CN107573386A - Complex of iridium containing thieno [2,3 d] pyrimidine group and the application in electroluminescent device - Google Patents

Abstract

The invention discloses an iridium complex containing a thieno[2,3-d]pyrimidine group and its application as a phosphorescent guest material in an organic electroluminescence device. The main ligands in this series of iridium complex molecules are derivatives containing thieno[2,3-d]pyrimidine heterocycles. Auxiliary ligands are acetylacetone, tetramethylheptanedione or 2-picolinic acid. Such iridium complexes not only have the characteristics of high luminous efficiency, stable chemical properties and easy purification, but also exhibit excellent luminous efficiency, electron mobility and stability when used as phosphorescent guest materials in organic electroluminescent devices. Through the modification of the main ligand, the luminescence wavelength and efficiency of the complex can be adjusted in the visible light band.

Description

Iridium complexes containing thieno[2,3-d]pyrimidine groups and their use in electroluminescent devices Applications

technical field

The invention belongs to the application field of metal organic phosphorescent materials and organic electroluminescence. In particular, it relates to a phosphorescent iridium complex based on a thieno[2,3-d]pyrimidine heterocycle, a preparation method thereof, and an application of the complex as a phosphorescent guest material in an organic electroluminescent device.

Background technique

Organic Light-Emitting Diodes (OLEDs) have attracted extensive attention from academia and industry due to their advantages such as high brightness, wide viewing angle, fast response speed, low driving voltage, and can be used in the preparation of large-area flexible displays. It shows great potential in the new generation of flat panel display and solid state lighting.

According to different luminescent principles, organic electroluminescent materials can be divided into two categories: fluorescent materials based on singlet exciton emission and phosphorescent materials based on triplet exciton emission. During organic electroluminescence, singlet and triplet excitons are generated simultaneously. According to the spin quantum statistical theory, the generation probability ratio of singlet excitons and triplet excitons is 1:3. For ordinary organic electroluminescent materials, only singlet excitons can be used to emit light, and triplet excitons are mainly lost through non-radiative transitions. Therefore, devices based on ordinary fluorescent materials have a maximum internal quantum efficiency of 25%. However, in heavy metal complexes of phosphorescent materials, due to the introduction of heavy metal atoms, a strong spin-orbit coupling occurs between the metal and the ligand, so that the excited triplet state has some singlet characteristics, so the phosphorescent material can be used at the same time Singlet and triplet excitons can theoretically make the internal quantum efficiency of the device reach 100%. Therefore, heavy metal complexes are widely used in the preparation of high-efficiency organic electroluminescent devices. Among them, the iridium complex is particularly important because it has a suitable triplet lifetime and high luminous efficiency, and can realize different wavelengths of luminescence by adjusting the first and second ligands.

Phosphorescent materials used as electroluminescent devices generally have long excited state lifetimes and thus severe triplet-triplet quenching. The maximum efficiency of the device usually appears at low current density. As the current density increases, the efficiency and brightness will decrease, which limits the application of phosphorescent materials in organic electroluminescent devices. Therefore, it is of great significance to develop phosphorescent materials with both high external quantum efficiency and low efficiency attenuation.

The object of the present invention is to provide a class of phosphorescent iridium complexes with high luminous efficiency. These phosphorescent complexes are used in the preparation of organic electroluminescent devices to improve device efficiency and reduce device decay rate.

Contents of the invention

The object of the present invention is to provide a class of phosphorescent iridium complexes with high luminous efficiency.

A second object of the present invention is to provide a method for the preparation of such complexes.

The third object of the present invention is to use this type of phosphorescent material in organic electroluminescent devices to solve the problems of low efficiency and fast roll-off of existing electroluminescent device materials.

Technical scheme of the present invention is as follows:

A new class of metal iridium complexes, with thieno[2,3-d]pyrimidine heterocyclic derivatives as the main ligand, acetylacetone (acac), tetramethylheptanedione (tmd) or 2-pyridinecarboxylic acid ( pic) is an auxiliary ligand, and its structure is shown in the following formula:

In the formula, L is selected from the following groups:

In the formula, Ar is selected from the following groups:

Wherein, R ₁ , R ₂ , R ₃ and R ₄ are independently selected from the following groups:

-H, -NH ₂ , -OCH ₃ , -CH ₃ , -C(CH ₃ ) ₃ , -CN, -F, -CF ₃ .

As some examples, the iridium complex has one of the following structures:

The method for preparing described phosphorescent iridium complex, comprises the steps:

(1) Under argon protection, add 4-chlorothieno[2,3-d]pyrimidine and a slight excess of boronic acid A to 1,4-dioxane, in Pd(dppf)Cl ₂ catalyst and 2M K The Suzuki coupling reaction was carried out under the action of ₂ CO ₃ (aq), and the ligand B based on the thiophene[2,3-d]pyrimidine heterocycle was obtained after separation and purification.

The structural formula of boric acid A is:

XB(OH) ₂ ;

The structural formula of Ligand B is:

In the formula, X is selected from the following groups:

Wherein, R ₁ , R ₂ , R ₃ and R ₄ are independently selected from the following groups:

-H, -NH ₂ , -OCH ₃ , -CH ₃ , -C(CH ₃ ) ₃ , -CN, -F, -CF ₃ .

The reaction formula is as follows:

(2) Under the protection of argon, dissolve iridium trichloride trihydrate with a molar ratio of 1:2.5 and the above-mentioned ligand B in a mixed solvent of ethylene glycol ether and distilled water, and react at 120°C for 24 hours to obtain a chlorine bridge dimer intermediate. Without further purification, the chlorine bridge dimer intermediate and acetylacetone, tetramethylheptanedione or 2-pyridinecarboxylic acid were dissolved in ethylene glycol ether, anhydrous sodium carbonate was added, and the reaction was carried out at 80°C for 12 hours. The target phosphorescent iridium complex was obtained by separation and purification.

The reaction formula is as follows:

The present invention also provides an electrophosphorescent light-emitting device, comprising a conductive glass substrate layer, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode layer; the light-emitting material of the light-emitting layer is the phosphorescent iridium complexes.

The phosphorescent guest material of the invention is applied to an electrophosphorescent device, and can obtain high-efficiency electroluminescence performance. The invention uses Ir-acac-01 as the object to prepare the orange photoelectric phosphorescent device, the maximum luminous efficiency can reach 67.8 cantera per ampere, the maximum lumen efficiency is 64.4 lumens per watt, the maximum external quantum efficiency is 24.5%, and at the same time, the Under the cantera per square meter, the device still maintains extremely high stability, and the external quantum efficiency remains at 24.3%. The invention uses Ir-tmd-22 as the object to prepare the orange photoelectric phosphorescent device, the maximum luminous efficiency can reach 30.2 cantera per ampere, the maximum lumen efficiency is 36.4 lumen per watt, the maximum external quantum efficiency is 19.8%, and at the same time at 1000 Under the cantera per square meter, the device still maintains extremely high stability, and the external quantum efficiency remains at 19.2%. The green photoelectric phosphorescent device prepared with Ir-pic-42 as the object of the present invention has a maximum luminous efficiency of 92.6 cantera per ampere, a maximum lumen efficiency of 99.8 lumen per watt, a maximum external quantum efficiency of 26.8%, and a maximum of 1000 Under the cantera per square meter, the device still maintains extremely high stability, and the external quantum efficiency remains at 25.4%. It can be seen that the present invention has beneficial technical effects.

Description of drawings

FIG. 1 is a schematic structural view of an organic electroluminescent device according to an embodiment.

Fig. 2 is the electroluminescent spectrum of the phosphorescent iridium complex Ir-acac-01 of Example 28.

FIG. 3 is an electroluminescence spectrum diagram of the phosphorescent iridium complex Ir-tmd-22 of Example 30. FIG.

FIG. 4 is an electroluminescence spectrum diagram of the phosphorescent iridium complex Ir-pic-42 of Example 32. FIG.

detailed description

The invention provides a phosphorescent organic compound and its application in organic electrophosphorescent light-emitting devices. The present invention is described in further detail below through specific examples, and its purpose is to help better understanding content, purpose, technical scheme and effect of the present invention, the raw material used in this embodiment is known compound, can be purchased on the market, several A typical phosphorescent guest molecule can be synthesized by the following method:

Embodiment 1: the preparation of compound Ir-acac-01

Synthesis of methyl 2-aminothiophene-3-carboxylate (abbreviated as intermediate 1)

In a 250 mL round bottom flask were added 1,4-dithio-2,5-diol (7.6 g, 50 mmol), methyl cyanoacetate (9.9 g, 100 mmol) and 20 mL of DMF, and the mixture was stirred at 0°C. Triethylamine (3.6g, 50mmol) was gradually added dropwise to the reaction system, and stirred at room temperature for 3h. It was quenched with water, extracted with dichloromethane, and the solvent was removed by a rotary evaporator. Purify and separate by column chromatography. A white solid (11 g, 64%) was obtained.

Synthesis of Thiopheno[2,3-d]pyrimidin-4-ol (Intermediate 2 for short)

Added methyl 2-aminothiophene-3-carboxylate (4.7g, 30mmol), ammonium formate (6.3g, 100mmol) and 25mL formamide into a 250mL round bottom flask, and heated and stirred the mixture at 150°C for 6h. After the reaction was completed, it was stored at 0°C for 24 h, and filtered with suction to obtain a brown solid (2.8 g, 58%).

Synthesis of 4-Chlorothieno[2,3-d]pyrimidine (Intermediate 3 for short)

Thiopheno[2,3-d]pyrimidin-4-ol (10.0 g, 66 mmol) and 100 mL of 1,4-dioxane were added to a 250 mL round bottom flask, and the mixture was stirred at 0°C. Phosphorus oxychloride (20 mL, 212 mmol) was gradually added dropwise to the reaction system, and the mixture was heated and stirred at 90° C. for 3 h. After cooling to room temperature, the reaction was quenched with aqueous sodium hydroxide solution, extracted with dichloromethane, and the solvent was removed by a rotary evaporator. Purify and separate by column chromatography. A white solid (9.1 g, 60%) was obtained.

Synthesis of 4-phenylthiophene[2,3-d]pyrimidine (Ligand L-01 for short)

Under argon protection, phenylboronic acid (4.3g, 35mmol), 4-chlorothieno[2,3-d]pyrimidine (5.1g, 30mmol), Pd(dppf)Cl ₂ (440mg, 0.6 mmol), K ₂ CO ₃ (5.5g, 40mmol), 60mL 1,4-dioxane and 20mL water, the mixture was heated and stirred at 90°C for 6h. Cool to room temperature, quench with water, extract with dichloromethane, and remove the solvent with a rotary evaporator. Purify and separate by column chromatography. A white solid (4.6 g, 72%) was obtained.

Synthesis of Target Molecule Ir-acac-01

Under argon protection, ligand L-01 (530mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round bottom flask were added the intermediate of chlorine bridged polymer (342mg, 0.4mmol), acetylacetone (200mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (223 mg, 31%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 714.04[M ⁺ ]

Elemental analysis: C ₂₉ H ₂₁ IrN ₄ O ₂ S ₂

Theoretical value (%): C 48.79, H 2.97, N 7.85

Actual value (%): C 48.41, H 2.38, N 7.46

Embodiment 2: the preparation of compound Ir-acac-04

Synthesis of 4-(4-methoxyphenyl)thiophene[2,3-d]pyrimidine (Ligand L-04 for short)

Under argon protection, 4-methoxyphenylboronic acid (5.3g, 35mmol), 4-chlorothiophene[2,3-d]pyrimidine (5.1g, 30mmol), Pd(dppf)Cl were added to a 250mL round bottom flask. ₂ (440mg, 0.6mmol), K ₂ CO ₃ (5.5g, 40mmol), 60mL 1,4-dioxane and 20mL water, the mixture was heated and stirred at 90°C for 6h. Cool to room temperature, quench with water, extract with dichloromethane, and remove the solvent with a rotary evaporator. Purify and separate by column chromatography. A white solid (5.4 g, 74%) was obtained.

Synthesis of Target Molecule Ir-acac-04

Under argon protection, ligand L-04 (605mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100 mL round-bottomed flask were added the chlorobridged polymer intermediate (412 mg, 0.4 mmol), tetramethylheptanedione (246 mg, 2 mmol), anhydrous sodium carbonate (210 mg, 2 mmol) and 10 mL of ethyl glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (248 mg, 32%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 774.15[M ⁺ ]

Elemental analysis: C ₃₁ H ₂₅ IrN ₄ O ₂ S ₂

Theoretical value (%): C 48.11, H 3.26, N 7.24

Actual value (%): C 48.05, H 3.28, N 7.33

Embodiment 3: the preparation of compound Ir-acac-06

Synthesis of 4-(4-methylphenyl)thiophene[2,3-d]pyrimidine (Ligand L-06 for short)

Under argon protection, add 4-methylphenylboronic acid (4.8g, 35mmol), 4-chlorothiophene[2,3-d]pyrimidine (5.1g, 30mmol), Pd(dppf)Cl ₂ into a 250mL round bottom flask (440mg, 0.6mmol), K ₂ CO ₃ (5.5g, 40mmol), 60mL 1,4-dioxane and 20mL water, the mixture was heated and stirred at 90°C for 6h. Cool to room temperature, quench with water, extract with dichloromethane, and remove the solvent with a rotary evaporator. Purify and separate by column chromatography. A white solid (4.5 g, 72%) was obtained.

Synthesis of Target Molecule Ir-acac-06

Under argon protection, ligand L-06 (560mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round bottom flask were added the chlorine-bridged intermediate (369mg, 0.4mmol), acetylacetone (200mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (222 mg, 30%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 742.05[M ⁺ ]

Elemental analysis: C ₃₁ H ₂₅ IrN ₄ O ₂ S ₂

Theoretical value (%): C 50.19, H 3.40, N 7.55

Actual value (%): C 50.15, H 3.42, N 7.48

Embodiment 4: the preparation of compound Ir-acac-09

Synthesis of 4-(4-cyanophenyl)thiophene[2,3-d]pyrimidine (Ligand L-09 for short)

Under the protection of argon, add 4-cyanophenylboronic acid (5.2g, 35mmol), 4-chlorothiophene[2,3-d]pyrimidine (5.1g, 30mmol) into a 250mL round bottom flask, Pd(dppf)Cl ₂ (440mg, 0.6mmol), K ₂ CO ₃ (5.5g, 40mmol), 60mL 1,4-dioxane and 20mL water, the mixture was heated and stirred at 90°C for 6h. Cool to room temperature, quench with water, extract with dichloromethane, and remove the solvent with a rotary evaporator. Purify and separate by column chromatography. A white solid (4.8 g, 68%) was obtained.

Synthesis of Target Molecule Ir-acac-09

Under argon protection, ligand L-09 (593mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round bottom flask were added chlorine-bridged intermediate (382mg, 0.4mmol), acetylacetone (200mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (267 mg, 35%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 764.06[M ⁺ ]

Elemental analysis: C ₃₁ H ₁₉ IrN ₆ O ₂ S ₂

Theoretical value (%): C 48.74, H 2.51, N 11.00

Actual value (%): C 48.68, H 2.53, N 11.02

Embodiment 5: the preparation of compound Ir-acac-12

Synthesis of 4-(2,4-difluorophenyl)thiophene[2,3-d]pyrimidine (Ligand L-12 for short)

Under argon protection, 2,4-difluorophenylboronic acid (5.9g, 35mmol), 4-chlorothieno[2,3-d]pyrimidine (5.1g, 30mmol), Pd(dppf) were added to a 250mL round bottom flask Cl ₂ (440mg, 0.6mmol), K ₂ CO ₃ (5.5g, 40mmol), 60mL 1,4-dioxane and 20mL water, the mixture was heated and stirred at 90°C for 6h. Cool to room temperature, quench with water, extract with dichloromethane, and remove the solvent with a rotary evaporator. Purify and separate by column chromatography. A white solid (6.1 g, 82%) was obtained.

Synthesis of Target Molecule Ir-acac-12

Under argon protection, ligand L-12 (620mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round bottom flask were added the intermediate of chlorine bridged polymer (397mg, 0.4mmol), acetylacetone (200mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (282 mg, 36%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 786.04[M ⁺ ]

Elemental analysis: C ₂₉ H ₁₇ IrN ₄ O ₂ S ₂

Theoretical value (%): C 44.33, H 2.18, N 7.13

Actual value (%): C 44.28, H 2.15, N 7.18

Embodiment 6: the preparation of compound Ir-acac-15

Synthesis of 4-(2,4-bistrifluoromethylphenyl)thiophene[2,3-d]pyrimidine (Ligand L-15 for short)

Under argon protection, 2,4-ditrifluoromethylphenylboronic acid (9.0g, 35mmol), 4-chlorothiophene[2,3-d]pyrimidine (5.1g, 30mmol), Pd (dppf)Cl ₂ (440mg, 0.6mmol), K ₂ CO ₃ (5.5g, 40mmol), 60mL 1,4-dioxane and 20mL water, the mixture was heated and stirred at 90°C for 6h. Cool to room temperature, quench with water, extract with dichloromethane, and remove the solvent with a rotary evaporator. Purify and separate by column chromatography. A white solid (8.6 g, 83%) was obtained.

Synthesis of Target Molecule Ir-acac-15

Under argon protection, ligand L-15 (870mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round bottom flask were added the intermediate of chlorine bridged polymer (415mg, 0.4mmol), acetylacetone (200mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (325 mg, 33%) was obtained.

Structure Identification:

Mass Spectrum (EI,m/z)986.02[M ⁺ ]

Elemental analysis: C ₃₃ H ₁₇ F ₁₂ IrN ₄ O ₂ S ₂

Theoretical value (%): C 40.21, H 1.74, N 5.68

Actual value (%): C 40.25, H 1.82, N 5.63

Embodiment 7: the preparation of compound Ir-tmd-16

Under argon protection, ligand L-16 (530mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round-bottomed flask were added the chlorobridged polymer intermediate (402mg, 0.4mmol), tetramethylheptanedione (246mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (255 mg, 32%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 798.17[M ⁺ ]

Elemental analysis: C ₃₅ H ₃₃ IrN ₄ O ₂ S ₂

Theoretical value (%): C 52.68, H 4.17, N 7.02

Actual value (%): C 52.61, H 4.19, N 6.95

Embodiment 8: the preparation of compound Ir-tmd-19

Under argon protection, ligand L-19 (605mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round-bottomed flask were added the intermediate of chlorine-bridged polymer (416mg, 0.4mmol), tetramethylheptanedione (246mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL of ethyl glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (308 mg, 36%) was obtained.

Structure Identification:

Mass Spectrum (EI,m/z)858.19[M ⁺ ]

Elemental analysis: C ₃₇ H ₃₇ IrN ₄ O ₄ S ₂

Theoretical value (%): C 51.79, H 4.35, N 6.53

Actual value (%): C 51.85, H 4.42, N 6.48

Embodiment 9: the preparation of compound Ir-tmd-21

Under argon protection, ligand L-21 (510mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round-bottomed flask were added the intermediate of chlorine-bridged polymer (416mg, 0.4mmol), tetramethylheptanedione (246mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL of ethyl glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (308 mg, 36%) was obtained.

Structure Identification:

Mass Spectrum (EI,m/z)841.22[M ⁺ ]

Elemental analysis: C ₃₈ H ₄₀ IrN ₄ O ₂ S ₂

Theoretical value (%): C 54.26, H 4.79, N 6.66

Actual value (%): C 54.31, H 4.75, N 6.49

Embodiment 10: the preparation of compound Ir-tmd-24

Under argon protection, ligand L-24 (592mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round-bottomed flask were added the chlorobridged polymer intermediate (416mg, 0.4mmol), tetramethylheptanedione (246mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (271 mg, 32%) was obtained.

Structure Identification:

Mass Spectrum (EI,m/z)848.17[M ⁺ ]

Elemental analysis: C ₃₇ H ₃₁ IrN ₆ O ₂ S ₂

Theoretical value (%): C 52.40, H 3.68, N 9.91

Actual value (%): C 52.45, H 3.72, N 9.85

Embodiment 11: Preparation of compound Ir-tmd-27

Under argon protection, ligand L-27 (620mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round-bottomed flask were added the chlorobridged polymer intermediate (450mg, 0.4mmol), tetramethylheptanedione (246mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (321 mg, 37%) was obtained.

Structure Identification:

Mass Spectrum (EI,m/z)870.15[M ⁺ ]

Elemental analysis: C ₃₅ H ₂₉ F ₄ IrN ₄ O ₂ S ₂

Theoretical value (%): C 48.32, H 3.36, N 6.44

Actual value (%): C 48.39, H 3.31, N 6.45

Embodiment 12: the preparation of compound Ir-tmd-30

Under argon protection, ligand L-30 (678mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100 mL round-bottomed flask were added the chlorobridged polymer intermediate (569 mg, 0.4 mmol), tetramethylheptanedione (246 mg, 2 mmol), anhydrous sodium carbonate (210 mg, 2 mmol) and 10 mL of ethyl glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (385 mg, 37%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 1070.15[M ⁺ ]

Elemental analysis: C ₃₉ H ₂₉ F ₁₂ IrN ₄ O ₂ S ₂

Theoretical value (%): C 43.78, H 2.73, N 5.24

Actual value (%): C 43.73, H 2.71, N 5.21

Example 13: Preparation of compound Ir-pic-31

Under argon protection, ligand L-31 (530mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100 mL round-bottomed flask were added the chlorine-bridged polymer intermediate (447 mg, 0.4 mmol), 2-pyridinecarboxylic acid (368 mg, 2 mmol), anhydrous sodium carbonate (210 mg, 2 mmol) and 10 mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (309 mg, 42%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 736.98[M ⁺ ]

Elemental analysis: C ₃₀ H ₁₈ IrN ₅ O ₂ S ₂

Theoretical value (%): C 48.90, H 2.46, N 9.50

Actual value (%): C 48.95, H 2.41, N 9.46

Example 14: Preparation of compound Ir-pic-34

Under argon protection, ligand L-34 (605mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100 mL round-bottom flask were added the chlorine-bridged polymer intermediate (512 mg, 0.4 mmol), 2-pyridinecarboxylic acid (368 mg, 2 mmol), anhydrous sodium carbonate (210 mg, 2 mmol) and 10 mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (358 mg, 45%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 797.05[M ⁺ ]

Elemental analysis: C ₃₂ H ₂₂ IrN ₅ O ₄ S ₂

Theoretical value (%): C 48.23, H 2.78, N 8.79

Actual value (%): C 48.19, H 2.71, N 8.75

Example 15: Preparation of compound Ir-pic-36

Under argon protection, ligand L-36 (565mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100 mL round-bottomed flask were added the chlorine-bridged polymer intermediate (475 mg, 0.4 mmol), 2-pyridinecarboxylic acid (368 mg, 2 mmol), anhydrous sodium carbonate (210 mg, 2 mmol) and 10 mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (320 mg, 41%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 781.15[M ⁺ ]

Elemental analysis: C ₃₃ H ₂₆ IrN ₅ O ₂ S ₂

Theoretical value (%): C 50.75, H 3.36, N 8.97

Actual value (%): C 50.67, H 3.41, N 8.95

Example 16: Preparation of compound Ir-pic-39

Under argon protection, ligand L-39 (592mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100 mL round-bottomed flask were added the chlorine-bridged polymer intermediate (488 mg, 0.4 mmol), 2-pyridinecarboxylic acid (368 mg, 2 mmol), anhydrous sodium carbonate (210 mg, 2 mmol) and 10 mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (370 mg, 47%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 787.01[M ⁺ ]

Elemental analysis: C ₃₂ H ₁₆ IrN ₇ O ₂ S ₂

Theoretical value (%): C 48.85, H 2.05, N 12.46

Actual value (%): C 48.81, H 2.08, N 12.44

Example 17: Preparation of compound Ir-pic-42

Under argon protection, ligand L-42 (600mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100 mL round-bottomed flask were added the chlorine-bridged polymer intermediate (460 mg, 0.4 mmol), 2-pyridinecarboxylic acid (368 mg, 2 mmol), anhydrous sodium carbonate (210 mg, 2 mmol) and 10 mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (223 mg, 30%) was obtained.

Structure Identification:

Mass Spectrum (EI,m/z)824.02[M ⁺ ]

Elemental analysis: C ₃₁ H ₁₇ F ₄ IrN ₅ O ₂ S ₂

Theoretical value (%): C 45.20, H 2.08, N 9.22

Actual value (%): C 45.48, H 2.25, N 9.14

Example 18: Preparation of compound Ir-pic-45

Under argon protection, ligand L-45 (870mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100 mL round-bottomed flask were added the chlorine-bridged polymer intermediate (610 mg, 0.4 mmol), 2-pyridinecarboxylic acid (368 mg, 2 mmol), anhydrous sodium carbonate (210 mg, 2 mmol) and 10 mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (464 mg, 46%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 1009.00[M ⁺ ]

Elemental analysis: C ₃₄ H ₁₄ F ₁₂ IrN ₅ O ₂ S ₂

Theoretical value (%): C 40.48, H 1.40, N 6.94

Actual value (%): C 40.45, H 1.38, N 6.99

Example 19: Preparation of Compound Ir-acac-47

Synthesis of 4-(4-pyridine)thiophene[2,3-d]pyrimidine (Ligand L-47 for short)

Under argon protection, 4-pyridineboronic acid (4.3g, 35mmol), 4-chlorothieno[2,3-d]pyrimidine (5.1g, 30mmol), Pd(dppf)Cl ₂ (440mg , 0.6mmol), K ₂ CO ₃ (5.5g, 40mmol), 60mL 1,4-dioxane and 20mL water, the mixture was heated and stirred at 90°C for 6h. Cool to room temperature, quench with water, extract with dichloromethane, and remove the solvent with a rotary evaporator. Purify and separate by column chromatography. A white solid (4.6 g, 72%) was obtained.

Synthesis of Target Molecule Ir-acac-47

Under argon protection, ligand L-47 (532mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round bottom flask were added chlorine bridged intermediate (366mg, 0.4mmol), acetylacetone (200mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (344mg, 48%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 716.03[M ⁺ ]

Elemental analysis: C ₂₇ H ₁₉ IrN ₆ O ₂ S ₂

Theoretical value (%): C 45.30, H 2.68, N 11.74

Actual value (%): C 45.26, H 2.61, N 11.69

Example 20: Preparation of Compound Ir-acac-49

Synthesis of 4-(2-naphthyl)thiophene[2,3-d]pyrimidine (Ligand L-49 for short)

Under argon protection, 4-naphthylboronic acid (6.0g, 35mmol), 4-chlorothiophene[2,3-d]pyrimidine (5.1g, 30mmol), Pd(dppf)Cl ₂ ( 440mg, 0.6mmol), K ₂ CO ₃ (5.5g, 40mmol), 60mL 1,4-dioxane and 20mL water, the mixture was heated and stirred at 90°C for 6h. Cool to room temperature, quench with water, extract with dichloromethane, and remove the solvent with a rotary evaporator. Purify and separate by column chromatography. A white solid (5.9 g, 75%) was obtained.

Synthesis of Target Molecule Ir-acac-49

Under argon protection, ligand L-49 (655mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round bottom flask were added the intermediate of chlorine bridged polymer (374mg, 0.4mmol), acetylacetone (200mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (333 mg, 41%) was obtained.

Structure Identification:

Mass Spectrum (EI,m/z)814.05[M ⁺ ]

Elemental analysis: C ₃₇ H ₂₅ IrN ₄ O ₂ S ₂

Theoretical value (%): C 54.60, H 3.10, N 6.88

Actual value (%): C 54.57, H 3.05, N 6.83

Example 21: Preparation of Compound Ir-acac-50

Synthesis of 4-(2-furyl)thiophene[2,3-d]pyrimidine (Ligand L-50 for short)

Under argon protection, 2-furan boronic acid (3.9g, 35mmol), 4-chlorothiophene[2,3-d]pyrimidine (5.1g, 30mmol), Pd(dppf)Cl ₂ (440mg , 0.6mmol), K ₂ CO ₃ (5.5g, 40mmol), 60mL 1,4-dioxane and 20mL water, the mixture was heated and stirred at 90°C for 6h. Cool to room temperature, quench with water, extract with dichloromethane, and remove the solvent with a rotary evaporator. Purify and separate by column chromatography. A white solid (4.5 g, 75%) was obtained.

Synthesis of Target Molecule Ir-acac-50

Under argon protection, ligand L-50 (505mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round bottom flask were added chlorine-bridged polymer intermediate (356mg, 0.4mmol), acetylacetone (200mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (326 mg, 47%) was obtained.

Structure Identification:

Mass Spectrum (EI,m/z)694.01[M ⁺ ]

Elemental analysis: C ₂₅ H ₁₇ IrN ₄ O ₄ S ₂

Theoretical value (%): C 43.28, H 2.47, N 8.08

Actual value (%): C 43.25, H 2.55, N 8.17

Example 22: Preparation of compound Ir-tmd-55

Under argon protection, ligand L-55 (532mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100mL round-bottomed flask were added the intermediate of chlorine-bridged polymer (416mg, 0.4mmol), tetramethylheptanedione (246mg, 2mmol), anhydrous sodium carbonate (210mg, 2mmol) and 10mL of ethyl glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (256 mg, 32%) was obtained.

Structure Identification:

Mass Spectrum (EI,m/z)800.12[M ⁺ ]

Elemental analysis: C ₃₃ H ₃₁ IrN ₆ O ₂ S ₂

Theoretical value (%): C 49.55, H 3.91, N 10.51

Actual value (%): C 49.52, H 3.93, N 10.48

Embodiment 23: Preparation of Compound Ir-tmd-57

Under argon protection, ligand L-57 (655mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100 mL round-bottomed flask were added the chlorobridged polymer intermediate (587 mg, 0.4 mmol), tetramethylheptanedione (246 mg, 2 mmol), anhydrous sodium carbonate (210 mg, 2 mmol) and 10 mL of ethyl glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (341 mg, 38%) was obtained.

Structure Identification:

Mass Spectrum (EI,m/z)898.15[M ⁺ ]

Elemental analysis: C ₄₃ H ₃₇ IrN ₄ O ₂ S ₂

Theoretical value (%): C 57.51, H 4.15, N 6.24

Actual value (%): C 57.44, H 4.12, N 6.33

Example 24: Preparation of compound Ir-tmd-58

Under argon protection, ligand L-58 (505mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100 mL round-bottomed flask were added the chlorobridged polymer intermediate (556 mg, 0.4 mmol), tetramethylheptanedione (246 mg, 2 mmol), anhydrous sodium carbonate (210 mg, 2 mmol) and 10 mL of ethyl glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (256 mg, 33%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 778.07[M ⁺ ]

Elemental analysis: C ₃₁ H ₂₉ IrN ₄ O ₄ S ₂

Theoretical value (%): C 47.86, H 3.76, N 7.20

Actual value (%): C 47.81, H 3.72, N 7.25

Example 25: Preparation of Compound Ir-pic-63

Under argon protection, ligand L-63 (592mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100 mL round-bottomed flask were added the chlorine-bridged polymer intermediate (488 mg, 0.4 mmol), 2-pyridinecarboxylic acid (368 mg, 2 mmol), anhydrous sodium carbonate (210 mg, 2 mmol) and 10 mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (273 mg, 37%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 739.02[M ⁺ ]

Elemental analysis: C ₂₈ H ₁₆ IrN ₇ O ₂ S ₂

Theoretical value (%): C 45.52, H 2.18, N 13.27

Actual value (%): C 45.55, H 2.12, N 13.25

Example 26: Preparation of Compound Ir-pic-65

Under argon protection, ligand L-65 (655mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100 mL round-bottomed flask were added the chlorine-bridged polymer intermediate (695 mg, 0.4 mmol), 2-pyridinecarboxylic acid (368 mg, 2 mmol), anhydrous sodium carbonate (210 mg, 2 mmol) and 10 mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (352 mg, 42%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 837.09[M ⁺ ]

Elemental analysis: C ₃₈ H ₂₂ IrN ₅ O ₂ S ₂

Theoretical value (%): C 54.53, H 2.65, N 8.37

Actual value (%): C 54.48, H 2.62, N 8.31

Example 27: Preparation of Compound Ir-pic-66

Under argon protection, ligand L-66 (505mg, 2.5mmol), iridium trichloride (three crystal water) (350mg, 1mmol), 15mL ethylene glycol ether and 5mL distilled water were added to a 100mL round bottom flask. The reaction was carried out at 120°C for 24h. After cooling to room temperature, pour into water. Filter the precipitate. Wash with water, ethanol and ether, respectively. Vacuum dry. Chlorine-bridged polymer intermediate was obtained as an orange solid. Without further purification, in a 100 mL round-bottomed flask were added the chlorine-bridged polymer intermediate (587 mg, 0.4 mmol), 2-pyridinecarboxylic acid (368 mg, 2 mmol), anhydrous sodium carbonate (210 mg, 2 mmol) and 10 mL of ethylene glycol ether. The reaction was carried out at 80° C. under an argon atmosphere for 12 hours. After cooling to room temperature, add water to quench, extract with dichloromethane, combine organic phases, dry over anhydrous sodium sulfate, and filter. Separation by silica gel column chromatography. An orange solid (322 mg, 45%) was obtained.

Structure Identification:

Mass Spectrum (EI, m/z) 717.05[M ⁺ ]

Elemental analysis: C ₂₆ H ₁₄ IrN ₅ O ₂ S ₂

Theoretical value (%): C 43.57, H 1.97, N 9.77

Actual value (%): C 43.52, H 1.93, N 9.72

Example 28: Preparation of phosphorescent organic electroluminescent device containing complex Ir-acac-01

The ITO glass was ultrasonically cleaned in detergent and deionized water for 30 minutes, dried in vacuum for 2 hours, and the ITO glass was treated with ozone plasma for 5 minutes, and then organic films and metal electrodes were prepared in a vacuum glove box. As shown in FIG. 1 , the phosphorescent material of the present invention is used as an electrophosphorescent device in a light-emitting layer. Can include glass and conductive glass (ITO) substrate layer 1, hole injection layer 2 (molybdenum trioxide MoO ₃ ), hole transport layer 3 (4,4'-cyclohexylbis[N,N-bis(4-methyl phenyl) aniline] TAPC), light emitting layer 4 (the mixture of phosphorescent guest material Ir-acac-01 of the present invention mixed with host material), electron transport layer 5 (4,7-diphenyl-1,10-phenanthrene phenoline Bphen), cathode layer 6 (lithium fluoride/aluminum LiF/Al).

The current-luminance-voltage characteristics of the device were completed by a Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with a calibrated silicon photodiode, and the electroluminescence spectrum was measured by a SPEX CCD3000 spectrometer from JY Company in France. All measurements All completed in room temperature atmosphere.

The device 1 (D1) structure is:

ITO/MoO ₃ (8nm)/TAPC(75nm)/NPB:Ir-acac-01(5wt%,12nm)/Bphen(70nm)/LiF(1nm)/Al(150nm)

The invention uses Ir-acac-01 as the object to prepare the orange photoelectric phosphorescent device, the maximum luminous efficiency can reach 67.8 cantera per ampere, the maximum lumen efficiency is 64.4 lumens per watt, the maximum external quantum efficiency is 24.5%, and at the same time, the Under the cantera per square meter, the device still maintains extremely high stability, and the external quantum efficiency remains at 24.3%.

Example 29: Preparation of phosphorescent organic electroluminescent device containing complex Ir-acac-06

Except that the phosphorescent guest material of the light-emitting layer was changed to Ir-acac-06, the same method as Example 28 was used to fabricate an organic electroluminescent device.

Device 2 (D2) structure:

ITO/MoO ₃ (8nm)/TAPC(75nm)/NPB:Ir-acac-06(5wt%,12nm)/Bphen(70nm)/LiF(1nm)/Al(150nm)

The invention uses Ir-acac-06 as the object to prepare the orange photoelectric phosphorescent device, the maximum luminous efficiency can reach 31.3 cantera per ampere, the maximum lumen efficiency is 37.8 lumens per watt, the maximum external quantum efficiency is 20.1%, and at the same time it can reach 1000 Under the cantera per square meter, the device still maintains extremely high stability, and the external quantum efficiency remains at 19.8%.

Example 30: Preparation of phosphorescent organic electroluminescent device containing complex Ir-tmd-22

Except that the phosphorescent guest material of the light-emitting layer was changed to Ir-tmd-22, the same method as Example 28 was used to fabricate an organic electroluminescent device.

Device 3 (D3) structure:

ITO/MoO ₃ (8nm)/TAPC(75nm)/NPB:Ir-tmd-22(5wt%,12nm)/Bphen(70nm)/LiF(1nm)/Al(150nm)

The invention uses Ir-tmd-22 as the object to prepare the orange photoelectric phosphorescent device, the maximum luminous efficiency can reach 30.2 cantera per ampere, the maximum lumen efficiency is 36.4 lumen per watt, the maximum external quantum efficiency is 19.8%, and at the same time at 1000 Under the cantera per square meter, the device still maintains extremely high stability, and the external quantum efficiency remains at 19.2%.

Example 31: Preparation of phosphorescent organic electroluminescent device containing complex Ir-tmd-30

Except that the phosphorescent guest material of the light-emitting layer was changed to Ir-tmd-30, the same method as Example 28 was used to fabricate an organic electroluminescent device.

Device 4 (D4) structure:

ITO/MoO ₃ (8nm)/TAPC(75nm)/NPB:Ir-tmd-30(5wt%,12nm)/Bphen(70nm)/LiF(1nm)/Al(150nm)

The invention uses Ir-tmd-30 as the object to prepare the orange photoelectric phosphorescent device, the maximum luminous efficiency can reach 34.1 cantera per ampere, the maximum lumen efficiency is 38.5 lumens per watt, the maximum external quantum efficiency is 24.2%, and at the same time, the Under the cantera per square meter, the device still maintains extremely high stability, and the external quantum efficiency remains at 22.3%.

Example 32: Preparation of phosphorescent organic electroluminescent device containing complex Ir-pic-42

Except that the phosphorescent guest material of the light-emitting layer was changed to Ir-pic-42, the same method as Example 28 was used to fabricate an organic electroluminescent device.

Device 5 (D5) structure:

ITO/MoO ₃ (8nm)/TAPC(75nm)/NPB:Ir-pic-42(5wt%,12nm)/Bphen(70nm)/LiF(1nm)/Al(150nm)

The green photoelectric phosphorescent device prepared with Ir-pic-42 as the object of the present invention has a maximum luminous efficiency of 92.6 cantera per ampere, a maximum lumen efficiency of 99.8 lumen per watt, a maximum external quantum efficiency of 26.8%, and a maximum of 1000 Under the cantera per square meter, the device still maintains extremely high stability, and the external quantum efficiency remains at 25.4%.

Example 33: Preparation of phosphorescent organic electroluminescent device containing complex Ir-pic-45

Except that the phosphorescent guest material of the light-emitting layer was changed to Ir-pic-45, the same method as Example 28 was used to fabricate an organic electroluminescent device.

Device 6 (D6) structure:

ITO/MoO ₃ (8nm)/TAPC(75nm)/NPB:Ir-pic-45(5wt%,12nm)/Bphen(70nm)/LiF(1nm)/Al(150nm)

The green photoelectric phosphorescent device prepared with Ir-pic-45 as the object of the present invention has a maximum luminous efficiency of 89.3 cantera per ampere, a maximum lumen efficiency of 85.1 lumen per watt, and a maximum external quantum efficiency of 23.5%. Under the cantera per square meter, the device still maintains extremely high stability, and the external quantum efficiency remains at 20.5%.

Example 34: Preparation of phosphorescent organic electroluminescent device containing complex Ir-tmd-57

Except that the phosphorescent guest material of the light-emitting layer was changed to Ir-tmd-57, the same method as Example 28 was used to fabricate an organic electroluminescent device.

Device 7 (D7) structure:

ITO/MoO ₃ (8nm)/TAPC(75nm)/NPB:Ir-tmd-57(5wt%,12nm)/Bphen(70nm)/LiF(1nm)/Al(150nm)

The green photoelectric phosphorescent device prepared with Ir-tmd-57 as the object of the present invention has a maximum luminous efficiency of 34.4 cantera per ampere, a maximum lumen efficiency of 36.7 lumen per watt, and a maximum external quantum efficiency of 22.9%. Under the cantera per square meter, the device still maintains extremely high stability, and the external quantum efficiency remains at 19.8%.

Example 35: Preparation of phosphorescent organic electroluminescent device containing complex Ir-pic-68

Except that the phosphorescent guest material of the light-emitting layer was changed to Ir-pic-68, the same method as Example 28 was used to fabricate an organic electroluminescent device.

Device 8 (D8) structure:

ITO/MoO ₃ (8nm)/TAPC(75nm)/NPB:Ir-pic-68(5wt%,12nm)/Bphen(70nm)/LiF(1nm)/Al(150nm)

The green photoelectric phosphorescent device prepared with Ir-pic-68 as the object of the present invention has a maximum luminous efficiency of 38.5 cantera per ampere, a maximum lumen efficiency of 40.2 lumen per watt, a maximum external quantum efficiency of 26.5%, and a maximum of 1000 Under the cantera per square meter, the device still maintains extremely high stability, and the external quantum efficiency remains at 22.7%.

The above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, on the basis of the above description, other changes or changes in different forms can also be made, and it is impossible to list all the implementation modes here. All obvious changes or changes derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims (4)

1. A class of metal iridium complexes, characterized in that, with thieno [2,3-d] pyrimidine heterocyclic derivatives as the main ligand, with acetylacetone, tetramethylheptanedione or 2-pyridine carboxylic acid as auxiliary Ligand, the structure is shown in the following formula: In the formula, L is selected from the following groups: In the formula, Ar is selected from the following groups: Wherein, R ₁ , R ₂ , R ₃ and R ₄ are independently selected from the following groups: -H, -NH ₂ , -OCH ₃ , -CH ₃ , -C(CH ₃ ) ₃ , -CN, -F, -CF ₃ . 2. The iridium complex according to claim 1, wherein the iridium complex has one of the following structures: 3. A method for preparing phosphorescent iridium complexes as claimed in claim 1, characterized in that: the synthetic method may further comprise the steps: (1) Under argon protection, add 4‐chlorothiophene[2,3‐d]pyrimidine and excess boronic acid A to 1,4‐dioxane, in Pd(dppf)Cl ₂ catalyst and 2M K ₂ Suzuki coupling reaction was carried out under the catalysis of CO ₃ (aq), and ligand B based on thiophene[2,3-d]pyrimidine heterocycle was obtained after separation and purification; (2) Under the protection of argon, dissolve iridium trichloride trihydrate and the above-mentioned ligand B in a mixed solvent of ethylene glycol ether and distilled water at a molar ratio of 1:2.5, and react at 120°C for 24 hours to obtain a chlorine bridge Dimer intermediate; without further purification, the chlorine-bridged dimer intermediate and acetylacetone, tetramethylheptanedione or 2‐pyridinecarboxylic acid were dissolved in ethylene glycol ether, anhydrous sodium carbonate was added, 80°C The reaction was carried out for 12 hours, and the target phosphorescent iridium complex was obtained by separation and purification; The structural formula of boric acid A is: XB(OH) ₂ ; The structural formula of Ligand B is: In the formula, X is selected from the following groups: Wherein, R ₁ , R ₂ , R ₃ and R ₄ are independently selected from the following groups: -H, -NH ₂ , -OCH ₃ , -CH ₃ , -C(CH ₃ ) ₃ , -CN, -F, -CF ₃ . 4. An electrophosphorescent light-emitting device, comprising a conductive glass substrate layer, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode layer; it is characterized in that: the light-emitting material of the light-emitting layer is the claim of the present invention The phosphorescent iridium complex described in 1 or 2.