example 27: Tetradentate cyclometalated platinum(II) complex phosphorescent luminescent material P77

[0152] Compound Pt77 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, yellow solid. MS: m / z 960.32 (M+H)+ .

[0153] Example 28: Tetradentate cyclometalated platinum(II) complex phosphorescent material P79

[0154] Compound Pt79 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, and it is a yellow solid. MS: m / z 996.39 (M+H) + .

[0155] Example 29: Tetradentate cyclometalated platinum(II) complex phosphorescent material P80

[0156] Compound Pt80 was synthesized according to the synthesis steps and reaction conditions of reference compound Pt1, and it is a yellow solid. MS: m / z 1010.40 (M+H) + .

[0157] Theoretical calculation illustration

[0158] The geometric structure of the ground state (S0) molecule was optimized using density functional theory (DFT). DFT calculations were performed using the B3LYP functional, where C, H, O, and N atoms used the 6-31G(d) basis set and the Pt atom used the LANL2DZ basis set.

[0159] Table 1. Frontier orbital energy levels of some metal complexes

[0160]

[0161]

[0162]

[0163] Figure 1 are the emission spectra of Pt1 at low concentration and at high concentration with different excitation wavelengths in toluene solution; Figure 2 is the high-resolution mass spectrometry data of Pt1; Figure 3 is the comparison of the theoretical calculation data between Pt1 and R1; From Figures 1 - 3As can be seen from Table 1, the complex materials provided by the present invention all have a large energy gap (>3.40 eV), which can meet the requirements of blue light materials. Importantly, the control R1 shows no obvious excimer emission, while the guest phosphorescent materials involved in the present invention are four-toothed cyclometalated platinum(II) complexes based on the diaza-carbazole structure. Diaza-carbazole can increase the intermolecular interaction and produce obvious excimer emission, so that both single molecule emission and excimer emission can be realized. Complex Pt1 can be used as a single molecule blue light material at low concentrations, and excimers are generated at high concentrations to achieve white light emission, and the white light color can be regulated according to the excitation wavelength. Compared with the control R1, the Pt(II) complexes based on diaza-carbazole of the present invention can lower the energy levels of HOMO and LUMO, maintain the energy gap difference and the triplet energy level, and at the same time, the orbital distribution does not change greatly, which is very beneficial for matching the host material of the device.

[0164] Fabrication of OLED devices:

[0165] As a reference preparation method for a device embodiment, in the present invention, a p-doped material is evaporated on the surface or anode of an ITO glass with a light-emitting area of 2 mm × 2 mm, or this p-doped material is co-evaporated with a hole injection material at a concentration of 1% to 50% to form a 5-100 nm hole injection layer (HIL) and a 5-200 nm hole transport layer (HTL). Subsequently, a 10-100 nm light-emitting layer (EML) (including a host material and a doping material, and the doping material may contain the platinum(II) complex described in the present invention) is formed on the hole transport layer, and an electron transport layer (ETL) of 20-200 nm and a cathode of 50-200 nm are formed; 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 fabricate an OLED device. And 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.

[0166] In a preferred specific embodiment, the structure of Device Example 1 provided by the present invention is:

[0167] ITO / HAT-CN(10nm) / NPD(60nm) / HTH-85(5nm) / 10wt% platinum(II) complex Pt1:60wt% HTH-85:30wt% ETH-45(25nm) / ETH-5(5nm) / BPyTP(40nm) / LiQ(1nm) / Al(100nm).

[0168] In a preferred specific embodiment, the structure of Device Example 30 provided by the present invention is:

[0169] ITO / HAT-CN(10 nm) / NPD(60 nm) / HTH-85(5 nm) / 10 wt% platinum(II) complex Pt1:1 wt% boron-containing compound BN1-4:59 wt%

[0170] HTH-85: 30 wt% ETH-45(25 nm) / ETH-5(5 nm) / BPyTP(40 nm) / LiQ(1 nm) / Al(100 nm).

[0171] Prepare Comparative Example R1 and Device Examples 2 - 29 respectively with structures similar to those of Device Example 1, and prepare Device Examples 31 - 40 respectively with structures similar to those of Device Example 30. The only difference is that the compounds listed in Table 2 are used as doping materials respectively to replace the doping materials in Device Examples 1 and 30. The luminescence characteristic data of the above-prepared Comparative Examples and each Device Example are shown in Table 2. The device structural formulas involved are as follows:

[0172]

[0173]

[0174] Table 2. Table of Devices and Electroluminescence Characteristics

[0175]

[0176]

[0177] As can be seen from Table 2, compared with Comparative Example R1, Device Examples 1 to 29 all exhibit good device performance in terms of current efficiency and lifetime. The performance improvement of each device application example is based on the tetradentate cyclometalated platinum(II) complex phosphorescent material with a bis(azacarbazole) structure of the present application. Furthermore, when the platinum(II) complex of the present application is used as a sensitizer, the device performance prepared with a boron-containing compound as a luminescent material also has a significant improvement, such as Device Examples 30 to 40. It can be seen that when it is used as a doping material for the light-emitting layer to prepare an electronic device, it has a higher current efficiency and lifetime while reducing the driving voltage. This indicates that the platinum(II) complex provided by the present invention has certain commercial application value. In addition, experiments show that by adding a boron-containing compound and adopting a sensitized device structure, the color purity of the device luminescence can be further improved.

[0178] The applicant declares that the above description is only the specific implementation manner 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 any person skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A multi-emissive tetradentate metal platinum(II) complex, characterized in that, The described platinum(II) metal complex has a structure shown in formula Pt-(I): Wherein, in formula Pt-(I), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represents from a single substituent to the maximum possible number of substituents or no substituent; R 1 , R 2 each independently represents any one of hydrogen, deuterium, halogen, cyano, C1–C30 alkyl, C1–C30 haloalkyl, C1–C30 deuterated alkyl, C6–C60 aryl, and C6–C60 arylsilane; R 3 , R 4 , R 5 and R 6 each independently represents hydrogen, deuterium, C1–C10 alkyl; R a and R b each independently represents C3–C30 alkyl, either the same or different.

2. The multi-emissive tetradentate metal platinum(II) complex according to claim 1, characterized in that, The R 1 is selected from one or more of hydrogen, deuterium, methyl, ethyl, tert-butyl, deuterated tert-butyl; R 2 is selected from one or more of hydrogen, deuterium, CN, CF3, methyl, ethyl, propyl, butyl, tert-butyl, pentyl, phenyl, triarylsilane.

3. The multi-emissive tetradentate metal platinum(II) complex according to claim 1, characterized in that, The R 3 , R 4 , R 5 and R 6 each independently represents one or more of hydrogen, deuterium, methyl, ethyl, propyl, butyl, and tert-butyl; R a and R b is selected from tert-butyl.

4. The multi-emissive tetradentate metal platinum(II) complex according to claim 1, characterized in that, The multi-emissive tetradentate platinum(II) metal complex is selected from any one of the following chemical structures, where "D" represents deuterium:

5. Use of the multi-emissive tetradentate metal platinum(II) complex according to any one of claims 1-4 in the preparation of an electronic device.

6. The use according to claim 5, characterized in that, The described electronic device is an organic optoelectronic device, an organic photovoltaic device, an organic electroluminescent device, an organic integrated circuit, an organic field effect transistor, an organic light emitting transistor, an organic solar cell, an organic optical detector, an organic photoreceptor, an organic field quenching device, a light-emitting electrochemical cell, and an organic laser diode.

7. The use according to claim 6, characterized in that, The described multi-emissive tetradentate platinum(II) metal complex is used as a light-emitting doping material in an electronic device.

8. An organic electroluminescent device, characterized in that, The described organic electroluminescent device includes a cathode, an anode, and at least one organic functional layer therebetween; the organic functional layer contains the multi-emissive tetradentate platinum(II) metal complex according to any one of claims 1-4.

9. An organic optoelectronic device, characterized in that, The described organic optoelectronic device includes: a substrate layer, a first electrode; a second electrode facing the first electrode; and a light-emitting material layer disposed between the first electrode and the second electrode; wherein the light-emitting material layer contains a host material and a doping material; the doping material contains the multi-emissive tetradentate platinum(II) metal complex according to any one of claims 1-4.

10. A composition, characterized in that, The described composition contains the multi-emissive tetradentate platinum(II) metal complex according to any one of claims 1-4.

11. A preparation, characterized in that, The described preparation contains the multi-emissive tetradentate platinum(II) metal complex according to any one of claims 1-4 and at least one solvent.

12. A display or lighting device, characterized in that, The described device contains one or more of the organic optoelectronic devices described in claim 9.

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