阅读说明：本技术 一类基于卤代芳香酮类衍生物的有机电致发光材料及其制备方法与应用 (Organic electroluminescent material based on halogenated aromatic ketone derivatives, and preparation method and application thereof ) 是由 唐本忠 赵祖金 徐静文 朱翔宇 秦安军 胡蓉蓉 王志明 于 2019-10-22 设计创作，主要内容包括：本发明公开了一类基于卤代芳香酮类衍生物的有机电致发光材料及其制备方法与应用。该类有机电致发光材料的结构如下：<Image he="78" wi="700" file="DDA0002243472210000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,R<Sub>1</Sub>为不同芳香环给电子基或卤代芳香环给电子基,R<Sub>2</Sub>为甲基、芳香环给电子基或卤代芳香环给电子基,X为氢原子或卤素原子；所述X、R<Sub>1</Sub>、R<Sub>2</Sub>中至少一个基团含有卤素原子。该类有机电致发光材料具有AIDF性质和高的固态荧光量子效率。而且合成方法简单、高效。基于此类有机电致发光材料的OLEDs器件具有高的非掺器件效率,并且在高亮度下效率滚降依然很低。本发明的有机电致发光材料适用性强,不同掺杂浓度下的OLEDs器件都表现出高的器件效率和高亮度下低的效率滚降,有望在照明与显示设备上得到广泛应用。(The invention discloses an organic electroluminescent material based on halogenated aromatic ketone derivatives, and a preparation method and application thereof. The structure of the organic electroluminescent material is as follows: wherein R is 1 Is an electron donating group of different aromatic rings or a halogenated aromatic ring, R 2 Is methyl, aromatic ring electron donating group or halogenated aromatic ring electron donating group, and X is hydrogen atom or halogen atom; the X, R 1 、R 2 At least one group contains a halogen atom. The organic electroluminescent material has AIDF propertyMass and high solid state fluorescence quantum efficiency. And the synthesis method is simple and efficient. OLEDs based on such organic electroluminescent materials have high non-doped device efficiency and the efficiency roll-off is still low at high brightness. The organic electroluminescent material has strong applicability, and OLEDs (organic light emitting diodes) devices with different doping concentrations show high device efficiency and low efficiency roll-off under high brightness, and are expected to be widely applied to lighting and display equipment.)

1. An organic electroluminescent material based on halogenated aromatic ketone derivatives is characterized by having the following structure:

wherein R is ₁Is an electron donating group or a halogenated aromatic ring electron donating group, R ₂Is methyl, aromatic ring electron donating group or halogenated aromatic ring electron donating group, and X is hydrogen atom or halogen atom; the X, R ₁、R ₂At least one group contains a halogen atom.

2. The organic electroluminescent material of claim 1, wherein the aromatic ring electron-donating group and the halogenated aromatic ring electron-donating group are phenyl, carbazolyl, carbazolylphenyl, phenoxazinyl, phenothiazinyl, acridinyl, fluorenyl, spirofluorenyl, dibenzofluorenyl, dibenzothienyl, dianilino, trianilino or phenylazino.

3. The organic electroluminescent material based on halogenated aromatic ketone derivatives as claimed in claim 2, wherein the structures of the aromatic ring electron-donating group and the halogenated aromatic ring electron-donating group are as follows:

wherein R' are the same or different halogen atoms or hydrogen atoms; r' is a halogen atom if X is a hydrogen atom; if X is a halogen atom, R' is a hydrogen atom or a halogen atom.

4. The organic electroluminescent material based on halogenated aromatic ketone derivatives as claimed in claim 1, wherein X is a halogen atom.

5. The method for preparing the organic electroluminescent material based on the halogenated aromatic ketone derivative as claimed in any one of claims 1 to 4, is characterized by comprising the following steps: the halogenated aromatic ring derivative and the p-fluorobenzoyl chloride are subjected to Friedel-crafts acylation reaction to obtain a corresponding organic intermediate, and then the organic intermediate and the R are subjected to the action of potassium tert-butoxide ₁The organic electroluminescent material based on the halogenated aromatic ketone derivative is obtained through reaction.

6. The process according to claim 5, wherein the halogenated aromatic ring derivative is

7. The application of the organic electroluminescent material based on halogenated aromatic ketone derivatives as claimed in any one of claims 1 to 4 in the field of organic photoelectricity.

8. Use according to claim 7, wherein the organic electroluminescent material based on halogenated aromatic ketone derivatives is used for the preparation of organic OLEDs.

Technical Field

The invention belongs to the field of organic electroluminescent materials, and particularly relates to an organic electroluminescent material based on halogenated aromatic ketone derivatives, and a preparation method and application thereof.

Background

Organic Light Emitting Diodes (OLEDs), which are a new generation of display devices, have the advantages of self-luminescence, wide viewing angle, high contrast, low power consumption, and extremely fast response speed. Due to the advantages, the OLED display technology is increasingly applied to the display fields of mobile phones, televisions, computers and the like. As a new generation of display equipment, the OLED has a wide development prospect, so that the research and development of novel high-efficiency and high-stability OLED materials have very important significance.

In the electroluminescent process, the traditional OLED material can only utilize 25% of singlet excitons to emit light, and the remaining 75% of triplet excitons can only be dissipated in a non-radiative transition mode, so that the improvement of the efficiency and the practical application are greatly limited. As a second generation luminescent material, the phosphorescent material of the transition metal complex can achieve 100% internal quantum efficiency due to the fact that singlet excitons and triplet excitons can be simultaneously utilized for luminescence, and therefore the efficiency of an OLED device is improved. However, for most phosphorescent materials, the transition metal complex is not only expensive and expensive to manufacture, but also has a serious roll-off in efficiency, thereby limiting the practical application of the transition metal complex in OLED devices. In 2012, Adachi et al developed a third generation of luminescent materials, namely Thermally Activated Delayed Fluorescence (TADF) materials. The material can utilize triplet excitons even under the condition of not using transition metals, and realizes a high-efficiency organic OLED device. However, the non-doped TADF material basically faces a serious efficiency roll-off problem, and the adverse effect must be reduced by doping treatment, which greatly increases the process requirements.

The aggregation-induced delayed fluorescence (AIDF) material has higher luminous efficiency in a solid state than a single-molecule state, unlike a conventional delayed fluorescence material. The material has a twisted configuration, can inhibit intermolecular accumulation, and reduces a non-radiative energy dissipation process, thereby improving the efficiency of a device. The organic OLED device of the material not only realizes high device efficiency, but also reduces the efficiency of the non-doped device under high brightness. After the material is modified by halogen atoms, the efficiency of the OLEDs can be further improved. Therefore, it is expected to be applied in practice.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide an organic electroluminescent material based on halogenated aromatic ketone derivatives. This class of materials has the property of Aggregation Induced Delay (AIDF). In addition, the invention provides a synthetic route of the halogenated aromatic ketone derivative, and the method is simple and efficient in synthesis. Moreover, the invention also provides application of the halogenated aromatic ketone derivative in an organic electroluminescent device.

The object of the present invention is achieved by the following means.

An organic electroluminescent material based on halogenated aromatic ketone derivatives has the following structure:

wherein R is ₁Is an electron donating group or a halogenated aromatic ring electron donating group, R ₂Is a firstThe group is an aromatic ring electron donating group or a halogenated aromatic ring electron donating group, and X is a hydrogen atom or a halogen atom; the X, R ₁、R ₂At least one group contains a halogen atom.

Preferably, the aromatic ring electron donating group and the halogenated aromatic ring electron donating group are phenyl, carbazolyl, phenoxazinyl, phenothiazinyl, acridinyl, fluorenyl, spirofluorenyl, dibenzofluorenyl, dibenzothienyl, dianilino, trianilino or phenylazedinyl.

More preferably, the structures of the aromatic ring electron-donating group and the halogenated aromatic ring electron-donating group are as follows:

wherein R' are the same or different halogen atoms or hydrogen atoms; r' is a halogen atom if X is a hydrogen atom; if X is a halogen atom, R' is a hydrogen atom or a halogen atom. I.e. X and R' are not both hydrogen atoms.

Preferably, X is a halogen atom.

The preparation method of the organic electroluminescent material based on the halogenated aromatic ketone derivative comprises the following steps: the halogenated aromatic ring derivative and the p-fluorobenzoyl chloride are subjected to Friedel-crafts acylation reaction to obtain a corresponding organic intermediate, and the organic intermediate is reacted with electron-donating groups of different aromatic derivatives under the action of potassium tert-butoxide to obtain the organic electroluminescent material based on the halogenated aromatic ketone derivative.

Preferably, the halogenated aromatic ring derivative is

Wherein X is hydrogen atom or halogen atom, R is aryl or halogenated aryl, methyl or hydrogen, and at least one group of X, R contains halogen atom.

The organic electroluminescent material based on the halogenated aromatic ketone derivative is applied to the field of organic photoelectricity.

Preferably, the organic electroluminescent material based on the halogenated aromatic ketone derivative is applied to the preparation of organic OLEDs.

Compared with the prior art, the invention has the following beneficial effects:

(1) the organic electroluminescent material based on the halogenated aromatic ketone derivative is simple to synthesize, high in efficiency and stable in property.

(2) The organic electroluminescent material based on the halogenated aromatic ketone derivative has AIDF (aid fluorescence) property and high solid-state fluorescence quantum efficiency.

(3) The OLEDs prepared by the organic electroluminescent material based on the halogenated aromatic ketone derivative have high efficiency of non-doped devices, and the efficiency roll-off is still low under high brightness. The material has strong applicability, and OLEDs (organic light emitting diodes) devices with different doping concentrations show high device efficiency and low efficiency roll-off under high brightness, and are expected to be widely applied to lighting and display equipment.

Drawings

FIG. 1 is a graph of external quantum efficiency versus luminance of undoped OLEDs obtained from organic electroluminescent molecules based on halogenated aromatic ketone derivatives of examples 1, 2 and 3.

FIG. 2 is a graph of external quantum efficiency versus luminance of doped OLEDs obtained from organic electroluminescent molecules based on halogenated aromatic ketone derivatives of example 1.

FIG. 3 is a graph of external quantum efficiency versus luminance of doped OLEDs obtained from organic electroluminescent molecules based on halogenated aromatic ketone derivatives of example 2.

FIG. 4 is a graph of external quantum efficiency versus luminance of doped OLEDs obtained from organic electroluminescent molecules based on halogenated aromatic ketone derivatives of example 3.

FIG. 5 is a graph showing the external quantum efficiency and luminance of undoped OLEDs obtained from the organic electroluminescent molecules based on halogenated aromatic ketone derivatives of example 4.

Detailed Description

The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.