Complex and preparation method thereof, phosphorescent material, organic electroluminescent device, display screen and solar cell
阅读说明：本技术 配合物及其制备方法、磷光材料、有机电致发光器件、显示屏、太阳能电池 (Complex and preparation method thereof, phosphorescent material, organic electroluminescent device, display screen and solar cell ) 是由 王辉 李小龙 李明 李建行 刘志远 段伟伟 马晓宇 于 2019-12-02 设计创作，主要内容包括：本发明涉及有机光电材料领域,具体公开了一种配合物及其制备方法、磷光材料、有机电致发光器件、显示屏、太阳能电池,所述配合物具有如下结构：<Image he="424" wi="700" file="DDA0002299636640000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>本发明实施例提供的配合物具有良好的发光效率,通过选择特定杂环的配体进行结合来调节配合物的波长,得到的配合物在制备成有机电致发光器件后能提高发光效率,而且使用寿命长,而本发明实施例提供的配合物的制备方法具有合成价格不高、合成工艺要求较低的优点,适合工业化生产,解决了现有磷光材料的发光效率存在不足的问题。(The invention relates to the field of organic photoelectric materials, and particularly discloses a complex and a preparation method thereof, a phosphorescent material, an organic electroluminescent device, a display screen and a solar cell, wherein the complex has the following structure: the complex provided by the embodiment of the invention has good luminous efficiencyThe wavelength of the complex is adjusted by selecting the ligand of a specific heterocycle for combination, the obtained complex can improve the luminous efficiency after being prepared into an organic electroluminescent device, and the service life is long.)
1. A complex has a structure shown in formula I:
m is 0, 1 or 2, n is 1, 2 or 3, and m + n is 3;
R1、R2、R3、R4、R5and R6Each independently selected from hydrogen, deuterium, nitro, amino,Hydroxyl, halogen, cyano, sulfydryl, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C4-C12 aromatic heterocyclic group, substituted or unsubstituted C10-C18 condensed ring group, substituted or unsubstituted C5-C15 spiro ring group.
2. The complex of claim 1, wherein R is1And R2Each independently represents a mono-substituent, a di-substituent, a tri-substituent, a tetra-substituent or no substituent, R3、R4And R6Each independently represents a mono-substituent, a di-substituent or no substituent, R5Represents a mono-substituent, a di-substituent, a tri-substituent or no substituent.
3. The complex of claim 1, wherein R is1、R2、R3、R4、R5And R6Independently form a substituted or unsubstituted C3-C30 aliphatic ring, a substituted or unsubstituted C6-C18 aromatic ring, a substituted or unsubstituted C4-C18 aromatic heterocycle, a substituted or unsubstituted C10-C18 fused ring or a substituted or unsubstituted C5-C18 spiro ring with each other.
4. A complex according to any one of claims 1 to 3, characterised in that the complex is selected from any one of the following structures:
5. a process for preparing a complex as claimed in any one of claims 1 to 4, comprising the steps of:
1) providing a compound X selected from any one of the following structures:
2) reacting the compound X provided in the step 1) with iridium trichloride to obtain an intermediate B;
3) reacting the intermediate B obtained in the step 2) with silver trifluoromethanesulfonate to obtain an intermediate C;
4) providing a compound Y selected from any one of the following structures:
5) reacting the intermediate C obtained in the step 3) with the compound Y provided in the step 4) to obtain the complex.
6. A complex prepared by the method of preparing the complex of claim 5.
7. A phosphorescent material comprising, in part or in whole, the complex as claimed in any of claims 1 to 4.
8. An organic electroluminescent device, characterized in that a part contains the phosphorescent material according to claim 7.
9. A display panel comprising, in part, the organic electroluminescent device according to claim 8.
10. A solar cell comprising, in part, the organic electroluminescent device of claim 8.
Technical Field
The invention relates to the field of organic photoelectric materials, in particular to a complex and a preparation method thereof, a phosphorescent material, an organic electroluminescent device, a display screen and a solar cell.
Background
Electroluminescent devices are widely used in the field of electronic product manufacture as a display device that emits light when an electroluminescent material is excited. Electroluminescent devices can be classified into ac and dc types according to the excitation voltage, and both can be manufactured using a powdered or thin film electroluminescent material. The technical key point of improving the performance of the electroluminescent device is to improve the photochromic purity and efficiency of the electroluminescent material.
In general, a phosphorescent material has a greater luminous efficiency than a fluorescent material, and thus, the phosphorescent material is mostly used in fabricating an organic electroluminescent device. However, the above technical solutions have the following disadvantages in practical use: the existing phosphorescent material has the problem of low luminous efficiency.
Disclosure of Invention
The embodiment of the invention aims to provide a complex and a preparation method thereof, a phosphorescent material, an organic electroluminescent device, a display screen and a solar cell, so as to solve the problem that the luminous efficiency of the existing phosphorescent material provided in the background technology is insufficient.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a complex has a structure shown in formula I:
m is 0, 1 or 2, n is 1, 2 or 3, and m + n is 3;
R1、R2、R3、R4、R5and R6Each independently selected from hydrogen, deuterium, nitro, amino, hydroxyl, halogen, cyano, mercapto, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C4-C12 aromatic heterocyclic group, substituted or unsubstituted C10-C18 condensed ring group, and substituted or unsubstituted C5-C15 spiro ring group.
As a further scheme of the invention: in the formula I, R1And R2Each independently represents a mono-substituent, a di-substituent, a tri-substituent, a tetra-substituent or no substituent, R3、R4And R6Each independently represents a mono-substituent, a di-substituent or no substituent, R5Represents a mono-substituent, a di-substituent, a tri-substituent or no substituent.
As a still further scheme of the invention: in the formula I, R1、R2、R3、R4、R5And R6The substituent position is any position of the ring.
As a still further scheme of the invention: the alkyl is straight-chain alkyl, branched-chain alkyl, cycloalkyl, straight-chain alkyl substituted by at least 1 substituent, branched-chain alkyl substituted by at least 1 substituent or cycloalkyl substituted by at least 1 substituent; wherein, the substituent is one or more of deuterium, nitro, amino, hydroxyl, halogen, cyano, carbonyl or sulfydryl.
As a still further scheme of the invention: the above-mentioned aryl group is an unsubstituted aryl group or an aryl group substituted with at least 1 substituent; wherein, the substituent is one or more of deuterium, nitro, amino, hydroxyl, halogen, cyano, carbonyl or sulfydryl.
As a still further scheme of the invention: the above aromatic heterocyclic group is an unsubstituted heteroaryl group or an aromatic heterocyclic group substituted with at least 1 substituent; wherein the heteroatom in the heteroaryl group is nitrogen, sulfur or oxygen; the substituents are independently selected from halogen, deuterium, amino, cyano, nitro, hydroxyl or mercapto.
As a still further scheme of the invention: in the formula I, R1、R2、R3、R4、R5And R6Each independently forms a substituted or unsubstituted C3-C30 aliphatic ring, a substituted or unsubstituted C6-C18 aromatic ring, a substituted or unsubstituted C4-C18 aromatic heterocycle, a substituted or unsubstituted C10-C18 fused ring, or a substituted or unsubstituted C5-C18 spiro ring with the ring; wherein, the substituent on the substituent group is at least one or more selected from hydrogen, deuterium, nitro, amino, hydroxyl, halogen, cyano, carbonyl or sulfydryl.
As a still further scheme of the invention: r1And R2、R3And R4、R5And R6Form a substituted or unsubstituted C3-C18 aliphatic ring, a substituted or unsubstituted C6-C18 aromatic ring, a substituted or unsubstituted C4-C18 aromatic heterocycle, a substituted or unsubstituted C10-C18 fused ring, or a substituted or unsubstituted C5-C18 spiro ring; wherein, the substituent on the substituent group is at least one or more selected from deuterium, nitro, amino, hydroxyl, halogen, cyano, carbonyl or sulfydryl.
As a still further scheme of the invention: the hydrogen in the above groups or substituents may be deuterated.
As a still further scheme of the invention: the complex is selected from any one of the following structures:
wherein R is1、R2、R3、R4、R5And R6The radicals and their number of substituents are as defined in formula I and are not described in detail here.
Preferably, the complex has a structure shown in formula 3.
Preferably, the complex has any one of the following specific structures:
it should be noted that, only some specific structural forms are listed above, but the series of complexes are not limited to the above molecular structures, and any simple group, substituted group and substituted position can be simply transformed to obtain other specific molecular structures, which are not described in detail herein.
It is a further object of an embodiment of the present invention to provide a method for preparing a complex of any one of the above, comprising the steps of:
1) providing a compound X selected from any one of the following structures:
2) fully reacting the compound X provided in the step 1) with iridium trichloride to obtain an intermediate B;
3) fully reacting the intermediate B obtained in the step 2) with silver trifluoromethanesulfonate to obtain an intermediate C;
4) providing a compound Y selected from any one of the following structures:
5) fully reacting the intermediate C obtained in the step 3) with the compound Y provided in the step 4) to obtain the complex shown in the formula I.
Wherein R is1、R2、R3、R4、R5And R6The radicals and their number of substituents are as defined in formula I and are not described in detail here.
As a still further scheme of the invention: in the full reaction of the compound X provided in the step 1) and iridium trichloride, the molar ratio of the compound X to the iridium trichloride is 1-5: 0.8-1.2.
Preferably, in the full reaction of the compound X provided in the step 1) and iridium trichloride, a solvent is a mixed solution of ethylene glycol ethyl ether and water, and the ratio of the ethylene glycol ethyl ether to the water is 3: 1; the dosage of the solvent is 15-30 times of the mass of the iridium trichloride.
As a still further scheme of the invention: in the step of fully reacting the intermediate B obtained in the step 2) with silver trifluoromethanesulfonate, the molar ratio of the intermediate B to the silver trifluoromethanesulfonate is 0.9-1.1: 2-5.
As a still further scheme of the invention: in the step of fully reacting the intermediate C obtained in the step 3) with the compound Y provided in the step 4), the molar ratio of the intermediate C to the compound Y is 1.9-2.1: 2-4.
As a still further scheme of the invention: the specific synthetic route of the preparation method of the complex shown in the formula 1 is as follows:
as a still further scheme of the invention: the specific synthetic route of the preparation method of the complex shown in the formula 2 is as follows:
as a still further scheme of the invention: the specific synthetic route of the preparation method of the complex shown in the formula 3 is as follows:
another object of the embodiments of the present invention is to provide a complex prepared by the above preparation method of the complex.
It is another object of the embodiments of the present invention to provide a phosphorescent material, which comprises the above complex partially or completely.
It is another object of an embodiment of the present invention to provide an organic electroluminescent device, which partially includes the above-mentioned phosphorescent material.
As a still further scheme of the invention: the organic electroluminescent device includes: the organic electroluminescent device comprises a first electrode, a second electrode and an organic layer arranged between the first electrode and the second electrode, wherein the organic layer is a light-emitting layer and contains the phosphorescent material; the phosphorescent material partially or completely comprises the complex, and the complex is in a single form or is mixed with other substances and exists in an organic layer.
As a still further scheme of the invention: the organic layer at least comprises one or more of a hole injection layer, a hole transport layer, a layer with hole injection and hole transport functions, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a layer with electron transport and electron injection functions.
As a still further scheme of the invention: the organic layer of the organic electroluminescent device comprises a main material and a doping material, wherein the doping material is the complex provided by the embodiment of the invention, and the mixing ratio of the main material to the doping material is 90-99.5:0.5-10 according to the mass ratio.
Another object of the embodiments of the present invention is to provide a display panel, which partially includes the above organic electroluminescent device.
Another object of the embodiments of the present invention is to provide a solar cell, which partially includes the above organic electroluminescent device.
Another object of the embodiments of the present invention is to provide an application of the organic electroluminescent device in the preparation of organic solar cells, electronic paper, organic photoreceptors or organic thin film transistors. The organic electroluminescent device provided by the embodiment of the invention can be used for preparing products such as a luminescent device, an organic solar cell, electronic paper, an organic photoreceptor or an organic thin film transistor.
Compared with the prior art, the invention has the beneficial effects that:
the complex provided by the embodiment of the invention has good luminous efficiency, the wavelength of the complex is adjusted by selecting the ligand of a specific heterocycle for combination, the luminous efficiency of the obtained complex can be improved after the complex is prepared into an organic electroluminescent device, and the service life is long.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
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