PLATINUM METAL COMPLEX AND USE THEREOF IN ORGANIC ELECTROLUMINESCENT DEVICE

Abstract

The present invention relates to a platinum metal complex and an application thereof in an organic light-emitting device. The platinum metal complex is a compound having a structure of chemical formula (I). An organic light-emitting device to which the compound is applied has a relatively low driving voltage, a relatively high luminous efficiency and improved service life to a certain extent; therefore, the complex has the potential of being applied in the field of organic light-emitting devices. Also provided is an organic light-emitting device, including a cathode, an anode, and an organic layer. The organic layer is one or more of a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer; and at least one layer in the organic layer contains the compound of structural formula (I).

##STR00001##

Claims

1. A platinum metal complex, being a compound having a structure as shown in Formula (I): ##STR00015## wherein: R.sup.1-R.sup.32 are each independently selected from: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl having 3-20 carbon atoms, substituted or unsubstituted alkoxy having 1-20 carbon atoms, substituted or unsubstituted aryl having 6-30 carbon atoms, substituted or unsubstituted heteroaryl having 3-30 carbon atoms, or cyano; Ar.sup.1 and Ar.sup.2 are independently selected from an aromatic group having 6-14 carbon atoms and an heteroaromatic group having 3-12 carbon atoms, respectively; heteroatom in the heteroaromatic group is selected from one or more of O, S and N; and the substitution refers to a substitution by deuterium, halogen and C1-8 alkyl.

2. The platinum metal complex according to claim 1, wherein the R.sup.1-R.sup.32 are independently selected from: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1-6 carbon atoms, substituted or unsubstituted cycloalkyl having 3-6 carbon atoms, substituted or unsubstituted aryl having 6-12 carbon atoms, substituted or unsubstituted heteroaryl having 3-6 carbon atoms, respectively; the Ar.sup.1 and the Ar.sup.2 are independently selected from phenyl and pyridine, respectively.

3. The platinum metal complex according to claim 2, wherein the R.sup.1-R.sup.32 are independently selected from: hydrogen, deuterium, substituted or unsubstituted alkyl having 1-4 carbon atoms, substituted or unsubstituted cycloalkyl having 3-6 carbon atoms, phenyl, tolyl or pyridyl, respectively; the Ar.sup.1 and the Ar.sup.2 are the same.

4. The platinum metal complex according to claim 3, wherein the R.sup.1-R.sup.32 are independently selected from: hydrogen, methyl, isopropyl or tert-butyl, respectively.

5. The platinum metal complex according to claim 4, wherein R1-R3, R12-R17 and R26-R30 in the R.sup.1-R.sup.32 are hydrogen; other groups are hydrogen, methyl, isopropyl or tert-butyl; the Ar.sup.1 and the Ar.sup.2 are phenyl.

6. The platinum metal complex according to claim 1, which is one of the following compounds: ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022##

7. The platinum metal complex according to claim 6, having one of the following structures: ##STR00023##

8. A precursor of the platinum metal complex according to any one of claims 1-7, namely, a ligand, having the following structural formula: ##STR00024##

9. An application of the platinum metal complex of any one of claims 1-7 in an organic light-emitting device, an organic thin film transistor, an organic photovoltaic device, a luminescent electrochemical cell and a chemical sensor.

10. An organic light-emitting device, comprising a cathode, an anode, and an organic layer, wherein the organic layer is one or more of a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron injection layer and an electron transport layer; and the organic layer comprises the platinum metal complex of any one of claims 1-7.

11. The organic light-emitting device according to claim 10, wherein the platinum metal complex of any one of claims 1-7 is located at the light-emitting layer.

12. The organic light-emitting device according to claim 10, wherein the organic layer has a total thickness of 1-1000 nm; and the organic layer forms a thin film via evaporation or a solution method.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0025] FIG. 1 is a structure diagram showing an organic light-emitting device of the present invention;

[0026] 10 represents glass substrate; 20 represents anode; 30 represents hole injection layer; 40 represents hole transport layer; 50 represents light-emitting layer; 60 represents electron transport layer; 70 represents electron injection layer; 80 represents cathode.

DETAILED DESCRIPTION OF EMBODIMENTS

[0027] The synthesis method of the material is not required in this present invention. To describe the present invention more specifically, examples are set forth below, but not limited thereto.

[0028] Raw materials used in the following synthesis are products available commercially.

Example 1

[0029] Synthesis of the Complex 1

##STR00011##

[0030] Synthesis of the Intermediate 1c

[0031] The compound 1a (4.9 g, 10.0 mmol) (Reference: J. Mater. Chem., 2014, 2, 2028 synthesis) was dissolved into tetrahydrofuran (50 mL) under the protection of nitrogen, and cooled to −78° C., then dropwisely added with n-butyllithium BuLi (2.0 M, 11 mL), and stirred for 30 min, afterwards, a tetrahydrofuran solution of the compound 1b (4.2 g, 25.0 mmol) (Reference: J. Am. Chem. Soc, 2008, 130, 9942 synthesis) was dropwisely added to the above solution, stirred for 30 min, and heated up to room temperature, and stirred for 1 h continuously. The above reaction liquid was added to a diluted hydrochloric acid solution (1 M, 100 mL), and stirred for 30 min. The mixture was extracted for three times with dichloromethane; organic phases were combined. The organic phase was dried by anhydrous sodium sulfate and subjected to rotary evaporation to remove solvent, thus obtaining a light yellow solid; the residue was separated by column chromatography to obtain a light yellow oily matter (2.8 g, yield: 51%). ESI-MS (m/z): 543.2 (M+1).

[0032] Synthesis of the Compound 1d:

[0033] 2-bromobiphenyl (2.3 g, 10.0 mmol) was dissolved into tetrahydrofuran (30 mL) under the protection of nitrogen, and cooled to −78° C., then dropwisely added with n-butyllithium BuLi (2.0 M, 11 mL), and stirred for 30 min, afterwards, the tetrahydrofuran solution (10 mL) of the compound 1c (2.6 g, 4.8 mmol) was dropwisely added to the above solution, stirred for 30 min, and heated up to room temperature, and stirred for 1 h continuously. The above reaction liquid was added to water and then extracted for three times with dichloromethane; organic phases were combined. The organic phase was dried by anhydrous sodium sulfate and subjected to rotary evaporation to remove solvent, thus obtaining a light yellow solid. The above solid was dissolved into acetic acid (50 mL), and added with concentrated sulfuric acid (4 mL) for reflux over the night under the protection of nitrogen. The above reaction liquid was cooled to room temperature and added to water, then extracted for three times with dichloromethane; organic phases were combined. The organic phase was dried by anhydrous sodium sulfate and subjected to rotary evaporation to remove solvent; the residue was separated by column chromatography to obtain a light yellow solid (2.8 g, yield: 71%). ESI-MS (m/z): 815.3 (M+1).

[0034] Synthesis of the Complex 1

[0035] The compound 1d (2.5 g, 3.1 mmol), potassium tetrachloroplatinate (1.5 g, 3.6 mmol) and 250 mL acetic acid were added to a flask and stirred for 48 h at reflux under the protection of nitrogen. The above reaction liquid was cooled to room temperature, then added to water and filtered to obtain a coarse product, and the coarse product was recrystallized to obtain a yellow solid (2.5 g, yield: 80%). ESI-MS (m/z): 1008.3 (M+1).

Example 2

[0036] Synthesis of the Complex 22

##STR00012##

[0037] Synthesis of the Intermediate 22b

[0038] The 2-bromobiphenyl was replaced with the compound 22a (Reference: Dyes Pigm., 2015, 121, 7 synthesis) to synthesize the intermediate 22b by reference to the preparation method of the compound 1d, thus obtaining 2.9 g of a light yellow solid with a yield of 69%. ESI-MS (m/z): 1039.6 (M+1).

[0039] Synthesis of the Complex 22

[0040] 1d was replaced with the compound 22b to synthesize the complex 22 by reference to the preparation method of the complex 1, thus obtaining 2.1 g of a yellow solid with a yield of 73%. ESI-MS (m/z): 1232.5 (M+1).

Example 3

[0041] A light-emitting device was prepared by using the complex light-emitting material of the present invention, and the device has a structure shown in FIG. 1.

[0042] Firstly, a transparent conductive ITO glass substrate 10 (an anode was provided) was successively cleaned with a detergent solution and deionized water, ethanol, acetone, and deionized water, and then subjected to plasma treatment with oxygen for 30 s.

[0043] HATCN having a thickness of 10 nm was then evaporated on the ITO as a hole injection layer 30.

[0044] A compound HT was then evaporated to form a hole transport layer 40 having a thickness of 40 nm.

[0045] A light-emitting layer 50 having a thickness of 20 nm was then evaporated on the hole transport layer; the light-emitting layer was obtained by mixing and doping the complex 1 (20%) with CBP (80%).

[0046] AlQ.sub.3 having a thickness of 40 nm was evaporated on the light-emitting layer as an electron transport layer 60.

[0047] Finally, 1 nm LiF was evaporated as an electron injection layer 70 and 100 nm Al was evaporated as a cathode 80 of the device.

Example 4

[0048] The complex 1 was replaced with the complex 22; a light-emitting device was prepared according to the method described in Example 3.

COMPARATIVE EXAMPLE

[0049] The complex 1 was replaced with Ir(PPy).sub.3; a light-emitting device was prepared according to the method described in Example 3.

[0050] HATCN, HT, AlQ.sub.3, Ir(PPy).sub.3 and CBP in the device have the following structural formulas:

##STR00013## ##STR00014##

[0051] Performance of the organic light-emitting devices in Examples 3-4 and Comparative Example at an electric current density of 10 mA/cm.sup.2 is listed in Table 1:

TABLE-US-00001 TABLE 1 Driving Luminous Device service Example Complex voltage efficiency life (LT95) 3 1 0.91 1.2 1.5 4 22 0.87 1.3 1.3 Comparative Example Ir(PPy).sub.3 1 1 1 Remarks: the performance test of the device is by reference to the Comparative Example; each index in the Comparative Example is set 1; LT95 shows the corresponding time when the device brightness attenuates to 95% of the initial brightness.

[0052] It can be seen from the data of Table 1 that under the same conditions, the efficiency of the organic light-emitting device prepared by the compound of the present invention is superior to that of the Comparative Example; compared with the common complex light-emitting material Ir(PPy).sub.3, the platinum metal complex material of the present invention is applied in an organic light-emitting device to have a lower driving voltage and a higher luminous efficiency. Moreover, the service life of the device is also improved to some extent, which conforms to the demands of the display industry for light-emitting materials. Therefore, the present invention has good industrialization prospect.

Example 5

[0053] Ratio (Φ.sub.a/Φ.sub.b) of luminescence quantum yields of the platinum complexes 1 and 22 in the state of aggregation and solution is listed in Table 2:

TABLE-US-00002 TABLE 2 Complex 2 22 Φ.sub.a/Φ.sub.b 2.1 2.5 Φ.sub.a: the luminescence quantum yield of the complex in the state of aggregation; Φ.sub.b: the luminescence quantum yield of the platinum complex in dichloromethane solution (1 × 10.sup.−5 M).

[0054] It can be seen from the data of Table 2 that the quantum yield of the platinum metal complex of the present invention in the state of aggregation is higher than that in solution. As can be seen, the platinum metal complex of the present invention further has the property of aggregation-induced emission enhancement.

[0055] The above multiple embodiments are merely set as examples, but are not construed as limiting the protection scope of the present invention. Multiple materials and structures of the present invention may be replaced by other materials and structures in the premise of not departing from the spirit of the present invention. It should be understood that a person skilled in the art can make lots of modifications and changes according to the idea of the present invention without inventive efforts. Therefore, any technical solution obtained by a person skilled in the art on the basis of the prior art and through analysis, reasoning or partial researches shall fall within the protection scope defined in the claims.