PREPARATION OF N^N^C^N TETRADENTATE PLATINUM (II) COMPLEX AND USES THEREOF

Abstract

Preparation of n{circumflex over ( )}n{circumflex over ( )}c{circumflex over ( )}n tetradentate platinum (ii) complex and uses thereof are provided. The complex of the present invention has a structure as shown in Formula (11). The performance of an organic electroluminescence device prepared from the complex of the present invention is better than that of a reference device. A great application value is realized on an OLED (organic light-emitting diode), and the N{circumflex over ( )}N{circumflex over ( )}C{circumflex over ( )}N tetradentate platinum (II) complex can be used as a phosphorescent doped material to manufacture an orange red light OLED device with a high luminous efficiency.

##STR00001##

Claims

1. A N{circumflex over ( )}N{circumflex over ( )}C{circumflex over ( )}N tetradentate platinum (II) complex, having a structure as shown in Formula (11): ##STR00029## wherein R.sub.1 to R.sub.16 are independently selected from hydrogen, deuterium, sulfur, halogen, a hydroxyl group, an acyl group, an alkoxy group, an acyloxy group, an amino group, a nitryl group, an acylamino group, a cyano group, a carboxyl group, a styryl group, an aminocarbonyl group, a carbamoyl group, a benzylcarbonyl group, an aryloxy group, a diarylamine group, a saturated alkyl group containing 1 to 30 carbon atoms, an unsaturated alkyl group containing 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 5 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group containing 5 to 30 carbon atoms, or adjacent R.sub.1 to R.sub.16 are connected to each other by a covalent bond to form a ring.

2. The complex according to claim 1, wherein R.sub.1 to R.sub.16 are independently selected from hydrogen, halogen, an amino group, a nitryl group, a cyano group, a diarylamine group, a saturated alkyl group containing 1 to 10 carbon atoms, an aryl group containing 5 to 20 carbon atoms and unsubstituted or substituted by halogen or one or more C1 to C4 alkyl groups, or a heteroaryl group containing 5 to 20 carbon atoms and unsubstituted or substituted by halogen or one or more C1 to C4 alkyl groups, or adjacent R.sub.1 to R.sub.16 are connected to each other by a covalent bond to form a ring, wherein the halogen is F, Cl or Br.

3. The complex according to claim 2, having a structure as shown in Formula (P): ##STR00030## wherein R.sub.1′ to R.sub.5′ are independently selected from hydrogen, halogen, a diarylamine group, a saturated alkyl group containing 1 to 10 carbon atoms, an aryl group containing 5 to 20 carbon atoms and unsubstituted or substituted by halogen or one or more C1 to C4 alkyl groups, or a heteroaryl group containing 5 to 20 carbon atoms and unsubstituted or substituted by halogen or one or more C1 to C4 alkyl groups, or adjacent R.sub.1′ to R.sub.5′ are connected to each other by a covalent bond to form a ring, wherein the halogen is F, Cl or Br.

4. The complex according to claim 3, wherein 0 to 3 of the 5 groups of R.sub.1′ to R.sub.5′ are independently represented as a diarylamine group, an aryl group containing 5 to 10 carbon atoms and unsubstituted or substituted by halogen or 1 to 3 C1 to C4 alkyl groups, or a heteroaryl group containing 5 to 10 carbon atoms and unsubstituted or substituted by halogen or 1 to 3 C1 to C4 alkyl groups; and other groups are independently represented as hydrogen, halogen or a saturated alkyl group containing 1 to 8 carbon atoms, wherein the halogen is F or Cl.

5. The complex according to claim 4, wherein 0 to 3 of the 5 groups of R.sub.1′ to R.sub.5′ are independently represented as a diphenylamine group, a phenyl group unsubstituted or substituted by C1 to C4 alkyl groups, a pyridyl group or a carbazolyl group, and other groups are independently represented as hydrogen, fluorine or a saturated alkyl group containing 1 to 4 carbon atoms.

6. The complex according to claim 1, having the following structure: ##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036##

7. The complex according to claim 6, having the following structure: ##STR00037##

8. A precursor, i.e., a ligand, of the complex according to any one of claims 1 to 7, having a structural formula as shown in Formula (12): ##STR00038## wherein R.sub.1 to R.sub.16 are independently selected from hydrogen, deuterium, sulfur, halogen, a hydroxyl group, an acyl group, an alkoxy group, an acyloxy group, an amino group, a nitryl group, an acylamino group, a cyano group, a carboxyl group, a styryl group, an aminocarbonyl group, a carbamoyl group, a benzylcarbonyl group, an aryloxy group, a diarylamine group, a saturated alkyl group containing 1 to 30 carbon atoms, an unsaturated alkyl group containing 1 to 20 carbon atoms, a substituted or unsubstituted aryl group containing 5 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group containing 5 to 30 carbon atoms, or adjacent R.sub.1 to R.sub.16 are connected to each other by a covalent bond to form a ring.

9. The precursor according to claim 8, having a structural formula as follows: ##STR00039## wherein R.sub.1′ to R.sub.5′ are independently selected from hydrogen, halogen, a diarylamine group, a saturated alkyl group containing 1 to 10 carbon atoms, an aryl group containing 5 to 20 carbon atoms and unsubstituted or substituted by halogen or one or more C1 to C4 alkyl groups, or a heteroaryl group containing 5 to 20 carbon atoms and unsubstituted or substituted by halogen or one or more C1 to C4 alkyl groups, or adjacent R.sub.1′ to R.sub.5′ are connected to each other by a covalent bond to form a ring, wherein the halogen is F, Cl or Br.

10. A synthetic method of the complex according to claim 3, comprising the following steps: performing a bromination reaction on a carbazole derivative S1 to obtain a substrate S2; performing a reaction on the S2 and bis(pinacolato)diboron to obtain a corresponding pinacol ester derivative S3; performing a Suzuki reaction on the S3 and a pyridine derivative S6 to obtain S7; performing a Suzuki reaction on the S7 and a pyridine derivative S8 to obtain S9; and performing a reaction on the S9 and K.sub.2PtCl.sub.4 to obtain a target product P, wherein the S6 is prepared from the S4 and the S5 through a Stille reaction, and a reaction formula is as follows: ##STR00040##

11. Application of the complex according to any one of claims 1 to 7 to an OLED light-emitting device.

12. The application according to claim 11, wherein the complex according to any one of claims 1 to 7 is applied to the OLED light-emitting device through thermal deposition, spin coating and ink-jet printing in a layered form.

13. The application according to claim 11, wherein the complex according to any one of claims 1 to 7 is a phosphorescent doped material achieving a photon emission effect in a light-emitting layer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0042] FIG. 1 is a schematic structure diagram of an organic electroluminescence device of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0043] The present invention will be further illustrated in detail in conjunction with Embodiments hereafter.

[0044] A preparation method of the complex includes the following steps:

[0045] As shown below, a carbazole derivative S1 takes a bromination reaction to obtain a substrate S2. The S2 takes a reaction with bis(pinacolato)diboron to obtain a corresponding pinacol ester derivative S3. The S3 takes a Suzuki reaction with a pyridine derivative S6 to obtain S7. The S7 takes a Suzuki reaction with a pyridine derivative S8 to obtain S9. The S9 takes a reaction with K.sub.2PtCl.sub.4 to obtain a target product P. The S6 is prepared from the S4 and the S5 through a Stille reaction.

##STR00015##

The present invention will be further illustrated in detail in conjunction with Embodiments hereafter.

[0046] Initial substrates and solvents used in the compound synthesis of the present invention were purchased from suppliers known to those skilled in the art, such as Energy, J&K and Aladdin.

Embodiment 1

[0047] ##STR00016##

Synthetic Routes:

[0048] ##STR00017##

Synthesis of Compound 2: 11.2 g (40.0 mmol) of Compound 1 was taken, and dissolved in 600 mL of acetic acid. Then, 16.0 g (2.5 eq., 100.0 mmol) of liquid bromine was dripped in for light shading reaction. After stirring at a room temperature for about 4 hr, rotary evaporation was performed to remove a solvent. Next, a proper amount of water and sodium hydrogen sulfite solution were added for washing, extraction was performed by using ethyl acetate, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, a proper amount of silica gel was added. Rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography, to obtain 15.7 g of white solids, the yield was 90%, and the purity was 99.9%.
Synthesis of Compound 6: 14.7 g (40.0 mmol) of Compound 5, 34.0 g of Compound 4 (3 eq., 120.0 mmol), and 924 mg of Pd(PPh.sub.3).sub.4 (0.02 eq., 0.8 mmol) were taken, and added into a three-necked flask. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Then, 200 mL of toluene was injected, and heating was performed to reach 105° C. After reaction for 12 hr under nitrogen gas protection, cooling was performed to reach the room temperature. A KF solution was used for quenching reaction. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography, to obtain 7.5 g of white solids, the yield was 80%, and the purity was 99.5%.
Synthesis of Compound 7: 10.3 g (20.0 mmol) of Compound 3, 4.7 g (20.0 mmol) of Compound 6, 3.4 g of potassium carbonate (1.25 eq., 25 mmol) and 462 mg of Pd(PPh.sub.3).sub.4 (0.02 eq., 0.4 mmol) were taken, and added into a three-necked flask. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Then, 60 mL of dioxane and 20 mL of water were injected, and heating was performed to reach 100° C. After reaction for 12 hr under nitrogen gas protection, cooling was performed to reach the room temperature. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography, to obtain 7.8 g of white solids, the yield was 70%, and the purity was 99.5%.
Synthesis of Compound 9: 5.6 g (10.0 mmol) of Compound 7, 1.9 g of Compound 8 (1.2 eq., 12.0 mmol), 1.7 g of potassium carbonate (1.25 eq., 12.5 mmol) and 230 mg of Pd(PPh.sub.3).sub.4 (0.02 eq., 0.2 mmol) were taken, and added into a three-necked flask. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Then, 30 mL of dioxane and 10 mL of water were injected, and heating was performed to reach 100° C. After reaction for 12 hr under nitrogen gas protection, cooling was performed to reach the room temperature. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography, to obtain 4.6 g of white solids, the yield was 90%, and the purity was 99.9%. Mass spectrum: (ESI.sup.−) ([M-H].sup.−). C.sub.36H.sub.35N.sub.3 theoretical value: 508.28. Measured value: 508.25.
Synthesis of Compound P1: 1.02 g (2.0 mmol) of Compound 9, 160 mg of tetrabutylammonium bromide (0.25 eq., 0.5 mmol) and 930 mg of potassium chloroplatinate (1.2 eq., 2.4 mmol) were taken, and dissolved in 25 mL of acetic acid. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Heating was performed under stirring to reach 130° C. for reaction for 12 Hr. After the reaction was completed, cooling and rotary evaporation were performed to remove a solvent. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography. An obtained crude product was subjected to vacuum sublimation to obtain 842 mg of dark red solids, the total yield was 60%, and the purity was 99.9%. Mass spectrum: (ESI.sup.−) ([M-H].sup.−). C.sub.36H.sub.32N.sub.3Pt theoretical value: 508.28. Measured value: 508.25.

Embodiment 2

[0049] ##STR00018##

Synthetic routes of P2 are basically identical to those of P1. Synthesis of partial compounds was shown as follows:

##STR00019##

Synthesis of Compound 11: 15.3 g (40.0 mmol) of Compound 10, 34.0 g of Compound 4 (3 eq., 120.0 mmol), and 924 mg of Pd(PPh.sub.3).sub.4 (0.02 eq., 0.8 mmol) were taken, and added into a three-necked flask. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Then, 200 mL of toluene was injected, and heating was performed to reach 105° C. After reaction for 12 hr under nitrogen gas protection, cooling was performed to reach the room temperature. A KF solution was used for quenching reaction. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography, to obtain 8.4 g of white solids, the yield was 85%, and the purity was 99.0%.
Synthesis of Compound 12: 10.3 g (20.0 mmol) of Compound 3, 5.0 g (20.0 mmol) of Compound 11, 3.4 g of potassium carbonate (1.25 eq., 25 mmol) and 462 mg of Pd(PPh.sub.3).sub.4 (0.02 eq., 0.4 mmol) were taken, and added into a three-necked flask. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Then, 60 mL of dioxane and 20 mL of water were injected, and heating was performed to reach 100° C. After reaction for 12 hr under nitrogen gas protection, cooling was performed to reach the room temperature. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography, to obtain 7.8 g of white solids, the yield was 68%, and the purity was 99.5%.
Synthesis of Compound 13: 5.7 g (10.0 mmol) of Compound 12, 1.9 g of Compound 8 (1.2 eq., 12.0 mmol), 1.7 g of potassium carbonate (1.25 eq., 12.5 mmol) and 230 mg of Pd(PPh.sub.3).sub.4 (0.02 eq., 0.2 mmol) were taken, and added into a three-necked flask. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Then, 30 mL of dioxane and 10 mL of water were injected, and heating was performed to reach 100° C. After reaction for 12 hr under nitrogen gas protection, cooling was performed to reach the room temperature. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography, to obtain 4.4 g of white solids, the yield was 85%, and the purity was 99.9%. Mass spectrum: (ESI.sup.−) ([M-H].sup.−). C.sub.37H.sub.36N.sub.3 theoretical value: 522.30. Measured value: 522.31.
Synthesis of Compound P2: 1.04 g (2.0 mmol) of Compound 13, 160 mg of tetrabutylammonium bromide (0.25 eq., 0.5 mmol) and 930 mg of potassium chloroplatinate (1.2 eq., 2.4 mmol) were taken, and dissolved in 25 mL of acetic acid. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Heating was performed under stirring to reach 130° C. for reaction for 12 Hr. After the reaction was completed, cooling and rotary evaporation were performed to remove a solvent. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography. An obtained crude product was subjected to vacuum sublimation to obtain 716 mg of dark red solids, the total yield was 50%, and the purity was 99.9%. Mass spectrum: (ESI.sup.−) ([M-H].sup.−). C.sub.37H.sub.35N.sub.3Pt theoretical value: 716.25. Measured value: 716.23.

Embodiment 3

[0050] ##STR00020##

Synthetic routes of P3 are basically identical to those of P1. Synthesis of partial compounds was shown as follows:

##STR00021##

Synthesis of Compound 15: 18.9 g (40.0 mmol) of Compound 14, 34.0 g of Compound 4 (3 eq., 120.0 mmol), and 924 mg of Pd(PPh.sub.3).sub.4 (0.02 eq., 0.8 mmol) were taken, and added into a three-necked flask. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Then, 200 mL of toluene was injected, and heating was performed to reach 105° C. After reaction for 12 hr under nitrogen gas protection, cooling was performed to reach the room temperature. A KF solution was used for quenching reaction. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography, to obtain 10.8 g of white solids, the yield was 80%, and the purity was 99.0%.
Synthesis of Compound 16: 10.3 g (20.0 mmol) of Compound 3, 6.8 g (20.0 mmol) of Compound 15, 3.4 g of potassium carbonate (1.25 eq., 25 mmol) and 462 mg of Pd(PPh.sub.3).sub.4 (0.02 eq., 0.4 mmol) were taken, and added into a three-necked flask. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Then, 60 mL of dioxane and 20 mL of water were injected, and heating was performed to reach 100° C. After reaction for 12 hr under nitrogen gas protection, cooling was performed to reach the room temperature. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography, to obtain 7.9 g of white solids, the yield was 60%, and the purity was 99.5%.
Synthesis of Compound 17: 6.6 g (10.0 mmol) of Compound 16, 1.9 g of Compound 8 (1.2 eq., 12.0 mmol), 1.7 g of potassium carbonate (1.25 eq., 12.5 mmol) and 230 mg of Pd(PPh.sub.3).sub.4 (0.02 eq., 0.2 mmol) were taken, and added into a three-necked flask. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Then, 30 mL of dioxane and 10 mL of water were injected, and heating was performed to reach 100° C. After reaction for 12 hr under nitrogen gas protection, cooling was performed to reach the room temperature. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography, to obtain 4.9 g of white solids, the yield was 80%, and the purity was 99.9%. Mass spectrum: (ESI.sup.−) ([M-H].sup.−). C.sub.44H.sub.42N.sub.3 theoretical value: 612.35. Measured value: 612.33.
Synthesis of Compound P3: 1.23 g (2.0 mmol) of Compound 17, 160 mg of tetrabutylammonium bromide (0.25 eq., 0.5 mmol) and 930 mg of potassium chloroplatinate (1.2 eq., 2.4 mmol) were taken, and dissolved in 25 mL of acetic acid. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Heating was performed under stirring to reach 130° C. for reaction for 12 Hr. After the reaction was completed, cooling and rotary evaporation were performed to remove a solvent. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography. An obtained crude product was subjected to vacuum sublimation to obtain 887 mg of dark red solids, the total yield was 55%, and the purity was 99.9%. Mass spectrum: (ESI.sup.−) ([M-H].sup.−). C.sub.44H.sub.41N.sub.3Pt theoretical value: 805.30. Measured value: 805.28.

Embodiment 4

[0051] ##STR00022##

Synthesis of Compound 19: 14.7 g (40.0 mmol) of Compound 5, 53.2 g of Compound 18 (3 eq., 120.0 mmol), and 924 mg of Pd(PPh.sub.3).sub.4 (0.02 eq., 0.8 mmol) were taken, and added into a three-necked flask. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Then, 200 mL of toluene was injected, and heating was performed to reach 105° C. After reaction for 12 hr under nitrogen gas protection, cooling was performed to reach the room temperature. A KF solution was used for quenching reaction. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography, to obtain 13.4 g of white solids, the yield was 85%, and the purity was 99.0%.
Synthesis of Compound 20: 10.3 g (20.0 mmol) of Compound 3, 7.9 g (20.0 mmol) of Compound 19, 3.4 g of potassium carbonate (1.25 eq., 25 mmol) and 462 mg of Pd(PPh.sub.3).sub.4 (0.02 eq., 0.4 mmol) were taken, and added into a three-necked flask. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Then, 60 mL of dioxane and 20 mL of water were injected, and heating was performed to reach 100° C. After reaction for 12 hr under nitrogen gas protection, cooling was performed to reach the room temperature. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography, to obtain 8.9 g of white solids, the yield was 62%, and the purity was 99.0%.
Synthesis of Compound 21: 7.2 g (10.0 mmol) of Compound 20, 1.9 g of Compound 8 (1.2 eq., 12.0 mmol), 1.7 g of potassium carbonate (1.25 eq., 12.5 mmol) and 230 mg of Pd(PPh.sub.3).sub.4 (0.02 eq., 0.2 mmol) were taken, and added into a three-necked flask. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Then, 30 mL of dioxane and 10 mL of water were injected, and heating was performed to reach 100° C. After reaction for 12 hr under nitrogen gas protection, cooling was performed to reach the room temperature. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography, to obtain 5.7 g of white solids, the yield was 85%, and the purity was 99.9%. Mass spectrum: (ESI.sup.−) ([M-H].sup.−). C.sub.48H.sub.50N.sub.3 theoretical value: 668.41. Measured value: 668.39.
Synthesis of Compound P4: 1.34 g (2.0 mmol) of Compound 21, 160 mg of tetrabutylammonium bromide (0.25 eq., 0.5 mmol) and 930 mg of potassium chloroplatinate (1.2 eq., 2.4 mmol) were taken, and dissolved in 25 mL of acetic acid. Vacuum pumping was performed, and nitrogen gas was introduced for replacement for many times. Heating was performed under stirring to reach 130° C. for reaction for 12 Hr. After the reaction was completed, cooling and rotary evaporation were performed to remove a solvent. Then, a proper amount of water and ethyl acetate were added for extraction, and an organic phase was collected. After drying by using anhydrous magnesium sulfate, rotary evaporation was performed to remove a solvent. A n-hexane/ethyl acetate system was used for column chromatography. An obtained crude product was subjected to vacuum sublimation to obtain 776 mg of dark red solids, the total yield was 45%, and the purity was 99.9%. Mass spectrum: (ESI.sup.−) ([M-H].sup.−). C.sub.48H.sub.48N.sub.3Pt theoretical value: 861.36. Measured value: 861.33.

[0052] The Pt (II) complex according to the embodiment showed obvious orange red light emission in a dichloromethane solution, and a wavelength range was between 617 nm and 619 nm, as shown in the following table.

TABLE-US-00001 P1 [00023] P2 [00024] P3 [00025] P4 [00026] Complex Emission (dichloromethane solution) λ.sub.max/nm P1 618 P2 617 P3 619 P4 618
Application examples of the compound of the present invention are provided hereafter.
ITO/TAPC (60 nm)/TCTA:Pt(II) (40 nm)/TmPyPb (30 nm)/LiF (1 nm)/Al (80 nm)

[0053] Preparation Mode of Device:

[0054] A transparent anodized tin indium tin (ITO, 20) (10 Ω/sq) glass substrate 10 was ultrasonically cleaned by using acetone, ethanol and distilled water in sequence, and was then subjected to plasma treatment for 5 minutes by using oxygen gas.

[0055] Next, the ITO substrate was mounted on a substrate holder of vacuum vapor deposition equipment. In the evaporation equipment, a system pressure was controlled at 10-6 torr.

[0056] Then, a hole transport layer (30) material TAPC with a thickness of 60 nm was evaporated onto the ITO substrate.

[0057] Then, a light-emitting layer material (40) TCTA with a thickness of 40 nm was evaporated, and platinum (II) complex dopants in different mass percentage were doped.

[0058] Then, an electron transport layer (50) material TmPyPb with a thickness of 30 nm was evaporated.

[0059] Then, LiF with a thickness of 1 nm was evaporated as an electron injection layer (60).

[0060] Finally, Al with a thickness of 80 nm was evaporated as a cathode (70), and device packaging was completed, as shown in FIG. 1.

##STR00027##

[0061] The structures and manufacturing methods of the device were completely identical, the differences were that the organic metal complexes P0, P1, P2, P3 and P4 were sequentially used as the dopants in the light-emitting layer, and the doping concentrations were different. Pt0 is a classic O{circumflex over ( )}N{circumflex over ( )}N{circumflex over ( )}O type red light material.

##STR00028##

[0062] Device comparative results were as shown in the following table:

TABLE-US-00002 Doping Pt (II) CE (cd/A) PE (lm/W) EQE (%) concentration complex V.sub.on (V) at 1000 cd/A  4 wt % P0 3.4 69.4 60.5 14.0 P1 3.1 72.6 64.8 16.2 P2 3.0 72.8 65.2 16.6 P3 3.0 73.5 67.6 17.5 P4 3.0 74.0 68.5 18.0  8 wt % P0 3.4 68.2 59.8 13.6 P1 3.1 73.6 66.7 17.2 P2 3.0 74.8 67.0 17.5 P3 3.0 75.7 67.5 18.0 P4 3.0 77.0 68.6 19.2 12 wt % P0 3.4 66.8 58.2 13.0 P1 3.1 74.6 67.5 17.8 P2 3.0 75.5 68.2 18.3 P3 3.0 76.5 69.2 18.6 P4 3.0 78.6 71.0 20.3

[0063] Under the condition that the doping concentrations of the tetradentate platinum (II) complexes were respectively 4 wt %, 8 wt % and 12 wt %, the device was prepared by using the above ITO/HTL-1 (60 nm)/EML-1:Pt(II)(40 nm)/ETL-1 (30 nm)/LiF(1 nm)/Al(80 nm) device basic structure. By taking the performance of a device based on P0 as a reference, start-up voltages V.sub.on of the devices of the tetradentate platinum (II) complexes P1, P2, P3 and P4 were reduced to different degrees through being compared to that of the device of P0. At the same time, under the condition of 1000 cd/A, the current efficiency (CE), power efficiency (PE) and external quantum efficiency (EQE) of devices based on P1, P2, P3 and P4 were improved to different degrees through being compared to those of the device based on P0. Particularly, the improvement of P4 in the current efficiency (CE), power efficiency (PE) and external quantum efficiency (EQE) was obvious. When the doping concentration of the tetradentate platinum (II) complex was increased, the efficiency of P0 was slightly improved or even decreased to a certain degree. Because of a strong planar structure of P0, the interaction among molecules was increased, and the luminous efficiency was reduced. P1, P2, P3 and P4 had larger steric hindrance groups than P0, so that the aggregation effect among molecules could be effectively reduced, the formation of an exciplex could be avoided, and the luminous efficiency could be improved.

[0064] The tetradentate platinum (II) complex according to the present invention has a ligand skeleton with a porphyrin-like structure, and a ligand central cavity can form strong chelate coordination with platinum (II), so it is beneficial to improve the complex stability, and beneficial to build long-life OLED devices. At the same time, the ligand skeleton has an excellent rigid structure, the non-radiative energy dissipation such as intramolecular rotation and vibration can be greatly reduced, and the luminous efficiency and performance improvement of the platinum (II) complex is facilitated.

[0065] Based on the above, the performance of an organic electroluminescence device prepared by the present invention is better than that of a reference device, and the related novel N{circumflex over ( )}N{circumflex over ( )}C{circumflex over ( )}N tetradentate platinum (II) complex metal organic material has greater application values. The N{circumflex over ( )}N{circumflex over ( )}C{circumflex over ( )}N tetradentate platinum (II) complex metal organic material prepared by the present invention has great application values to organic light-emitting diodes, and can be used as a phosphorescent doped material to manufacture an orange red light OLED device with a high