Metal palladium complex and organic electroluminescent device

Abstract

The present application relates to the technical field of electronic materials, and in particular to a metal palladium complex and an organic electroluminescent device. The present application provides a metal palladium complex having a structure as shown in formula 1: [Formula 1]. The metal palladium complex provided by the present application has excellent photoluminescent and electroluminescent properties, and a manufactured luminescent device has long service life and high luminous efficiency.

Description

Metallic palladium complex and organic electroluminescent device

[0001] Cross-reference to related applications

[0002] This application claims priority to the Chinese patent application No. 202410529208.6, filed on April 29, 2024, and entitled “Metallic palladium complex and organic electroluminescent device”, the entire content of which is incorporated herein by reference. TECHNICAL FIELD

[0003] The present application relates to the technical field of electronic materials, in particular to a metallic palladium complex and an organic electroluminescent device. BACKGROUND

[0004] Organic light-emitting diode (OLED) technology, as an advanced optoelectronic device capable of realizing electrical-to-optical conversion, has shown great potential in the fields of lighting and display due to its significant advantages such as low operating voltage, high energy conversion efficiency, flexible structure, fast response, and wide working temperature range.

[0005] In the organic light-emitting diode (OLED) technology, the light-emitting material has a crucial impact on the optoelectronic performance of the device. Since in the working process of OLED, about 75% of the excitons generated under the action of the electric field are triplet excitons, and 25% are singlet excitons, therefore, efficient conversion of triplet excitons becomes the core to improve the performance of OLED. Currently, the research of OLED light-emitting materials mainly focuses on two strategies to capture and utilize triplet excitons: phosphorescent light-emitting materials and thermally activated delayed fluorescence (TADF) materials. TADF materials have become a research hotspot due to their advantages in conversion efficiency and cost control.

[0006] TADF materials can be divided into two categories: pure organic TADF materials and metal complex TADF materials. Pure organic TADF materials often face the problems of long emission lifetime and severe efficiency roll-off under high brightness. Long emission lifetime may lead to a decrease in the stability of the device, because excitons with longer lifetime are more likely to be affected by various degradation pathways in the device.

[0007] Metal complex TADF materials, especially linear complexes with carbene-metal-amine ligands, are less studied at present, and the device lifetime and efficiency of these materials are generally low. Metal complex materials are still a research hotspot due to their unique photoelectric properties. For example, the research of palladium (II) complexes in the field of organic electroluminescent materials (OLED) mainly focuses on exploring their unique optical properties and how to apply these properties to high-efficiency and high-stability OLED devices. Palladium (II) complexes can exhibit characteristics different from traditional fluorescent and phosphorescent materials due to their special electronic structure and coordination environment.

[0008] Although palladium (II) complexes have the potential to be applied in organic electroluminescent diodes (OLEDs), the linear carbene-metal-amine palladium (II) complex materials in the prior art have insufficient performance, and the device lifetime and external quantum efficiency of the organic electroluminescent devices prepared therefrom are low. SUMMARY

[0009] Therefore, the technical problem to be solved by the present application is to overcome the defects of insufficient performance of the carbene-metal-amine palladium (II) complex TADF material in the prior art, and the low device lifetime and external quantum efficiency of the organic electroluminescent devices prepared therefrom. Thus, a metal complex and an organic electroluminescent device are provided.

[0010] In the definition of the terms in the present application:

[0011] As used herein, the term "halogen" can include fluorine, chlorine, bromine or iodine.

[0012] As used herein, the term "C1-C30 alkyl" refers to a monovalent substituent derived from a straight-chain or branched saturated hydrocarbon having 1 to 30 carbon atoms, examples of which include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0013] The aryl group and the arylene group in the present application include monocyclic, polycyclic or fused ring aryl groups, which can be interrupted by short non-aromatic units between the rings and can contain a spiro structure, and the aryl group includes but is not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl, fluorenyl, spirobifluorenyl, etc., and the arylene group includes but is not limited to phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, anthrylene, fluorenylene, spirobifluorenylene, etc.

[0014] Heteroaryl and heteroarylene groups in the present application include monocyclic, polycyclic or fused ring heteroaryl groups, the rings of which can be interrupted by short non-aromatic units, and the heteroatoms of which include nitrogen, oxygen, sulfur. Heteroaryl groups include, but are not limited to, furanyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoaxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, derivatives thereof, and the like. Heteroarylene groups include, but are not limited to, furanylene, thiophenylene, pyrrolylene, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, triazolylene, tetrazolylene, furazanylene, pyridylylene, pyrazinylyene, pyrimidinylene, pyridazinylyene, benzofuranylene, benzothiophenylene, isobenzofuranylene, dibenzofuranylene, dibenzothiophenylene, benzoimidazolylene, benzothiazolylene, benzoisothiazolylene, benzoisoxazolylene, benzoaxazolylene, isoindolylene, indolylene, indazolylene, benzothiadiazolylene, quinolinylene, isoquinolinylene, cinnolinylene, quinazolinylene, quinoxalinylene, carbazolylene, phenoxazinylene, phenothiazinylene, phenanthridinylene, benzodioxolylyene, dihydroacridinylene, derivatives thereof, and the like.

[0015] In the present application, "C" refers to carbon, not as other abbreviations.

[0016] The solutions adopted in the present application are as follows:

[0017] The present application provides a metal palladium complex, which has the structure shown as follows:

[0018] wherein W1 is selected from C 1-10 alkyl, C 6-12 aryl;

[0019] R1, R2 are each independently selected from H, halogen, C 1-10 alkyl, C 2-6 alkenyl, C 3-20 aryl, C 3-20 heteroaryl;

[0020] D is an electron-donating group;

[0021] A is selected from H, halogen, C 1-10alkyl, C 1-10 alkoxy, C 2-6 alkenyl, C 3-20 aryl, C 3-20 heteroaryl;

[0022] X1is selected from N or C-T1; X2is selected from N or C-T2;

[0023] wherein T1, T2are each independently selected from H, halogen, C 1-10 alkyl, C 2-6 alkenyl, C 3-20 aryl, C 3-20 heteroaryl;

[0024] when X 1、 is C-T1, X2is C-T2, A, T1, T2are not simultaneously H.

[0025] optionally, W1is selected from C 1-3 alkyl, C 6-12 aryl;

[0026] W1is selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, phenyl, naphthyl, biphenyl.

[0027] optionally, R1, R2are each independently selected from H, halogen, C 1-6 alkyl, C 2-6 alkenyl, C 6-20 aryl, C 6-20 heteroaryl;

[0028] optionally, R1, R2are each independently selected from H, halogen, methyl, ethyl, propyl, i-propyl, n-butyl, phenyl, naphthyl, biphenyl, ethenyl, propenyl;

[0029] optionally, R1, R2are each independently present, or R1, R2are bonded to form a C 3-20 aromatic ring;

[0030] optionally, R1, R2are each independently present, or R1, R2are bonded to form a C 6-20 aromatic ring;

[0031] optionally, R1, R2are each independently present, or R1, R2are bonded to form a benzene ring.

[0032] optionally, D is selected from one of the following groups:

[0033] optionally, A is selected from H, C 1-6 alkyl, C 1-6 alkoxy, C 2-6 alkenyl, C 6-20 aryl, C6-20 heteroaryl;

[0034] Optionally, A is selected from H, cyano, trihalomethyl, halogen, tert-butyl, methyl, methoxy, nitro, carboxyl.

[0035] Optionally, X1 is selected from N or C-T1, and X2 is selected from N or C-T2;

[0036] wherein, T1 and T2 are each independently selected from H, halogen, C 1-6 alkyl, C 2-6 alkenyl, C 6-20 aryl, C 6-20 heteroaryl;

[0037] Optionally, T1 and T2 are each independently selected from H, halogen, methyl, tert-butyl, cyano, trihalomethyl.

[0038] Optionally, the metal palladium complex has any one of the following structures:

[0039] The application also provides an organic electroluminescent device, comprising a first electrode, a second electrode, and a light-emitting layer between the first electrode and the second electrode, wherein the light-emitting layer comprises any one or a combination of at least two of the metal palladium complexes described above.

[0040] Optionally, the light-emitting layer comprises the metal palladium complex and an organic functional material, wherein the metal palladium complex accounts for 0.01% to 100% by mass percentage, and the organic functional material accounts for 0 to 99.9% by mass percentage.

[0041] The application also provides the use of the organic electroluminescent device described above in an electronic device.

[0042] The application also provides a preparation method of the metal palladium complex described above, comprising the following steps:

[0043] Step 1: under the conditions of nitrogen atmosphere, alkaline conditions, and a solvent, refluxing compound a with compound b to obtain compound c; wherein R1, R2, X1, X2, and A are the same as defined above.

[0044] wherein: in the alkaline conditions, the alkali source is potassium carbonate; the catalyst is cuprous iodide; the ligand is L-proline; and the solvent is dimethyl sulfoxide;

[0045] Step 2: reacting compound c obtained in step 1 with compound d under solvent and refluxing conditions to obtain compound e; wherein W1 is the same as defined above;

[0046] wherein the solvent is acetonitrile;

[0047] Step 3: reacting compound e with dry dichloropalladium under solvent and refluxing conditions to obtain compound f;

[0048] wherein the solvent is N,N-dimethylformamide;

[0049] Step 4: reacting compound f with D-H to obtain a compound having the structure of formula 1

[0050] wherein D is the same as defined above;

[0051] wherein in the basic condition, the base source is selected from an organic base or an inorganic base, for example, the base source is selected from potassium tert-butoxide.

[0052] The synthesis method of the compound having the structure of D-H is as follows:

[0053] (1) Synthesis of the compound having the structure of D-H as follows:

[0054] wherein P1 is independently selected from H, trimethyl;

[0055] The synthesis steps are as follows:

[0056] reacting compound D1’ and compound D1” under the conditions of nitrogen atmosphere, basic condition and solvent to obtain D1

[0057] wherein in the basic condition, the base source is sodium tert-butoxide; the catalyst is bis(dibenzylideneacetone)palladium; the additive is 1,1-bis(diphenylphosphino)ferrocene; and the solvent is toluene.

[0058] (2) Synthesis of the compound having the structure of D-H as follows:

[0059] wherein P1 is independently selected from H, trimethyl;

[0060] reacting compound D2’ under the conditions of nitrogen atmosphere, basic condition and solvent to obtain compound D2;

[0061] The base source is sodium tert-butoxide; the catalyst is bis(dibenzylideneacetone)palladium; the additive is 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl; and the solvent is xylene.

[0062] (3) Synthesis of the D-H compound with the following structure:

[0063] a. Compound D3' and compound D3" are reacted in the presence of a nitrogen atmosphere, basic conditions, and a solvent to obtain D3"

[0064] The base source is sodium tert-butoxide; the catalyst is bis(dibenzylideneacetone)palladium; the additive is 1,1-bis(diphenylphosphino)ferrocene; and the solvent is toluene.

[0065] b. Compound D3" is subjected to a ring closure reaction in the presence of a nitrogen atmosphere, basic conditions, and a solvent to obtain compound D3.

[0066] The base source is sodium tert-butoxide; the catalyst is bis(dibenzylideneacetone)palladium; the additive is 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl; and the solvent is xylene.

[0067] (4) Synthesis of the D-H compound with the following structure:

[0068] The synthesis steps are as follows:

[0069] Compound D4' and compound D4" are reacted in the presence of a nitrogen atmosphere, basic conditions, and a solvent to obtain D4

[0070] The base source is cesium carbonate; and the solvent is dimethyl sulfoxide.

[0071] (5) Synthesis of the D-H compound with the following structure:

[0072] The synthesis steps are as follows:

[0073] Compound D5' and compound D5" are reacted in the presence of a nitrogen atmosphere, basic conditions, and a solvent to obtain D5

[0074] The base source is potassium carbonate; the catalyst is cuprous iodide; and the solvent is dimethyl sulfoxide.

[0075] (6) Synthesis of the D-H compound with the following structure:

[0076] The synthesis steps are as follows:

[0077] Compound D6' and compound D6" are reacted to obtain D5 under the condition of nitrogen atmosphere, alkaline condition and solvent

[0078] In the alkaline condition, the base source is sodium tert-butoxide; the catalyst is bisbenzylideneacetone palladium; the additive is 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl; and the solvent is xylene.

[0079] (6) Synthesis of D-H compound with the following structure:

[0080] The synthesis steps are as follows:

[0081] Compound D6 is reacted with selenium dioxide, selenium powder and iodine under the condition of nitrogen atmosphere and solvent to obtain D7.

[0082] The solvent is sulfolane.

[0083] It can be understood that the above compounds D1-D7 belong to different D-H.

[0084] The application also provides an organic electroluminescent device, which comprises a first electrode, a second electrode and a light-emitting layer between the first electrode and the second electrode, and the light-emitting layer comprises any one or a combination of at least two of the above-mentioned metal complexes.

[0085] Optionally, the light-emitting layer comprises the above-mentioned metal complex and organic functional material, and the mass percentage of the metal complex is 0.01%-100%, and the mass percentage of the organic functional material is 0-99.9%.

[0086] It should be noted that the application of the metal complex described in the application is not limited to the composition of the device, and the film thickness or composition material of each layer can be appropriately changed according to the basic physical properties of the structure of the specific compound in the application.

[0087] The preparation method of the organic device described in the application is a conventional method in the art. Alternatively, the preparation of the organic electroluminescent device comprises the following steps: taking a glass substrate with ITO evaporation as a transparent support substrate, and sequentially evaporating each organic layer and metal electrode on the ITO film of the transparent support substrate.

[0088] The application also provides the application of the above-mentioned organic electroluminescent device in electronic equipment.

[0089] The application has the following advantages:

[0090] The metal palladium complex provided in the application has a structure of Formula 1. The metal palladium complex in the application is based on a linear divalent palladium complex with a carbene-metal-amine ligand. By changing the electron-donating and electron-withdrawing abilities of the donor and acceptor, the energy levels of the molecule are changed correspondingly, the stability of the metal complex is enhanced, in the field of organic electroluminescent materials, this configuration reduces the energy difference between the triplet and singlet excitons through the intramolecular charge transfer mechanism between the ligands, thereby realizing effective thermal activation transition, so that the triplet exciton can participate in delayed fluorescence emission, thereby improving the luminous efficiency of the OLED device; the linear molecular structure of the metal palladium complex provided in the application promotes the stable stacking between molecules, thereby improving the charge transfer rate, and further enhancing the current efficiency and brightness of the light-emitting device; further, the strong spin-orbit coupling of the palladium element itself can accelerate the process of reverse intersystem crossing, inhibit the non-radiative transition process, and effectively shorten the luminescence lifetime of the molecule, thereby further improving the luminous efficiency of the light-emitting device; in addition, the metal palladium complex provided in the application, in which the charge transfer between the ligands enables palladium to act as a metal bridge and more effectively participate in the formation of the excited state of the molecule, thereby enhancing the photophysical properties of the molecule and further improving the stability of the light-emitting device. In summary, the metal palladium complex provided in the application has excellent photoluminescence and electroluminescence properties, and the light-emitting device prepared therefrom has a long device lifetime, high luminous efficiency, and high external quantum efficiency.

[0091] Further, the metal palladium complex provided in the application can effectively adjust the molecular light color and improve the molecular luminescence performance by changing the electron-donating and electron-withdrawing abilities of the donor and acceptor, so that the energy levels of the molecule are changed correspondingly.

[0092] Further, the flexibility of the carbene-metal-amine ligand in the metal palladium complex provided in the application allows the luminescence wavelength to be adjusted by molecular engineering means and the spectral characteristics of the device to be optimized.

[0093] Further, the metal palladium complex provided in the application has an external quantum efficiency as high as 25.9%, and the device lifetime is up to 100 cdm -2 The LT95 lifetime is close to 80000 hours. BRIEF DESCRIPTION OF DRAWINGS

[0094] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the drawings needed in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor on the basis of these drawings.

[0095] FIG. 1 is a structure diagram of an organic electroluminescent device in device embodiments 1-11 of the present application.

[0096] Figure 2 is an absorption spectrum of the metal palladium complex Pd-2 prepared in Example 1 of the present application in toluene solution;

[0097] Figure 3 is an absorption spectrum of the metal palladium complex Pd-9 prepared in Example 1 of the present application in toluene solution;

[0098] Figure 4 is an absorption spectrum of the metal palladium complex Pd-41 prepared in Example 5 of the present application in toluene solution;

[0099] Figure 5 is an absorption spectrum of the metal palladium complex Pd-42 prepared in Example 5 of the present application in toluene solution;

[0100] Figure 6 is an absorption spectrum of the metal palladium complex Pd-49 prepared in Example 5 of the present application in toluene solution;

[0101] Figure 7 is an absorption spectrum of the metal palladium complex Pd-52 prepared in Example 6 of the present application in toluene solution;

[0102] Figure 8 is an absorption spectrum of the metal palladium complex Pd-54 prepared in Example 6 of the present application in toluene solution;

[0103] Figure 9 is an absorption spectrum of the metal palladium complex Pd-59 prepared in Example 6 of the present application in toluene solution;

[0104] Figure 10 is an absorption spectrum of the metal palladium complex Pd-62 prepared in Example 7 of the present application in toluene solution;

[0105] Figure 11 is an absorption spectrum of the metal palladium complex Pd-69 prepared in Example 7 of the present application in toluene solution;

[0106] Figure 12 is an absorption spectrum of the metal palladium complex Pd-71 prepared in Example 8 of the present application in toluene solution;

[0107] Figure 13 is an absorption spectrum of the metal palladium complex Pd-72 prepared in Example 8 of the present application in toluene solution;

[0108] Figure 14 is an absorption spectrum of the metal palladium complex Pd-77 prepared in Example 8 of the present application in toluene solution;

[0109] Figure 15 is an absorption spectrum of the metal palladium complex Pd-79 prepared in Example 8 of the present application in toluene solution;

[0110] Figure 16 is an absorption spectrum of the metal palladium complex Pd-139 prepared in Example 14 of the present application in toluene solution;

[0111] Figure 17 is an absorption spectrum of a metal palladium complex DphCz prepared from an intermediate in the present application in toluene solution;

[0112] Figure 18 is an emission spectrum of a metal palladium complex Pd-2 prepared from Example 1 in the present application in toluene solution;

[0113] Figure 19 is an emission spectrum of a metal palladium complex Pd-9 prepared from Example 1 in the present application in toluene solution;

[0114] Figure 20 is an emission spectrum of a metal palladium complex Pd-41 prepared from Example 5 in the present application in dichloromethane solution;

[0115] Figure 21 is an emission spectrum of a metal palladium complex Pd-42 prepared from Example 5 in the present application in toluene solution;

[0116] Figure 22 is an emission spectrum of a metal palladium complex Pd-49 prepared from Example 5 in the present application in toluene solution;

[0117] Figure 23 is an emission spectrum of a metal palladium complex Pd-52 prepared from Example 6 in the present application in toluene solution;

[0118] Figure 24 is an emission spectrum of a metal palladium complex Pd-54 prepared from Example 6 in the present application in toluene solution;

[0119] Figure 25 is an emission spectrum of a metal palladium complex Pd-59 prepared from Example 6 in the present application in toluene solution;

[0120] Figure 26 is an emission spectrum of a metal palladium complex Pd-62 prepared from Example 7 in the present application in toluene solution;

[0121] Figure 27 is an emission spectrum of a metal palladium complex Pd-71 prepared from Example 8 in the present application in toluene solution;

[0122] Figure 28 is an emission spectrum of a metal palladium complex Pd-72 prepared from Example 8 in the present application in toluene solution;

[0123] Figure 29 is an emission spectrum of a metal palladium complex Pd-73 prepared from Example 8 in the present application in toluene solution;

[0124] Figure 30 is an emission spectrum of a metal palladium complex Pd-79 prepared from Example 8 in the present application in toluene solution;

[0125] Figure 31 is an emission spectrum of a metal palladium complex Pd-139 prepared from Example 14 in the present application in toluene solution;

[0126] Figure 32 is an emission spectrum of a metal palladium complex paddle-shaped ligand DphCz prepared in the application in toluene solution;

[0127] Figure 33 is an emission spectrum of a metal palladium complex Pd-2 prepared in Example 1 of the application in polymethyl methacrylate film;

[0128] Figure 34 is an emission spectrum of a metal palladium complex Pd-9 prepared in Example 1 of the application in polymethyl methacrylate film at different temperatures;

[0129] Figure 35 is an emission spectrum of a metal palladium complex Pd-44 prepared in Example 5 of the application in polymethyl methacrylate film;

[0130] Figure 36 is an emission spectrum of a metal palladium complex Pd-49 prepared in Example 5 of the application in polymethyl methacrylate film;

[0131] Figure 37 is an emission spectrum of a metal palladium complex Pd-54 prepared in Example 6 of the application in polymethyl methacrylate film;

[0132] Figure 38 is an emission spectrum of a metal palladium complex Pd-59 prepared in Example 6 of the application in polymethyl methacrylate film;

[0133] Figure 39 is an emission spectrum of a metal palladium complex Pd-62 prepared in Example 7 of the application in polymethyl methacrylate film;

[0134] Figure 40 is an emission spectrum of a metal palladium complex Pd-69 prepared in Example 7 of the application in polymethyl methacrylate film;

[0135] Figure 41 is an emission spectrum of a metal palladium complex Pd-72 prepared in Example 8 of the application in polymethyl methacrylate film;

[0136] Figure 42 is an emission spectrum of a metal palladium complex Pd-79 prepared in Example 8 of the application in polymethyl methacrylate film;

[0137] Figure 43 is an emission spectrum of a metal palladium complex Pd-139 prepared in Example 14 of the application in polymethyl methacrylate film;

[0138] Figure 44 is a lifetime decay curve of a metal palladium complex Pd-2 prepared in Example 1 of the application in polymethyl methacrylate film;

[0139] Figure 45 is a lifetime decay curve of a metal palladium complex Pd-9 prepared in Example 1 of the application in polymethyl methacrylate film;

[0140] Figure 46 is a plot of the lifetime decay curve of metal palladium complex Pd-49 prepared in Example 5 of the present application in polymethyl methacrylate film;

[0141] Figure 47 is a plot of the lifetime decay curve of metal palladium complex Pd-59 prepared in Example 6 of the present application in polymethyl methacrylate film;

[0142] Figure 48 is a plot of the lifetime decay curve of metal palladium complex Pd-69 prepared in Example 7 of the present application in polymethyl methacrylate film;

[0143] Figure 49 is a plot of the lifetime decay curve of metal palladium complex Pd-71 prepared in Example 8 of the present application in polymethyl methacrylate film;

[0144] Figure 50 is a plot of the lifetime decay curve of metal palladium complex Pd-72 prepared in Example 8 of the present application in polymethyl methacrylate film;

[0145] Figure 51 is a plot of the lifetime decay curve of metal palladium complex Pd-79 prepared in Example 8 of the present application in polymethyl methacrylate film;

[0146] Figure 52 is a plot of the lifetime decay curve of metal palladium complex Pd-139 prepared in Example 8 of the present application in polymethyl methacrylate film;

[0147] Figure 53 is a plot of the electroluminescence of devices Examples 1-5 based on Pd-2 of the present application;

[0148] Figure 54 is a plot of the electroluminescence quantum efficiency of devices Examples 1-5 based on Pd-2 of the present application;

[0149] Figure 55 is a plot of the electroluminescence of devices Examples 6-9 based on Pd-9 of the present application;

[0150] Figure 56 is a plot of the electroluminescence quantum efficiency of devices Examples 6-9 based on Pd-9 of the present application;

[0151] Figure 57 is a plot of the stability testing of the provided organic electroluminescent device in device Example 6;

[0152] Figure 58 is a plot of the electroluminescence of devices Examples 10-13 based on Pd-49 of the present application;

[0153] Figure 59 is a plot of the electroluminescence quantum efficiency of devices Examples 10-13 based on Pd-49 of the present application;

[0154] Figure 60 is a plot of the electroluminescence of devices Examples 14-17 based on Pd-79 of the present application;

[0155] Figure 61 shows the electroluminescence quantum efficiency diagram of Pd-79 based on device embodiments 14-17 of this application;

[0156] Figure 62 shows the stability test results of the organic electroluminescent device provided in Device Example 16;

[0157] Figure 63 shows the electroluminescence patterns of Pd-139 based on the device embodiments 18-21 of this application;

[0158] Figure 64 shows the electroluminescence quantum efficiency of Pd-139 in embodiments 18-21 of this application;

[0159] Reference numerals: 100-glass substrate, 1-anode layer, 2-hole injection layer, 3-hole transport layer, 4-electron blocking layer, 5-light emitting layer, 6-electron transport layer, 7-electron injection layer, and 8-cathode layer. Detailed Implementation

[0160] The following embodiments are provided to better understand this application and are not limited to the preferred embodiments described herein. They do not constitute a limitation on the content and scope of protection of this application. Any product that is the same as or similar to this application, derived by anyone under the guidance of this application or by combining features of this application with other prior art, falls within the scope of protection of this application.

[0161] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0162] The preparation methods for some intermediates used in the preparation of palladium metal complexes are as follows:

[0163] Preparation of tridentate ligand metal chloride CCC:

[0164] The synthesis route is shown below:

[0165] S1, CCC1 4,6-dibromopyrimidine (238 mg, 1 mmol), imidazole (102 mg, 1.5 mmol), K2CO3 (830 mg, 6 mmol), cuprous iodide (19 mg, 0.1 mmol), and L-proline (58 mg, 0.5 mmol) were dissolved in 30 ml of ultra-dry DMSO solution, stirred, and slowly heated to 140 °C. The reaction was carried out for 48 h, extracted with dichloromethane and water, purified by vacuum distillation and column chromatography (eluent: petroleum ether: dichloromethane = 2:1) to obtain colorless solid CCC1 (yield 80%).

[0166] S2, the product CCC1 (212 mg, 1 mmol), n-butyl bromide (1370 mg, 10 mmol) were dissolved in 30 ml of acetonitrile solution, stirred, slowly warmed to 80 °C, reacted for 72 h, filtered, distilled under reduced pressure to obtain the intermediate 1 (yield 60%) as a colorless solid;

[0167] S3, the intermediate 1 (487 mg, 1 mmol), palladium dichloride (177 mg, 2 mmol) and sodium acetate (320 mg, 4 mmol) were dissolved in 20 mL of DMAc (N,N-dimethylacetamide), stirred, slowly warmed to 140 °C, reacted for 72 h, then the solvent was removed under reduced pressure, purified by column chromatography (eluent petroleum ether: dichloromethane = 1:2) to obtain the final product CCC (yield 36%).

[0168] Preparation of the tridentate ligand metal chloride CCC-CN

[0169] The synthesis route is shown below:

[0170] S1, similar to S1 of the preparation process of the metal palladium chloride CCC, except that CCC-CN1 was used to replace CCC1, the reaction obtained CCC-CN2 (yield 80%), 1 H NMR (500 MHz, DMSO) δ (ppm) 8.53 (s, 2H), 8.34 (t, J = 2.0 Hz, 1H), 8.25 (d, J = 2.0 Hz, 2H), 8.01 (t, J = 1.2 Hz, 2H), 7.18 (s, 2H);

[0171] S2, similar to S2 of the preparation process of the metal palladium chloride CCC, except that CCC-CN2 was used to replace CCC2, the reaction obtained intermediate 2 (yield 80%), 1 H NMR (500 MHz, DMSO) δ (ppm) 10.22 (s, 2H), 8.85 (t, J = 2.0 Hz, 1H), 8.66 (d, J = 2.0 Hz, 2H), 8.56 (t, J = 1.8 Hz, 2H), 8.18 - 8.15 (m, 2H), 4.32 (t, J = 7.2 Hz, 4H), 1.92 (p, J = 7.4 Hz, 4H), 1.36 (h, J = 7.4 Hz, 4H), 0.96 (t, J = 7.4 Hz, 6H);

[0172] S3, similar to S3 of the preparation process of the metal palladium chloride CCC, except that intermediate 2 was used to replace intermediate 1, the reaction obtained the final product CCC-CN (yield 60%), 1H NMR (400 MHz, CDC13) δ (ppm) 7.37 (d, J = 1.9 Hz, 2H), 7.16 (d, J = 4.3 Hz, 2H), 6.99 (d, J = 2.0 Hz, 2H), 4.76 (dt, J = 24.0, 7.4 Hz, 4H), 1.88 (q, J = 7.3 Hz, 4H), 1.27 (d, J = 11.9 Hz, 4H), 0.98 (t, J = 7.4 Hz, 6H).

[0173] Preparation of tridentate ligand metal chloride CCC-CF3

[0174] The synthesis route is shown below:

[0175] S1, similar to S1 of the process for the preparation of metal palladium chloride CCC, except that CCC-CF3-1 is used instead of CCC1, the reaction gives CCC-CF3-2 (yield 75%), 1 H NMR (500 MHz, DMSO) δ (ppm) 8.57 (s, 2H), 8.31 (s, 1H), 8.06 (s, 4H), 7.18 (s, 2H);

[0176] S2, similar to S2 of the process for the preparation of metal palladium chloride CCC, except that CCC-CF3-2 is used instead of CCC2, the reaction gives intermediate 3 (yield 80%), 1 H NMR (400 MHz, DMSO) δ (ppm) 10.26 (s, 2H), 8.80 (s, 1H), 8.63 (t, J = 1.8 Hz, 2H), 8.54 - 8.48 (m, 2H), 8.19 - 8.13 (m, 2H), 4.32 (t, J = 7.2 Hz, 4H), 1.93 (p, J = 7.4 Hz, 4H), 1.37 (h, J = 7.4 Hz, 4H), 0.96 (t, J = 7.4 Hz, 6H);

[0177] S3, similar to S3 of the process for the preparation of metal palladium chloride CCC, except that intermediate 3 is used instead of intermediate 1, the reaction gives the final product metal palladium chloride CCC-CF3 (yield 36%), 1 H NMR (500 MHz, DMSO) δ (ppm) 8.24 (d, J = 2.0 Hz, 2H), 7.74 (s, 2H), 7.54 (d, J = 2.0 Hz, 2H), 4.68 (t, J = 7.3 Hz, 4H), 1.77 (p, J = 7.6 Hz, 4H), 1.40 - 1.30 (m, 4H), 0.92 (t, J = 7.4 Hz, 6H).

[0178] Preparation of tridentate ligand metal chloride CCC-tBu

[0179] The synthetic route is shown below:

[0180] S1, similar to S1 of the preparation process of metal palladium chloride CCC, except that CCC-tBu1 is used to replace CCC1, and the reaction gives CCC-tBu2 (yield 40%), 1 H NMR (400 MHz, DMSO) δ (ppm) 8.42 (s, 2H), 7.92 (s, 2H), 7.78 (t, J = 2.0 Hz, 1H), 7.58 (d, J = 2.0 Hz, 2H), 7.14 (s, 2H), 1.39 (s, 9H);

[0181] S2, similar to S2 of the preparation process of metal palladium chloride CCC, except that CCC-tBu2 is used to replace CCC2, and the reaction gives intermediate 4 (yield 50%), 1 H NMR (500 MHz, DMSO) δ (ppm) 8.63 (s, 2H), 8.30 (s, 1H), 8.16 (s, 2H), 8.03 (d, J = 1.7 Hz, 2H), 7.96 (s, 4H), 4.32 (t, J = 7.2 Hz, 4H), 1.95 - 1.90 (m, 4H), 1.43 (s, 9H), 0.97 - 0.88 (m, 10H);

[0182] S3, similar to S3 of the preparation process of metal palladium chloride CCC, except that intermediate 4 is used to replace intermediate 1, and the reaction gives the final product metal palladium chloride CCC-tBu (yield 46%), 1 H NMR (500 MHz, DMSO) δ (ppm) 8.12 (d, J = 1.9 Hz, 2H), 7.45 (d, J = 1.9 Hz, 2H), 7.30 (s, 2H), 4.64 (t, J = 7.3 Hz, 4H), 1.75 (p, J = 7.5 Hz, 4H), 1.36 (s, 13H), 0.91 (t, J = 7.4 Hz, 6H).

[0183] Preparation of tridentate ligand metal chloride CCC-CH3O

[0184] The synthetic route is shown below:

[0185] S1, similar to S1 of the preparation process of metal palladium chloride CCC, except that CCC-CH3O1 is used to replace CCC1, and the reaction gives CCC-CH3O2 (yield 30%), 1H NMR (500 MHz, DMSO) δ (ppm) 8.44 (s, 2H), 7.93 (s, 2H), 7.57 (t, J = 1.8 Hz, 1H), 7.25 (d, J = 1.8 Hz, 2H), 7.15 (s, 2H), 3.92 (s, 3H);

[0186] S2, similar to S2 of the preparation process of metal palladium chloride CCC, except that CCC-CH30 2 is used instead of CCC2 to react to obtain intermediate 5 (yield 60%), 1 H NMR (400 MHz, DMSO) δ (ppm) 10.25 (s, 2H), 8.57 (t, J = 1.8 Hz, 2H), 8.22 - 8.13 (m, 2H), 8.07 (t, J = 1.8 Hz, 1H), 7.69 (d, J = 1.8 Hz, 2H), 4.31 (t, J = 7.2 Hz, 4H), 4.01 (s, 3H), 1.93 (p, J = 7.4 Hz, 4H), 1.36 (h, J = 7.4 Hz, 4H), 0.95 (t, J = 7.4 Hz, 6H);

[0187] S3, similar to S3 of the preparation process of metal palladium chloride CCC, except that intermediate 5 is used instead of intermediate 1, and the reaction obtains the final product metal palladium chloride CCC-CH30 (yield 60%), 1 H NMR (400 MHz, DMSO) δ (ppm) 8.05 (d, J = 2.0 Hz, 2H), 7.46 (d, J = 2.0 Hz, 2H), 6.99 (s, 2H), 4.64 (t, J = 7.3 Hz, 4H), 3.83 (s, 3H), 1.76 (p, J = 7.5 Hz, 4H), 1.35 (h, J = 7.4 Hz, 4H), 0.92 (t, J = 7.4 Hz, 6H).

[0188] Preparation of tridentate ligand metal chloride CCC-CH3

[0189] The synthesis route is shown below:

[0190] S1, similar to S1 of the preparation process of metal palladium chloride CCC, except that CCC-CH3-1 is used instead of CCC1, and the reaction obtains CCC-CH3-2;

[0191] S2, similar to S2 of the preparation process of metal palladium chloride CCC, except that CCC-CH3-2 is used instead of CCC2 to react to obtain intermediate 6;

[0192] S3, similar to S3 of the preparation process of metal palladium chloride CCC, the difference is that intermediate 6 is used instead of intermediate 1, and the reaction obtains the final product metal palladium chloride CCC-CH3.

[0193] Preparation of tridentate ligand metal chloride CCC-BMZ

[0194] The synthetic route is as follows:

[0195] S1, 4, 6-dibromopyrimidine (238 mg, 1 mmol), benzimidazole (236 mg, 2 mmol) and K2CO3 (830 mg, 6 mmol), cuprous iodide (19 mg, 0.1 mmol), L-proline (58 mg, 0.5 mmol) were dissolved in 30 ml of super dry DMSO solution, stirred, slowly warmed to 140℃, reacted for 48 h, extracted with dichloromethane and water, distilled under reduced pressure, and purified by column chromatography (eluent ethyl acetate) to obtain a white solid (yield 40%);

[0196] S2, the above product (312 mg, 1 mmol), n-butyl bromide (1370 mg, 10 mmol) were dissolved in 30 ml of N, N-dimethylformamide solution, stirred, slowly warmed to 80℃, reacted for 72 h, filtered, distilled under reduced pressure, and white solid intermediate 7 was obtained (yield 60%);

[0197] S3, intermediate 7 ligand (584 mg, 1 mmol), palladium dichloride (177 mg, 2 mmol) and potassium acetate (492 mg, 4 mmol) were dissolved in 20 mL of DMF (N, N-dimethylformamide), stirred, slowly warmed to 140℃, reacted for three days, distilled under reduced pressure to remove the solvent, and purified by column chromatography (eluent petroleum ether: dichloromethane = 1:2) to obtain the final product CCC-BMZ (yield 30%).

[0198] Preparation of tridentate ligand metal chloride CCC-BMZ-CF3

[0199] The synthetic route is as follows:

[0200] S1, similar to S1 of the preparation process of metal palladium chloride CCC-BMZ, the difference is that CCC-BMZ-CF3-1 is used instead of CCC-BMZ1, and the reaction obtains CCC-BMZ-CF3-2;

[0201] S2, similar to S2 of the preparation process of metal palladium chloride CCC-BMZ, the difference is that CCC-BMZ-CF3-2 is used instead of CCC-BMZ2 to obtain intermediate 8;

[0202] S3. Similar to S3 of the preparation of metal palladium chloride CCC-BMZ, except that intermediate 8 is used in place of intermediate 7, the reaction yields the final product metal palladium chloride CCC-BMZ-CF3.

[0203] Preparation of tridentate ligand metal chloride CCC-BMZ-CN

[0204] The synthesis route is shown below:

[0205] S1. Similar to S1 of the preparation of metal palladium chloride CCC-BMZ, except that CCC-BMZ-CN1 is used in place of CCC-BMZ1, the reaction yields CCC-BMZ-CN2 (yield 60%), 1 H NMR (500 MHz, DMSO) δ (ppm) 8.77 (s, 2H), 8.32 (s, 1H), 8.24 (s, 3H), 7.83 (dd, J = 14.0, 7.9 Hz, 4H), 7.79 (s, 1H), 7.42 - 7.33 (m, 4H);

[0206] S2. Similar to S2 of the preparation of metal palladium chloride CCC-BMZ, except that CCC-BMZ-CN2 is used in place of CCC-BMZ2, the reaction yields intermediate 9 (yield 50%), 1 H NMR (500 MHz, DMSO) δ (ppm) 10.41 (s, 2H), 8.61 (dd, J = 12.8, 1.9 Hz, 3H), 8.44 (s, 1H), 8.26 (d, J = 8.0 Hz, 4H), 8.11 (d, J = 8.0 Hz, 2H), 7.97 (s, 1H), 7.85 - 7.74 (m, 4H), 4.64 (t, J = 7.3 Hz, 4H), 2.02 (p, J = 7.5 Hz, 4H), 1.46 (h, J = 7.3 Hz, 4H), 0.97 (t, J = 7.4 Hz, 6H);

[0207] S3. Similar to S3 of the preparation of metal palladium chloride CCC-BMZ, except that intermediate 9 is used in place of intermediate 7, the reaction yields the final product metal palladium chloride CCC-BMZ-CN (yield 30%), 1 H NMR (500 MHz, CDCl3) δ (ppm) 7.89 (d, J = 8.0 Hz, 2H), 7.58 - 7.50 (m, 6H), 7.47 (t, J = 7.6 Hz, 2H), 5.07 - 4.98 (m, 4H), 1.95 (q, J = 7.6 Hz, 4H), 1.27 (d, J = 15.6 Hz, 4H), 0.99 (td, J = 7.4, 2.7 Hz, 6H).

[0208] Preparation of tridentate ligand metal chloride CCC-BMZ-CH3

[0209] The synthetic route is shown below:

[0210] S1. Similar to S1 of the preparation of metal palladium chloride CCC-BMZ, except that CCC-BMZ1 is replaced by CCC-BMZ-CH3-1, the reaction gives CCC-BMZ-CH3-2;

[0211] S2. Similar to S2 of the preparation of metal palladium chloride CCC-BMZ, except that CCC-BMZ2 is replaced by CCC-BMZ-CH3-2, the reaction gives intermediate 10;

[0212] S3. Similar to S3 of the preparation of metal palladium chloride CCC-BMZ, except that intermediate 7 is replaced by intermediate 10, the reaction gives the final product metal palladium chloride CCC-BMZ-CH3.

[0213] Preparation of paddle-shaped ligand DphCZ:

[0214] The synthetic route is shown below:

[0215] 1 -amino-2-chloronaphthalene (178 mg, 1 mmol), 1 -iodonaphthalene (254 mg, 1 mmol) (DphCZ-1) and Pd2(dba)3(46 mg, 0.05 mmol), DPPF (55 mg, 0.1 mmol), t BuONa (288 mg, 3 mmol) was dissolved in 20 ml of toluene solution, stirred, slowly warmed to 105 °C, reacted for 9 h, filtered with diatomite, the filtrate was distilled under reduced pressure, purified by column chromatography (eluent ethyl acetate: petroleum ether = 1 :3), and intermediate 11 was obtained (yield 60%).

[0216] Intermediate 11 (303 mg, 1 mmol) and Pd2(dba)3(46 mg, 0.05 mmol), X-Phos (48 mg, 0.1 mmol), t BuONa (288 mg, 3 mmol) was dissolved in 20 ml of toluene solution, stirred, slowly warmed to 105 °C, reacted for 9 h, filtered with diatomite, the filtrate was distilled under reduced pressure, purified by column chromatography (eluent ethyl acetate: petroleum ether = 1 :3), and intermediate 11 was obtained (yield 60%). 1H NMR (500 MHz, CDC13) δ (ppm) 9.51 (s, 1H), 8.28 (d, J = 8.1 Hz, 2H), 8.18 (d, J = 8.5 Hz, 2H), 8.03 (d, J = 8.1 Hz, 2H), 7.71 (d, J = 8.5 Hz, 2H), 7.67 - 7.61 (m, 2H), 7.54 (td, J = 7.5, 7.0, 1.1 Hz, 2H).

[0217] Preparation of chelating ligand DphCZ-2:

[0218] The synthetic route is shown below:

[0219] Similar to the preparation of chelating ligand DphCZ, the difference is that DphCZ-2-1 is used instead of DphCZ-1 to prepare chelating ligand DphCZ-2.

[0220] Preparation of chelating ligand DphCZ-3:

[0221] The synthetic route is shown below:

[0222] Similar to the preparation of chelating ligand DphCZ, the difference is that DphCZ-3-1 is used instead of DphCZ-1 to prepare chelating ligand DphCZ-3.

[0223] Preparation of chelating ligand DphCZ-O:

[0224] The synthetic route is shown below:

[0225] DphCZ-O was prepared by dissolving 1-amino-2-naphthol (159 mg, 1 mmol), 2-bromo-1-chloronaphthalene (241 mg, 1 mmol) and CS2CO3 (1.3 g mg, 4 mmol) in anhydrous dimethyl sulfoxide solution, stirring, slowly warming to 140 °C, reacting for 12 h, filtering with diatomite, distilling the filtrate under reduced pressure, and purifying by column chromatography.

[0226] Preparation of chelating ligand DphCZ-S:

[0227] The synthetic route is shown below:

[0228] A 250 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser was charged with 1,1"-dinaphthylamine (269 mg, 1 mmol), selenium dioxide (110 mg, 1 mmol), iodine (12.7 mg, 0.05 mmol), selenium (40 mg, 0.5 mmol) and 20 mL of sulfolane. The mixture was stirred at 150 °C for 12 h, then cooled to room temperature. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered over celite, then the filtrate was extracted with dichloromethane / water. Distilled under reduced pressure, and purified by silica gel column chromatography using dichloromethane / petroleum ether (1:4) as eluent to obtain DphCZ-Se.

[0229] Preparation of chelating ligand DphCZ-Se:

[0230] The synthetic route is shown below:

[0231] A 250 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser was charged with 1,1"-dinaphthylamine (269 mg, 1 mmol), selenium dioxide (110 mg, 1 mmol), iodine (12.7 mg, 0.05 mmol), selenium (40 mg, 0.5 mmol) and 20 mL of sulfolane. The mixture was stirred at 150 °C for 12 h, then cooled to room temperature. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered over celite, then the filtrate was extracted with dichloromethane / water. Distilled under reduced pressure, and purified by silica gel column chromatography using dichloromethane / petroleum ether (1:4) as eluent to obtain DphCZ-Se.

[0232] Example 1

[0233] This example provides a method for preparing metal palladium complex Pd-2, which specifically comprises the following steps:

[0234] The synthetic route is shown below:

[0235] A 250 mL round bottom flask equipped with a magnetic stir bar and a reflux condenser was charged with 1,1"-dinaphthylamine (269 mg, 1 mmol), selenium dioxide (110 mg, 1 mmol), iodine (12.7 mg, 0.05 mmol), selenium (40 mg, 0.5 mmol) and 20 mL of sulfolane. The mixture was stirred at 150 °C for 12 h, then cooled to room temperature. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered over celite, then the filtrate was extracted with dichloromethane / water. Distilled under reduced pressure, and purified by silica gel column chromatography using dichloromethane / petroleum ether (1:4) as eluent to obtain DphCZ-Se. 1H NMR (400 MHz, DMSO) δ (ppm) 8.16 (d, J = 1.9 Hz, 2H), 8.03 (d, J = 7.6 Hz, 2H), 7.89 (s, 2H), 7.43 (d, J = 8.1 Hz, 2H), 7.38 (d, J = 1.9 Hz, 2H), 7.16 - 7.11 (m, 2H), 6.87 (t, J = 7.3 Hz, 2H), 3.10 - 3.02 (m, 4H), 1.03 - 0.93 (m, 4H), 0.18 (t, J = 7.1 Hz, 6H), 0.07 (dt, J = 15.2, 6.8 Hz, 4H).

[0236] Referring to the preparation process of metal palladium complex Pd-2, metal palladium complex Pd-1, metal palladium complex Pd-3, metal palladium complex Pd-4, metal palladium complex Pd-5, metal palladium complex Pd-6, metal palladium complex Pd-7, metal palladium complex Pd-8, metal palladium complex Pd-10 metal palladium complex Pd-9 ((yield 80%), metal palladium complex Pd-11 ((yield 80%) are prepared according to the following steps: 1 H NMR (500 MHz, CDCl3) δ (ppm) 8.17 (d, J = 7.7 Hz, 2H), 8.00 (d, J = 8.3 Hz, 2H), 7.78 (s, 2H), 7.62 (d, J = 8.1 Hz, 2H), 7.52 (t, J = 7.8 Hz, 2H), 7.39 (t, J = 7.7 Hz, 2H), 7.32 (d, J = 8.1 Hz, 2H), 7.24 - 7.21 (m, 2H), 7.02 (t, J = 7.3 Hz, 2H), 3.48 - 3.41 (m, 3H), 1.18 - 1.10 (m, 4H), 0.29 (t, J = 7.3 Hz, 6H), 0.19 - 0.11 (m, 4H)).

[0237] Example 2

[0238] The present embodiment provides a preparation method of metal palladium complex Pd-12, which specifically comprises the following steps:

[0239] phenoxazine (36.6 mg, 0.2 mmol), sodium hydride (4.8 mg, 2 mmol) are dissolved in 20 mL of super dry tetrahydrofuran solution, stirred at room temperature for 5 h, then metal palladium chloride CCC-CN (100 mg, 0.2 mmol) is added, and the reaction is carried out at room temperature overnight. The reaction is filtered on filter paper, the filtrate is distilled under reduced pressure, and then recrystallized with dichloromethane: n-hexane = 1:100 ratio to obtain metal palladium complex Pd-12.

[0240] Reference to the preparation process of metal palladium complex Pd-12, metal palladium complex Pd-11, metal palladium complex Pd-13, metal palladium complex Pd-14, metal palladium complex Pd-15, metal palladium complex Pd-16, metal palladium complex Pd-17, metal palladium complex Pd-18, metal palladium complex Pd-19, metal palladium complex Pd-20 are prepared.

[0241] Example 3

[0242] The embodiment provides a preparation method of metal palladium complex Pd-22, and specifically comprises the following steps:

[0243] phenothiazine (40 mg, 0.2 mmol), sodium hydride (4.8 mg, 2 mmol) are dissolved in 20 mL of super dry tetrahydrofuran solution, stirred at room temperature for 5 h, then metal palladium chloride CCC-CN (100 mg, 0.2 mmol) is added, and the reaction is carried out at room temperature overnight. The reaction is filtered on filter paper, the filtrate is distilled under reduced pressure, and then recrystallized with dichloromethane:n-hexane=1:100, to obtain metal palladium complex Pd-22.

[0244] Reference to the preparation process of metal palladium complex Pd-22, metal palladium complex Pd-21, metal palladium complex Pd-23, metal palladium complex Pd-24, metal palladium complex Pd-25, metal palladium complex Pd-26, metal palladium complex Pd-27, metal palladium complex Pd-28, metal palladium complex Pd-29, metal palladium complex Pd-30 are prepared.

[0245] Example 4

[0246] The embodiment provides a preparation method of metal palladium complex Pd-32, and specifically comprises the following steps:

[0247] phenothiazine (40 mg, 0.2 mmol), sodium hydride (4.8 mg, 2 mmol) are dissolved in 20 mL of super dry tetrahydrofuran solution, stirred at room temperature for 5 h, then metal palladium chloride CCC-CN (100 mg, 0.2 mmol) is added, and the reaction is carried out at room temperature overnight. The reaction is filtered on filter paper, the filtrate is distilled under reduced pressure, and then recrystallized with dichloromethane:n-hexane=1:100, to obtain metal palladium complex Pd-22.

[0248] Reference to the preparation process of metal palladium complex Pd-32, metal palladium complex Pd-31, metal palladium complex Pd-33, metal palladium complex Pd-34, metal palladium complex Pd-35, metal palladium complex Pd-36, metal palladium complex Pd-37, metal palladium complex Pd-38, metal palladium complex Pd-39, metal palladium complex Pd-40 are prepared.

[0249] Example 5

[0250] The present example provides a method for preparing metal palladium complex Pd-42, which specifically comprises the following steps:

[0251] tert-butyl carbazole (55.9 mg, 0.2 mmol), potassium tert-butoxide (112 mg, 1 mmol) were dissolved in 20 mL of super dry tetrahydrofuran solution, stirred at room temperature for 5 h, then metal palladium chloride CCC-CN (100 mg, 0.2 mmol) was added, and the reaction was carried out at room temperature overnight. The reaction was filtered on filter paper, and the filtrate was distilled under reduced pressure. Then, recrystallization was carried out with dichloromethane: n-hexane = 1:100 ratio, and green powder complex Pd-42 was obtained (yield 80%), 1 H NMR (500 MHz, DMSO) δ (ppm) 8.15 (d, J = 1.8 Hz, 2H), 8.02 (d, J = 1.8 Hz, 2H), 7.88 (s, 2H), 7.38 (d, J = 1.8 Hz, 2H), 7.31 (d, J = 8.5 Hz, 2H), 7.19 (dd, J = 8.5, 1.9 Hz, 2H), 3.07 - 3.03 (m, 4H), 1.40 (s, 18H), 1.09 - 1.02 (m, 4H), 0.25 (t, J = 7.3 Hz, 6H), 0.06 (s, 4H);

[0252] Referring to the preparation process of metal palladium complex Pd-42, metal palladium complexes Pd-41 1 H NMR (500 MHz, DMSO) δ (ppm) 8.15 (d, J = 1.8 Hz, 2H), 8.02 (d, J = 1.8 Hz, 2H), 7.88 (s, 2H), 7.38 (d, J = 1.8 Hz, 2H), 7.31 (d, J = 8.5 Hz, 2H), 7.19 (dd, J = 8.5, 1.9 Hz, 2H), 3.07 - 3.03 (m, 4H), 1.40 (s, 18H), 1.09 - 1.02 (m, 4H), 0.25 (t, J = 7.3 Hz, 6H), 0.06 (s, 4H); 1H NMR (500 MHz, DMSO) δ (ppm) 8.12 (s, 2H), 8.00 (s, 2H), 7.37 - 7.33 (m, 4H), 7.27 (s, 2H), 7.18 (d, J = 8.6 Hz, 2H), 3.06 - 3.01 (m, 5H), 1.40 (s, 27H), 1.06 (s, 5H), 0.26 (t, J = 7.3 Hz, 7H)), metal palladium complex Pd-45, metal palladium complex Pd-46, metal palladium complex Pd-47, metal palladium complex Pd-48, metal palladium complex Pd-49 ((yield 80%), 1 H NMR (500 MHz, CDCl3) δ (ppm) 8.17 (s, 2H), 8.02 (d, J = 8.2 Hz, 2H), 7.79 (s, 2H), 7.52 (dd, J = 18.7, 8.1 Hz, 4H), 7.40 (t, J = 7.7 Hz, 2H), 7.34 (d, J = 8.1 Hz, 2H), 7.27 (s, 2H), 3.51 - 3.45 (m, 4H), 1.48 (s, 19H), 1.26 - 1.16 (m, 5H), 0.37 (t, J = 7.2 Hz, 6H), 0.17 (dt, J = 15.3, 7.4 Hz, 4H)) metal palladium complex Pd-50.

[0253] Example 6

[0254] The present example provides a preparation method of metal palladium complex Pd-52, which specifically comprises the following steps:

[0255] Take 1,3,6,8-tetramethyl-9H-carbazole (44.6 mg, 0.2 mmol), potassium tert-butoxide (112 mg, 1 mmol), dissolve in 20 mL of super dry tetrahydrofuran solution, stir at room temperature for 5 h, then add metal palladium chloride CCC-CN (100 mg, 0.2 mmol), react at room temperature overnight, filter the reaction paper, distill the filtrate under reduced pressure, then recrystallize with dichloromethane:n-hexane = 1:100 ratio, get orange powder complex Pd-52 (yield 80%), 1 H NMR (500 MHz, DMSO) δ (ppm) 8.14 (d, J = 1.9 Hz, 2H), 7.87 (s, 2H), 7.59 (s, 2H), 7.38 (d, J = 1.9 Hz, 2H), 6.72 (s, 2H), 3.15 - 3.09 (m, 4H), 2.87 (s, 5H), 2.39 (s, 5H), 1.00 (s, 4H), 0.20 (t, J = 6.8 Hz, 6H), 0.17 - 0.10 (m, 4H);

[0256] Referring to the preparation process of metal palladium complex Pd-52, metal palladium complex Pd-51 can be prepared, metal palladium complex Pd-53 is prepared, metal palladium complex Pd-54 ((yield 80%) is prepared, 1 H NMR (500 MHz, DMSO) δ (ppm) 8.10 (d, J = 1.6 Hz, 2H), 7.57 (s, 2H), 7.36 (s, 2H), 7.27 (d, J = 1.6 Hz, 2H), 6.70 (s, 2H), 3.13 - 3.06 (m, 4H), 2.93 (s, 6H), 2.38 (s, 6H), 1.40 (s, 10H), 1.00 (s, 5H), 0.21 (t, J = 6.9 Hz, 6H), 0.16 - 0.10 (m, 4H)), metal palladium complex Pd-55, metal palladium complex Pd-56, metal palladium complex Pd-57, metal palladium complex Pd-58, metal palladium complex Pd-59 ((yield 60%), 1 H NMR (500 MHz, DMSO) δ (ppm) 8.10 (d, J = 1.6 Hz, 2H), 7.57 (s, 2H), 7.36 (s, 2H), 7.27 (d, J = 1.6 Hz, 2H), 6.70 (s, 2H), 3.13 - 3.06 (m, 4H), 2.93 (s, 6H), 2.38 (s, 6H), 1.40 (s, 10H), 1.00 (s, 5H), 0.21 (t, J = 6.9 Hz, 6H), 0.16 - 0.10 (m, 4H)), metal palladium complex Pd-55, metal palladium complex Pd-56, metal palladium complex Pd-57, metal palladium complex Pd-58, metal palladium complex Pd-59 ((yield 60%),

[0257] Example 7

[0258] The present embodiment provides a preparation method of metal palladium complex Pd-62, which specifically comprises the following steps:

[0259] Take N3,N3,N6,N6-tetraphenyl-9H-carbazole-3,6-diamine (100 mg, 0.2 mmol), potassium tert-butoxide (112 mg, 1 mmol), dissolve in 20 mL of super dry tetrahydrofuran solution, stir at room temperature for 5 h, then add metal palladium chloride CCC-CN (100 mg, 0.2 mmol), react at room temperature overnight, filter the reaction paper, distill the filtrate under reduced pressure, then recrystallize with dichloromethane:n-hexane=1:100 ratio, and obtain orange powder complex Pd-62 (yield 80%), 1H NMR (500 MHz, DMSO) δ (ppm) 8.18 (d, J = 1.8 Hz, 2H), 7.90 (s, 2H), 7.81 (d, J = 1.9 Hz, 2H), 7.49 (d, J = 8.5 Hz, 2H), 7.44 (d, J = 1.8 Hz, 2H), 7.16 (t, J = 7.9 Hz, 8H), 6.99 (dd, J = 8.5, 2.0 Hz, 2H), 6.95 (d, J = 7.9 Hz, 8H), 6.85 (t, J = 7.3 Hz, 4H), 3.25 - 3.19 (m, 4H), 1.10 (s, 4H), 0.35 (d, J = 3.0 Hz, 10H);

[0260] Referring to the preparation process of metal palladium complex Pd-62, metal palladium complex Pd-61, metal palladium complex Pd-63, metal palladium complex Pd-64, metal palladium complex Pd-65, metal palladium complex Pd-66, metal palladium complex Pd-67, metal palladium complex Pd-68, metal palladium complex Pd-69 ((yield 80%), metal palladium complex Pd-70 are prepared, 1 H NMR (400 MHz, THF) δ (ppm) 10.83 (s, 1H), 8.40 (d, J = 8.3 Hz, 2H), 8.10 (s, 2H), 7.85 (d, J = 2.0 Hz, 2H), 7.64 - 7.52 (m, 6H), 7.45 (t, J = 7.5 Hz, 2H), 7.12 - 7.02 (m, 17H), 6.78 (t, J = 7.0 Hz, 4H), 3.73 (dd, J = 9.4, 7.0 Hz, 4H), 1.27 (dd, J = 14.0, 6.8 Hz, 4H), 0.51 (s, 10H)), metal palladium complex Pd-70.

[0261] Example 8

[0262] The present embodiment provides a preparation method of metal palladium complex Pd-72, which specifically comprises the following steps:

[0263] Take the chelating ligand DphCZ (53.5 mg, 0.2 mmol), potassium tert-butoxide (112 mg, 1 mmol), dissolve in 20 mL of super dry tetrahydrofuran solution, stir at room temperature for 5 h, then add metal palladium chloride CCC-CN (100 mg, 0.2 mmol), react at room temperature overnight, filter the reaction paper, distill the filtrate under reduced pressure, then recrystallize with dichloromethane: n-hexane = 1:100 ratio, get green powder complex Pd-72 (yield 80%), 1H NMR (500 MHz, DMSO) d (ppm) 10.16 (d, J = 8.2 Hz, 2H), 8.29 (d, J = 8.4 Hz, 2H), 8.19 (d, J = 1.7 Hz, 2H), 8.01 (s, 2H), 7.91 (d, J = 7.7 Hz, 2H), 7.45 (d, J = 8.4 Hz, 2H), 7.31 - 7.24 (m, 4H), 7.21 (t, J = 7.2 Hz, 2H), 2.91 - 2.81 (m, 4H), 0.58 (s, 4H), -0.21 (dd, J = 16.3, 6.2 Hz, 10H);

[0264] Referring to the procedure for the preparation of metal palladium complex Pd-72, metal palladium complex Pd-71 was prepared ((yield 80%) from 2,6-dimethylpyridine (0.5 g, 4.2 mmol), 2,6-dimethylpyridine (0.5 g, 4.2 mmol), Pd(OAc)2(0.1 g, 0.42 mmol) and 2,6-dimethylpyridine (0.5 g, 4.2 mmol) in 1,4-dioxane (10 ml) at 100 °C for 16 h. 1 H NMR (500 MHz, DMSO) d (ppm) 10.34 (d, J = 8.1 Hz, 2H), 8.28 (d, J = 8.4 Hz, 2H), 8.09 (d, J = 1.9 Hz, 2H), 7.90 (d, J = 7.3 Hz, 2H), 7.45 - 7.39 (m, 4H), 7.36 (d, J = 6.9 Hz, 1H), 7.28 - 7.23 (m, 2H), 7.23 - 7.18 (m, 4H), 2.87 - 2.81 (m, 4H), 0.61 - 0.54 (m, 4H), -0.16 - -0.25 (m, 10H)), metal palladium complex Pd-73 ((yield 80%) from 2,6-dimethylpyridine (0.5 g, 4.2 mmol), 2,6-dimethylpyridine (0.5 g, 4.2 mmol), Pd(OAc)2(0.1 g, 0.42 mmol) and 2,6-dimethylpyridine (0.5 g, 4.2 mmol) in 1,4-dioxane (10 ml) at 100 °C for 16 h. 1 H NMR (500 MHz, DMSO) d (ppm) 10.22 (d, J = 8.2 Hz, 2H), 8.30 (dd, J = 5.1, 3.3 Hz, 4H), 7.94 - 7.89 (m, 4H), 7.45 (d, J = 8.5 Hz, 2H), 7.29 - 7.24 (m, 4H), 7.23 - 7.19 (m, 2H), 2.89 - 2.84 (m, 4H), 0.59 (s, 4H), -0.21 (dd, J = 17.5, 6.1 Hz, 10H)), metal palladium complex Pd-74, metal palladium complex Pd-75, metal palladium complex Pd-76, metal palladium complex Pd-77, metal palladium complex Pd-78, metal palladium complex Pd-79 (yield 80%) from 2,6-dimethylpyridine (0.5 g, 4.2 mmol), 2,6-dimethylpyridine (0.5 g, 4.2 mmol), Pd(OAc)2(0.1 g, 0.42 mmol) and 2,6-dimethylpyridine (0.5 g, 4.2 mmol) in 1,4-dioxane (10 ml) at 100 °C for 16 h. 1H NMR (400 MHz, DMSO) δ (ppm) 10.21 (d, J = 8.0 Hz, 2H), 8.65 (d, J = 8.3 Hz, 2H), 8.47 (s, 2H), 8.38 (d, J = 8.4 Hz, 2H), 7.93 (d, J = 7.4 Hz, 2H), 7.53 (q, J = 9.0 Hz, 6H), 7.45 - 7.38 (m, 2H), 7.27 - 7.17 (m, 4H), 3.29 - 3.23 (m, 4H), 0.63 (s, 4H), -0.18 (d, J = 4.2 Hz, 10H), metal palladium complex Pd-80.

[0265] Example 9

[0266] The present example provides a preparation method of metal palladium complex Pd-82, which specifically comprises the following steps:

[0267] Take the chelating ligand DphCZ-2 (54 mg, 0.2 mmol), potassium tert-butoxide (112 mg, 1 mmol), dissolve in 20 mL of super dry tetrahydrofuran solution, stir at room temperature for 5 h, then add metal palladium chloride CCC-CN (100 mg, 0.2 mmol), react at room temperature overnight, filter the reaction paper, distill the filtrate under reduced pressure, then recrystallize with dichloromethane:n-hexane = 1:100 ratio, to obtain the powder complex Pd-82.

[0268] Referring to the preparation process of metal palladium complex Pd-82, metal palladium complex Pd-81, metal palladium complex Pd-83, metal palladium complex Pd-84, metal palladium complex Pd-85, metal palladium complex Pd-86, metal palladium complex Pd-87, metal palladium complex Pd-88, metal palladium complex Pd-89, and metal palladium complex Pd-90 are prepared.

[0269] Example 10

[0270] The present example provides a preparation method of metal palladium complex Pd-92, which specifically comprises the following steps:

[0271] Take the chelating ligand DphCZ-3 (75.8 mg, 0.2 mmol), potassium tert-butoxide (112 mg, 1 mmol), dissolve in 20 mL of super dry tetrahydrofuran solution, stir at room temperature for 5 h, then add metal palladium chloride CCC-CN (100 mg, 0.2 mmol), react at room temperature overnight, filter the reaction paper, distill the filtrate under reduced pressure, then recrystallize with dichloromethane:n-hexane = 1:100 ratio, to obtain the powder complex Pd-92.

[0272] Reference to the preparation process of metal palladium complex Pd-92, metal palladium complex Pd-91, metal palladium complex Pd-93, metal palladium complex Pd-94, metal palladium complex Pd-95, metal palladium complex Pd-96, metal palladium complex Pd-97, metal palladium complex Pd-98, metal palladium complex Pd-99, metal palladium complex Pd-100 are prepared.

[0273] Example 11

[0274] The embodiment provides a preparation method of metal palladium complex Pd-102, and specifically comprises the following steps:

[0275] The chelating ligand DphCZ-O (54 mg, 0.2 mmol) and sodium hydride (4.8 mg, 2 mmol) are dissolved in 20 mL of ultradry tetrahydrofuran solution, stirred at room temperature for 5 h, then metal palladium chloride CCC-CN (100 mg, 0.2 mmol) is added, and the reaction is carried out at room temperature overnight. The reaction is filtered on filter paper, the filtrate is distilled under reduced pressure, and then recrystallized with dichloromethane:n-hexane=1:100 to obtain the powder complex Pd-102.

[0276] Reference to the preparation process of metal palladium complex Pd-102, metal palladium complex Pd-101, metal palladium complex Pd-103, metal palladium complex Pd-104, metal palladium complex Pd-105, metal palladium complex Pd-106, metal palladium complex Pd-107, metal palladium complex Pd-108, metal palladium complex Pd-109, metal palladium complex Pd-110.

[0277] Example 12

[0278] The embodiment provides a preparation method of metal palladium complex Pd-112, and specifically comprises the following steps:

[0279] The chelating ligand DphCZ-S (60 mg, 0.2 mmol) and sodium hydride (4.8 mg, 2 mmol) are dissolved in 20 mL of ultradry tetrahydrofuran solution, stirred at room temperature for 5 h, then metal palladium chloride CCC-CN (100 mg, 0.2 mmol) is added, and the reaction is carried out at room temperature overnight. The reaction is filtered on filter paper, the filtrate is distilled under reduced pressure, and then recrystallized with dichloromethane:n-hexane=1:100 to obtain the powder complex Pd-112.

[0280] Reference to the preparation process of metal palladium complex Pd-112, metal palladium complex Pd-111, metal palladium complex Pd-113, metal palladium complex Pd-114, metal palladium complex Pd-115, metal palladium complex Pd-116, metal palladium complex Pd-117, metal palladium complex Pd-118, metal palladium complex Pd-119, metal palladium complex Pd-120 are prepared.

[0281] Example 13

[0282] The present embodiment provides a preparation method of metal palladium complex Pd-122, which specifically comprises the following steps:

[0283] Take the chelating ligand DphCZ-Se (70 mg, 0.2 mmol), sodium hydride (4.8 mg, 2 mmol), dissolve in 20 mL of super dry tetrahydrofuran solution, stir at room temperature for 5 h, then add metal palladium chloride CCC-CN (100 mg, 0.2 mmol), react at room temperature overnight, filter the reaction paper, distill the filtrate under reduced pressure, then recrystallize with dichloromethane: n-hexane = 1:100 ratio, and obtain the powder complex Pd-122.

[0284] Reference to the preparation process of metal palladium complex Pd-122, metal palladium complex Pd-121, metal palladium complex Pd-123, metal palladium complex Pd-124, metal palladium complex Pd-125, metal palladium complex Pd-126, metal palladium complex Pd-127, metal palladium complex Pd-128, metal palladium complex Pd-129, metal palladium complex Pd-130 are prepared.

[0285] Example 14

[0286] The present embodiment provides a preparation method of metal palladium complex Pd-132, which specifically comprises the following steps:

[0287] To 9H-carbazole-3-carbonitrile (26 mg, 0.2 mmol), potassium tert-butoxide (112 mg, 1 mmol) in 20 mL of super dry tetrahydrofuran was stirred at room temperature for 5 h, then palladium metal chloride CCC-CN (100 mg, 0.2 mmol) was added and the reaction was allowed to proceed at room temperature overnight. The reaction was filtered on paper, the filtrate was distilled under reduced pressure, then recrystallized with dichloromethane: n-hexane = 1:100 to give the powder complex Pd-132.1H NMR (500 MHz, CDCl3) δ (ppm) 8.42 (d, J = 1.3 Hz, 1H), 8.12 (d, J = 7.7 Hz, 1H), 7.64 (d, J = 8.1 Hz, 1H), 7.56 (d, J = 8.4 Hz, 1H), 7.45 (dd, J = 8.4, 1.5 Hz, 1H), 7.42 (d, J = 1.9 Hz, 2H), 7.31 (t, J = 7.5 Hz, 1H), 7.25 (s, 4H), 7.11 (t, J = 7.4 Hz, 1H), 6.84 (d, J = 1.9 Hz, 2H), 3.08 (t, J = 8.0 Hz, 4H), 1.09 - 1.01 (m, 4H), 0.28 (t, J = 7.0 Hz, 6H), 0.20 (dt, J = 14.4, 7.0 Hz, 4H).

[0288] Referring to the preparation process of metal palladium complex Pd-132, metal palladium complexes Pd-131, Pd-133, Pd-134, Pd-135, Pd-136, Pd-137, Pd-138, Pd-139 (1H NMR (500 MHz, CDCl3) δ (ppm) 8.48 (s, 1H), 8.18 (d, J = 7.8 Hz, 1H), 8.01 (d, J = 8.3 Hz, 2H), 7.78 (s, 2H), 7.71 (d, J = 8.0 Hz, 1H), 7.63 (d, J = 8.5 Hz, 1H), 7.54 (t, J = 7.7 Hz, 2H), 7.46 (dd, J = 8.4, 1.3 Hz, 1H), 7.41 (t, J = 7.7 Hz, 2H), 7.34 (d, J = 8.3 Hz, 3H), 7.15 (t, J = 7.3 Hz, 1H), 3.40 (t, J = 8.4 Hz, 4H), 1.13 (q, J = 7.3 Hz, 4H), 0.30 (t, J = 7.3 Hz, 6H), 0.14 (dt, J = 14.0, 6.8 Hz, 4H)), and metal palladium complex Pd-140 were prepared.

[0289] Device Example 1

[0290] The embodiment provides an organic electroluminescent device, as shown in Figure 1, which comprises, from bottom to top, an anode layer 1, a hole injection layer 2, a hole transport layer 3, an electron blocking layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7 and a cathode layer 8 arranged on a glass substrate 100 in sequence;

[0291] The materials for manufacturing the organic electroluminescent device are as follows:

[0292] The anode layer is made of ITO material, i.e. indium tin oxide material; the hole injection layer with a thickness of 5 nm is made of 1,2-hexaazatriphenylene (HAT-CN); the hole transport layer with a thickness of 40 nm is made of N4,N4,N4',N4'-tetrakis(4-biphenyl)-biphenyl-4,4'-diamine (TBBD); the electron blocking layer with a thickness of 10 nm is made of N-([1,1'-biphenyl]-2-yl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobi[fluorene]-2-amine (o-SFAF); the light-emitting layer with a thickness of 40 nm is formed by co-doping of a host material and a guest material, wherein the host material is 5-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-7,7-dimethyl-5,7-dihydroinden[2,1-b]carbazole (DMIC-TRZ), and the guest material is the metal complex Pd-2 of the present application, and the doping amount of the guest material accounts for 1% of the total mass of the host material and the guest material; the electron transport layer with a thickness of 30 nm is made of (1-(4-(10-([1,1'-biphenyl]-4-yl)anthracen-9-yl)phenyl)-2-ethyl-1H-benzo[d]-imidazole) (ANT-BIZ); the electron injection layer with a thickness of 1.2 nm is made of Liq (lithium 8-hydroxyquinoline); and the cathode layer with a thickness of 100 nm is made of metal Al material.

[0293] Device embodiment 2

[0294] The embodiment provides an organic electroluminescent device, which is different from the organic electroluminescent device provided in device embodiment 1 in that the doping amount of the guest material metal complex Pd-2 in the light-emitting layer accounts for 3% of the total mass of the host material and the guest material.

[0295] Device embodiment 3

[0296] The embodiment provides an organic electroluminescent device, which is different from the organic electroluminescent device provided in device embodiment 1 in that the doping amount of the guest material metal complex Pd-2 in the light-emitting layer accounts for 6% of the total mass of the host material and the guest material.

[0297] Device embodiment 4

[0298] The embodiment provides an organic electroluminescence device, which is different from the organic electroluminescence device provided in the device embodiment 1 in that the doping amount of the guest material metal complex Pd-2 in the light-emitting layer accounts for 9% of the total mass of the host material and the guest material.

[0299] Device embodiment 5

[0300] The embodiment provides an organic electroluminescence device, which is different from the organic electroluminescence device provided in the device embodiment 1 in that the doping amount of the guest material metal complex Pd-2 in the light-emitting layer accounts for 18% of the total mass of the host material and the guest material.

[0301] Device embodiment 6

[0302] The embodiment provides an organic electroluminescence device, which is different from the organic electroluminescence device provided in the device embodiment 1 in that the guest material in the light-emitting layer is replaced by the metal complex Pd-9.

[0303] Device embodiment 7

[0304] The embodiment provides an organic electroluminescence device, which is different from the organic electroluminescence device provided in the device embodiment 6 in that the doping amount of the guest material metal complex Pd-9 in the light-emitting layer accounts for 3% of the total mass of the host material and the guest material.

[0305] Device embodiment 8

[0306] The embodiment provides an organic electroluminescence device, which is different from the organic electroluminescence device provided in the device embodiment 6 in that the doping amount of the guest material metal complex Pd-9 in the light-emitting layer accounts for 6% of the total mass of the host material and the guest material.

[0307] Device embodiment 9

[0308] The embodiment provides an organic electroluminescence device, which is different from the organic electroluminescence device provided in the device embodiment 6 in that the doping amount of the guest material metal complex Pd-9 in the light-emitting layer accounts for 9% of the total mass of the host material and the guest material.

[0309] Device embodiment 10

[0310] The embodiment provides an organic electroluminescence device, which is different from the organic electroluminescence device provided in the device embodiment 1 in that the guest material in the light-emitting layer is replaced by the metal complex Pd-49.

[0311] Device embodiment 11

[0312] The embodiment provides an organic electroluminescent device, which is different from the organic electroluminescent device provided in the device embodiment 10 in that the doping amount of the guest material metal complex Pd-49 in the light-emitting layer accounts for 3% of the total mass of the host material and the guest material.

[0313] Device embodiment 12

[0314] The embodiment provides an organic electroluminescent device, which is different from the organic electroluminescent device provided in the device embodiment 10 in that the doping amount of the guest material metal complex Pd-49 in the light-emitting layer accounts for 6% of the total mass of the host material and the guest material.

[0315] Device embodiment 13

[0316] The embodiment provides an organic electroluminescent device, which is different from the organic electroluminescent device provided in the device embodiment 10 in that the doping amount of the guest material metal complex Pd-49 in the light-emitting layer accounts for 9% of the total mass of the host material and the guest material.

[0317] Device embodiment 14

[0318] The embodiment provides an organic electroluminescent device, which is different from the organic electroluminescent device provided in the device embodiment 7 in that the guest material in the light-emitting layer is the metal complex Pd-79, and the doping amount accounts for 3% of the total mass of the host material and the guest material.

[0319] Device embodiment 15

[0320] The embodiment provides an organic electroluminescent device, which is different from the organic electroluminescent device provided in the device embodiment 7 in that the guest material in the light-emitting layer is the metal complex Pd-79, and the doping amount accounts for 6% of the total mass of the host material and the guest material.

[0321] Device embodiment 16

[0322] The embodiment provides an organic electroluminescent device, which is different from the organic electroluminescent device provided in the device embodiment 7 in that the guest material in the light-emitting layer is the metal complex Pd-79, and the doping amount accounts for 9% of the total mass of the host material and the guest material.

[0323] Device embodiment 17

[0324] The embodiment provides an organic electroluminescent device, which is different from the organic electroluminescent device provided in the device embodiment 7 in that the guest material in the light-emitting layer is the metal complex Pd-79, and the doping amount accounts for 18% of the total mass of the host material and the guest material.

[0325] Device embodiment 18

[0326] The embodiment provides an organic electroluminescence device, which is different from the organic electroluminescence device provided in the device embodiment 1 in that the guest material in the light-emitting layer is replaced by the metal complex Pd-139.

[0327] Device embodiment 19

[0328] The embodiment provides an organic electroluminescence device, which is different from the organic electroluminescence device provided in the device embodiment 18 in that the doping amount of the guest material metal complex Pd-139 in the light-emitting layer accounts for 3% of the total mass of the host material and the guest material.

[0329] Device embodiment 20

[0330] The embodiment provides an organic electroluminescence device, which is different from the organic electroluminescence device provided in the device embodiment 18 in that the doping amount of the guest material metal complex Pd-139 in the light-emitting layer accounts for 6% of the total mass of the host material and the guest material.

[0331] Device embodiment 21

[0332] The embodiment provides an organic electroluminescence device, which is different from the organic electroluminescence device provided in the device embodiment 18 in that the doping amount of the guest material metal complex Pd-139 in the light-emitting layer accounts for 9% of the total mass of the host material and the guest material.

[0333] Test and characterization of the metal palladium complex:

[0334] The absorption spectrum and the emission spectrum of the metal palladium complex solution in the application are tested, wherein the solution is a toluene solution, the concentration of the metal complex in the toluene solution is 1x10 -5 mol L -1 , FIG. 2 is an absorption spectrum diagram of Pd-2 in a toluene solution; FIG. 3 is an absorption spectrum diagram of Pd-9 in a toluene solution; FIG. 4 is an absorption spectrum diagram of Pd-41 in a dichloromethane solution; FIG. 5 is an absorption spectrum diagram of Pd-42 in a toluene solution; FIG. 6 is an absorption spectrum diagram of Pd-49 in a toluene solution; FIG. 7 is an absorption spectrum diagram of Pd-52 in a toluene solution; FIG. 8 is an absorption spectrum diagram of Pd-54 in a toluene solution; FIG. 9 is an absorption spectrum diagram of Pd-59 in a toluene solution; FIG. 10 is an absorption spectrum diagram of Pd-62 in a toluene solution; FIG. 11 is an absorption spectrum diagram of Pd-69 in a toluene solution; FIG. 12 is an absorption spectrum diagram of Pd-71 in a toluene solution; FIG. 13 is an absorption spectrum diagram of Pd-72 in a toluene solution; FIG. 14 is an absorption spectrum diagram of Pd-77 in a toluene solution; FIG. 15 is an absorption spectrum diagram of Pd-79 in a toluene solution; FIG. 16 is an absorption spectrum diagram of Pd-139 in a toluene solution; and FIG. 17 is an absorption spectrum diagram of the chelating ligand DphCz in a toluene solution.

[0335] Figure 18 is an emission spectrum of Pd-2 in toluene solution; Figure 19 is an emission spectrum of Pd-9 in toluene solution; Figure 20 is an emission spectrum of Pd-41 in dichloromethane solution; Figure 21 is an emission spectrum of Pd-42 in toluene solution; Figure 22 is an emission spectrum of Pd-49 in toluene solution; Figure 23 is an emission spectrum of Pd-52 in toluene solution; Figure 24 is an emission spectrum of Pd-54 in toluene solution; Figure 25 is an emission spectrum of Pd-59 in toluene solution; Figure 26 is an emission spectrum of Pd-62 in toluene solution; Figure 27 is an emission spectrum of Pd-71 in toluene solution; Figure 28 is an emission spectrum of Pd-72 in toluene solution; Figure 29 is an emission spectrum of Pd-73 in toluene solution; Figure 30 is an emission spectrum of Pd-79 in toluene solution; Figure 31 is an emission spectrum of Pd-139 in toluene solution; Figure 32 is an emission spectrum of paddle-shaped ligand DphCz in toluene solution.

[0336] The emission spectra and lifetime of the metal palladium complexes of the present application in polymethyl methacrylate films were tested, and the incorporation concentration of the metal complexes in the polymethyl methacrylate films was 3 wt%. Figure 33 is an emission spectrum of Pd-2 in a polymethyl methacrylate film; Figure 34 is an emission spectrum of Pd-9 in a polymethyl methacrylate film at different temperatures; Figure 35 is an emission spectrum of Pd-44 in a polymethyl methacrylate film; Figure 36 is an emission spectrum of Pd-49 in a polymethyl methacrylate film; Figure 37 is an emission spectrum of Pd-54 in a polymethyl methacrylate film; Figure 38 is an emission spectrum of Pd-59 in a polymethyl methacrylate film; Figure 39 is an emission spectrum of Pd-62 in a polymethyl methacrylate film; Figure 40 is an emission spectrum of Pd-69 in a polymethyl methacrylate film; Figure 41 is an emission spectrum of Pd-72 in a polymethyl methacrylate film; Figure 42 is an emission spectrum of Pd-79 in a polymethyl methacrylate film; Figure 43 is an emission spectrum of Pd-139 in a polymethyl methacrylate film.

[0337] Figure 44 is a plot of lifetime decay of Pd-2 in polymethyl methacrylate film; Figure 45 is a plot of lifetime decay of Pd-9 in polymethyl methacrylate film; Figure 46 is a plot of lifetime decay of Pd-49 in polymethyl methacrylate film; Figure 47 is a plot of lifetime decay of Pd-59 in polymethyl methacrylate film; Figure 48 is a plot of lifetime decay of Pd-69 in polymethyl methacrylate film; Figure 49 is a plot of lifetime decay of Pd-71 in polymethyl methacrylate film; Figure 50 is a plot of lifetime decay of Pd-72 in polymethyl methacrylate film; Figure 51 is a plot of lifetime decay of Pd-79 in polymethyl methacrylate film; Figure 52 is a plot of lifetime decay of Pd-139 in polymethyl methacrylate film.

[0338] Test Example 1

[0339] The provided organic electroluminescent devices in device examples 1-5 were tested, and the guest material was selected as metal palladium complex Pd-2. The current-brightness-voltage characteristics of the devices were determined by a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a corrected silicon photodiode, and all tests were completed in room temperature atmosphere. The test results are shown in Table 1 and Figures 53-54, wherein Figure 53 is an electroluminescence diagram of device examples 1-5 based on metal palladium complex Pd-2, and Figure 54 is an electroluminescence quantum efficiency diagram of device examples 1-5 based on metal palladium complex Pd-2.

[0340] Table 1 Device performance test results

[0341] [a] maximum brightness; [b] current efficiency; [c] lumen efficiency; [d] external quantum efficiency;

[0342] As shown in Figures 53-54, the organic electroluminescent device prepared by using metal palladium complex Pd-2 as the guest material and at a doping concentration of 1% has a maximum luminous brightness of 59947 cd m -2 , a maximum current efficiency of 57.5 cd A -1 , a maximum lumen efficiency of 57.9 lm W - 1 , and a maximum external quantum efficiency of up to 18.9%.

[0343] Test Example 2

[0344] The provided organic electroluminescent devices in device examples 6-9 were tested, and the guest material was selected as metal palladium complex Pd-9, the current-brightness-voltage characteristics of the device were determined by a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a corrected silicon photodiode, and all tests were completed in room temperature atmosphere, and the test results are shown in Table 2 and Figs. 55-56, wherein Fig. 55 is an electroluminescence diagram of device examples 6-9 based on compound Pd-9 of the present application, and Fig. 56 is an electroluminescence quantum efficiency diagram of device examples 6-9 based on metal palladium complex Pd-9 of the present application.

[0345] Table 2 Device performance test results

[0346] [a] maximum brightness; [b] current efficiency; [c] luminous efficiency; [d] external quantum efficiency;

[0347] As shown in Figs. 55-56, the organic electroluminescent device prepared by using metal palladium complex Pd-9 as the guest material and at a doping concentration of 1% in the present application has a maximum luminous brightness of 166924 cd m -2 , a maximum current efficiency of 90.2 cd A -1 , a maximum luminous efficiency of 95.3 lm W -1 , and a maximum external quantum efficiency of up to 25.9%.

[0348] Test Example 3

[0349] The provided organic electroluminescent devices in device example 6 were tested for stability, and the guest material was selected as metal palladium complex Pd-9, which was packaged with a glass cover by ultraviolet light curing adhesive in a nitrogen-filled glove box, and then the working device was taken out from the glove box and measured for brightness at a constant current density using an OLED lifetime test system (FS-MP64, Suzhou FSTAR Scientific Instruments Co., Ltd., China), and all tests were completed in room temperature atmosphere. As shown in Fig. 57, the doped light-emitting OLED prepared by using metal palladium complex Pd-9 as the guest material and at a doping concentration of 1% in the present application has an initial brightness of 3000 cd m -2 , an LT 95 (LT 95 defined as the time used for a 5% decay in brightness) of 246 hours, an initial brightness of 1000 cd m -2 , and an LT 95 (LT 95 defined as the time used for a 5% decay in brightness) of 1592 hours.

[0350] Test Example 4

[0351] The provided organic electroluminescence devices in device examples 10-13 were tested, the guest material was selected as metal palladium complex Pd-49, the current-brightness-voltage characteristics of the devices were determined by Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with corrected silicon photodiode, all tests were completed in room temperature atmosphere, the test results are shown in Table 3 and Figs. 58-59, wherein Fig. 58 is the electroluminescence diagram of device examples 10-13 based on compound Pd-49 of the present application, Fig. 59 is the electroluminescence quantum efficiency diagram of device examples 10-13 based on metal palladium complex Pd-49 of the present application.

[0352] Table 3 Device performance test results

[0353] [a] maximum brightness; [b] current efficiency; [c] luminous efficiency; [d] external quantum efficiency;

[0354] As shown in Figs. 58-59, the organic electroluminescence device prepared by the present application with metal palladium complex Pd-49 as the guest material and at a doping concentration of 1% has a maximum luminous brightness of 119062 cd m-2, a maximum current efficiency of 75.1 cd A-1, a maximum luminous efficiency of 71.5 lm W-1, and a maximum external quantum efficiency of up to 24.3%.

[0355] Test Example 5

[0356] The provided organic electroluminescence devices in device examples 14-17 were tested, the guest material was selected as metal palladium complex Pd-79, the current-brightness-voltage characteristics of the devices were determined by Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with corrected silicon photodiode, all tests were completed in room temperature atmosphere, the test results are shown in Table 4 and Figs. 60-61, wherein Fig. 60 is the electroluminescence diagram of device examples 14-17 based on compound Pd-79 of the present application, Fig. 61 is the electroluminescence quantum efficiency diagram of device examples 14-17 based on metal palladium complex Pd-79 of the present application.

[0357] Table 4 Device performance test results

[0358] [a] maximum brightness; [b] current efficiency; [c] luminous efficiency; [d] external quantum efficiency;

[0359] As shown in FIGS. 60-61, the present application takes Pd-79 as the guest material, and the maximum luminous brightness can reach 84076 cd m -2 , the maximum current efficiency is 77.8 cd A -1 , the maximum luminous efficiency is 79.9 lm W -1 , and the maximum external quantum efficiency is 24.0%.

[0360] Test Example 6

[0361] The provided organic electroluminescent device in device example 16 was subjected to stability test, the guest material was selected to be metal palladium complex Pd-79, encapsulated by glass cover in nitrogen-filled glove box by ultraviolet light curing adhesive, then taken out from the glove box and used OLED lifetime test system (FS-MP64, Suzhou FSTAR Scientific Instrument Co., Ltd., China) to measure the brightness of the working device under constant current density, and all tests were completed in room temperature atmosphere. As shown in FIG. 62, the organic electroluminescent device prepared by taking metal palladium complex Pd-79 as the guest material and with a doping concentration of 9% has an initial brightness of 1000 cd m -2 , the LT 95 (LT 95 defined as the time used for 5% luminance decay) is 35 hours, and the initial brightness of 100 cd m -2 , the LT 95 (LT 95 defined as the time used for 5% luminance decay) is 1751 hours.

[0362] Test Example 7

[0363] The provided organic electroluminescent device in device examples 18-21 was subjected to test, the guest material was selected to be metal palladium complex Pd-139, the current-brightness-voltage characteristics of the device were determined by Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with corrected silicon photodiode, and all tests were completed in room temperature atmosphere, and the test results are shown in Table 5 and FIGS. 63-64, wherein FIG. 63 is the electroluminescence diagram of device examples 18-21 of the present application based on metal palladium complex Pd-139, and FIG. 64 is the electroluminescence quantum efficiency diagram of device examples 18-21 of the present application based on metal palladium complex Pd-139.

[0364] Table 5 Device performance test results

[0365] [a] maximum brightness; [b] current efficiency; [c] luminous efficiency; [d] external quantum efficiency;

[0366] [a] maximum brightness; [b] current efficiency; [c] luminous efficiency; [d] external quantum efficiency;

[0367] As shown in Figs. 63-64, the organic electroluminescent device of the present application with metal palladium complex Pd-139 as guest material and prepared at a doping concentration of 6% has a maximum luminous brightness of 131504 cd m-2, a maximum current efficiency of 76.1 cd A-1, a maximum luminous efficiency of 83.1 lm W-1, and a maximum external quantum efficiency of up to 25.1%.

[0368] Obviously, the above embodiments are merely exemplary but not limiting to the present application. Based on the above description, other different forms of changes or modifications can be made by those skilled in the art. Here, it is not necessary or possible to enumerate all the embodiments. The obvious changes or modifications derived therefrom are still within the protection scope of the present application.

Claims

1. A metal palladium complex characterized in that, having the structure shown below: wherein W1is selected from C 1-10 alkyl, C 6-12 aryl; R1, R2are each independently selected from the group consisting of H, halogen, C 1-10 alkyl, C 2-6 alkenyl, C 3-20 aryl, C 3-20 heteroaryl; D is an electron donating group; A is selected from H, halogen, C 1-10 alkyl, C 1-10 alkoxy, C 2-6 alkenyl, C 3-20 aryl, C 3-20 heteroaryl; X1is selected from N or C-T1; X2is selected from N or C-T2; wherein T1, T2are each independently selected from the group consisting of H, halogen, C 1-10 alkyl, C 2-6 alkenyl, C 3-20 aryl, C 3-20 heteroaryl; When X 1、 When C-T1 and X2 is C-T2, A, T1, and T2 are not simultaneously H.

2. The metal palladium complex of claim 1, wherein W1is selected from C 1-3 alkyl, C 6-12 aryl; W1is selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, phenyl, naphthyl, biphenyl.

3. The metal palladium complex according to claim 1 or 2, characterized in that, R1, R2are each independently selected from the group consisting of H, halogen, C 1-6 alkyl, C 2-6 alkenyl, C 6-20 aryl, C 6-20 heteroaryl; Preferably, R1, R2are each independently selected from H, halogen, methyl, ethyl, propyl, i-propyl, n-butyl, phenyl, naphthyl, biphenyl, vinyl, propenyl; Preferably, R1, R2 are each present independently, or R1, R2 are bonded to form a C 3-20 aromatic ring; Preferably, R1, R2 are each present independently, or R1, R2 are bonded to form a C 6-20 aromatic ring; Preferably, R1, R2are each independently present, or R1, R2are bonded to form a benzene ring.

4. The metal palladium complex according to any one of claims 1 to 3, characterized in that, D is selected from one of the following groups:

5. The metal palladium complex according to any one of claims 1 to 4, characterized in that, A is selected from H, C 1-6 alkyl, C 1-6 alkoxy, C 2-6 alkenyl, C 6-20 aryl, C 6-20 heteroaryl; Preferably, A is selected from H, cyano, trihalomethyl, halogen, t-butyl, methyl, methoxy, nitro, carboxyl.

6. The metal palladium complex according to any one of claims 1 to 5, characterized in that, X1is selected from N or C-T1; X2is selected from N or C-T2; wherein T1, T2are each independently selected from the group consisting of H, halogen, C 1-6 alkyl, C 2-6 alkenyl, C 6-20 aryl, C 6-20 heteroaryl; Preferably, T1, T2are each independently selected from H, halogen, methyl, t-butyl, cyano, trihalomethyl.

7. The metal palladium complex according to any one of claims 1 to 6, characterized in that, The metal palladium complex has any one of the following structures:

8. An organic electroluminescent device, characterized by The organic electroluminescent device comprises a first electrode, a second electrode and a light-emitting layer between the first electrode and the second electrode, and the light-emitting layer comprises any one or a combination of at least two of the metal palladium complexes according to any one of claims 1-7.

9. The organic electroluminescent device according to claim 8, characterized in that The light-emitting layer comprises the metal palladium complex according to any one of claims 1-7 and an organic functional material, and the mass percentage of the metal palladium complex is 0.01%-100% and the mass percentage of the organic functional material is 0-99.9%.

10. Use of the organic electroluminescent device according to claim 8 or 9 in an electronic device.

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