阅读说明：本技术 一种七元杂环为主体的有机电致发光材料及其应用 (Organic electroluminescent material with seven-membered heterocycle as main body and application thereof ) 是由 宋有永 陈倩倩 李燕藏 衣秀羽 蔡庆功 于 2019-11-18 设计创作，主要内容包括：本发明涉及一种七元杂环为主体的有机电致发光材料,所述七元杂环为主体的有机电致发光材料的结构如通式[I]：<Image he="425" wi="425" file="DDA0002277620240000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>所述的R取代基为C6～C80之间的芳基或杂芳基及其衍生物,所述的X原子为O或S中的一种,所述七元杂环为主体的有机电致发光材料的结构中含有咔唑或螺环结构。所述的七元杂环为主体的有机电致发光材料应用于有机电致发光器件的发光层或空穴传输层。所述的七元杂环为主体的有机电致发光材料应用在有机电致发光器件上表现出较好的热稳定性、较好的色纯度、较好的发光效率、较高的外部量子效率、较低的驱动电压,尤其具有较长的使用寿命。(The invention relates to an organic electroluminescent material taking seven-membered heterocycle as a main body, and the structure of the organic electroluminescent material taking seven-membered heterocycle as the main body is shown as a general formula (I)]： The R substituent is aryl or heteroaryl between C6-C80 and derivatives thereof, the X atom is one of O or S, and the structure of the organic electroluminescent material taking the seven-membered heterocycle as the main body contains a carbazole or spiro structure. The seven-membered heterocycle is an organic capacitor with a main bodyThe electroluminescent material is applied to a light-emitting layer or a hole transport layer of an organic electroluminescent device. The organic electroluminescent material with seven-membered heterocycle as the main body shows better thermal stability, better color purity, better luminous efficiency, higher external quantum efficiency and lower driving voltage when being applied to an organic electroluminescent device, and particularly has longer service life.)

1. An organic electroluminescent material with seven-membered heterocycle as a main body is characterized in that the structure of the organic electroluminescent material with seven-membered heterocycle as the main body is shown as a general formula [ I ]:

the R substituent is aryl or heteroaryl between C6-C80 and derivatives thereof, and the X atom is one of O or S.

2. The organic electroluminescent material with a seven-membered heterocycle as a main body according to claim 1, wherein the structure of the organic electroluminescent material with a seven-membered heterocycle as a main body contains a carbazole or spiro structure.

3. The organic electroluminescent material with a seven-membered heterocycle as the main body as claimed in claim 1, wherein the structure of the organic electroluminescent material with a seven-membered heterocycle as the main body is any one of the following structural formulas:

4. the use of the seven-membered heterocyclic ring-based organic electroluminescent material according to any one of claims 1 to 3, wherein the seven-membered heterocyclic ring-based organic electroluminescent material is used in an organic electroluminescent device.

5. The use of the organic electroluminescent material with a seven-membered heterocycle as the main component according to claim 4, wherein the organic electroluminescent material with a seven-membered heterocycle as the main component is used in a light-emitting layer of an organic electroluminescent device, and the organic electroluminescent material with a seven-membered heterocycle as the main component is used as the light-emitting material.

6. The use of the organic electroluminescent material with a seven-membered heterocycle as the main component according to claim 4, wherein the organic electroluminescent material with a seven-membered heterocycle as the main component is used in a hole transport layer of an organic electroluminescent device, and the organic electroluminescent material with a seven-membered heterocycle as the main component is used as a hole transport material.

Technical Field

The invention relates to an organic electroluminescent material with seven-membered heterocycle as a main body and application thereof, belonging to the technical field of electronic luminescent materials.

Background

Organic electroluminescent diodes (O L ED) were discovered by dune cloud, et al, kodak corporation, usa, in the 80 th century, and first produced organic light emitting devices with a double-layered structure having a charge transport layer.

O L ED is generally composed of ITO anode, low work function metal cathode and organic thin film active material, wherein, the organic active layer for light emission can be subdivided into hole injection/transport layer, light emitting layer, hole blocking/electron transport layer, etc. organic small molecule material can be formed into film by vacuum thermal evaporation technique, while polymer material is formed into film by solution processing technique such as spin coating, ink jet printing, etc. O L ED has similar working principle as inorganic light emitting diode, belonging to the injection-composite light emission of electron and hole, which is the process of converting electric energy into light energy.

The electroluminescent material always occupies the main position in the O L ED technology, good electroluminescent material is one of the key factors for determining the performance of the luminescent device, the indexes for determining the performance of the luminescent material mainly comprise three indexes, namely thermal stability, quantum efficiency and color purity, the better the thermal stability of the luminescent material is in the luminescent process, the better the performance of the luminescent device is, the higher the quantum efficiency of the luminescent material is, the better the color purity is, the performance of the luminescent device is, but the problems of short service life, poor thermal stability, low luminescent efficiency and the like of the luminescent material at present seriously limit the popularization of the luminescent device, so how to develop the luminescent material with good thermal stability, high quantum efficiency, high color purity and long service life is better, and the research personnel pay attention to the luminescent material widely.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides an organic luminescent material taking seven-membered heterocycle with a novel structure as a main body and application thereof, and overcomes the defects of short service life, poor thermal stability, low luminous efficiency and the like in the existing luminescent material.

The technical scheme for solving the technical problems is as follows: an organic electroluminescent material with seven-membered heterocycle as a main body is characterized in that the structure of the organic electroluminescent material with seven-membered heterocycle as the main body is shown as a general formula [ I ]:

the R substituent is aryl or heteroaryl between C6-C80 and derivatives thereof, and the X atom is one of O or S.

Preferably, the structure of the organic electroluminescent material mainly containing the seven-membered heterocycle contains a carbazole or spiro structure.

Preferably, the seven-membered heterocycle-based organic electroluminescent material has a structure represented by any one of the following structural formulas, but is not limited to the following structures:

the invention also discloses a method for synthesizing the seven-membered heterocyclic main body structure I and the main body structure II, which comprises the following steps: the specific synthetic route of the seven-membered heterocyclic main body structure I is as follows:

the synthesis method of the seven-membered heterocyclic main body structure I comprises the following steps:

a. under the protection of inert gas, uniformly mixing a compound 3-chloro-2-bromobenzoate, potassium carbonate, purified water and toluene, adding tetratriphenylphosphine palladium, dropwise adding an ethanol solution of o-methoxyphenylboronic acid at controlled temperature, and keeping the temperature for 2-20 hours to completely react. Washing with water, passing through a column, and recrystallizing to obtain a compound A, wherein the total yield is as follows: 55.0-75.0%, GC: not less than 99.0 percent.

b. And under the protection of inert gas, controlling the temperature, slowly dropwise adding a THF solution of the compound A into a THF solution containing phenylmagnesium chloride, keeping the temperature for reaction for 1-10 h, completely reacting, hydrolyzing, extracting, washing with water, passing through a column, and recrystallizing to obtain a compound B, wherein the total yield is 70.0-90.0%, and the total yield of HP L C is more than or equal to 99.0%.

c. And (2) under the protection of inert gas, controlling the temperature, dropwise adding a dichloroethane solution of methanesulfonic acid into the dichloroethane solution of the compound B, keeping the temperature for 2-20 h after dropwise adding, completely reacting, and performing hydrolysis, water washing, column chromatography and recrystallization on the post-treatment to obtain a compound C, wherein the total yield is 75.0-95.0%, and the total yield of HP L C is more than or equal to 99.5%.

d. Under the protection of inert gas, uniformly mixing the compound C, pinacol ester diboron borate, potassium acetate and dioxane, adding diphenylphosphine palladium dichloride, keeping the temperature for 2-20 h, completely reacting, performing post-treatment, hydrolyzing, extracting, washing with water, decoloring, passing through a column, and recrystallizing to obtain a compound D, wherein the total yield is 45.0-65.0%, and the total yield of HP L C is more than or equal to 99.0%.

e. Under the protection of inert gas, uniformly mixing a compound 3-fluoro-2-bromonitrobenzene, potassium carbonate, water and toluene, adding palladium acetate and xanthene, controlling the temperature, dropwise adding a THF solution of the compound D, keeping the temperature for 2-20 h after dropwise adding is finished, completely reacting, carrying out aftertreatment, washing with water, passing through a column, and recrystallizing to obtain a compound E, wherein the total yield is 50.0-70.0%, and the HP L C is more than or equal to 99.0%.

f. Under the protection of inert gas, controlling the temperature, dropwise adding boron tribromide into a dichloroethane solution containing the compound D, preserving the temperature for 1-10 h, completely reacting, performing post-treatment, hydrolyzing, washing and passing through a column to obtain a compound F, wherein the total yield is 80.0-100.0%, and the HP L C is more than or equal to 98.0%.

g. And (2) under the protection of inert gas, uniformly mixing the compound F, potassium carbonate and DMF, preserving the temperature for 1-10 h, completely reacting, and carrying out post-treatment, filtration, extraction and washing, column chromatography and recrystallization to obtain a compound G, wherein the total yield is 75.0-95.0%, and the HP L C is more than or equal to 99.5%.

h. Under the protection of inert gas, uniformly mixing the compound G, triphenylphosphine and o-dichlorobenzene, keeping the temperature for 2-20 h, completely reacting, washing the obtained product with water, passing through a column, and recrystallizing to obtain a compound with a main structure, wherein the total yield is 65.0-85.0%, and the HP L C content is not less than 99.5%.

The specific synthetic route of the seven-membered heterocyclic main body structure II is as follows:

the synthesis method of the seven-membered heterocyclic main body structure II comprises the following steps:

a. under the protection of inert gas, uniformly mixing a compound 3-chloro-2-bromobenzoate, sodium carbonate, purified water, toluene and phenylboronic acid, adding palladium tetratriphenylphosphine, and keeping the temperature for 2-20 h to completely react. And (3) carrying out water washing, column chromatography and recrystallization on the post-treatment to obtain a compound H, wherein the total yield is as follows: 70.0-90.0%, GC: not less than 99.0 percent.

b. And under the protection of inert gas, controlling the temperature, slowly dropwise adding a THF solution of a compound H into a THF solution containing phenylmagnesium chloride, preserving the temperature for 1-10H after dropwise adding, completely reacting, performing post-treatment, hydrolyzing, extracting, washing with water, passing through a column, and recrystallizing to obtain a compound I, wherein the total yield is 75.0-95.0%, and the total yield of HP L C is not less than 99.0%.

c. And (2) under the protection of inert gas, controlling the temperature, dropwise adding a dichloroethane solution of methanesulfonic acid into the dichloroethane solution of the compound I, keeping the temperature for 2-20 h after dropwise adding, completely reacting, and performing hydrolysis, water washing, column chromatography and recrystallization on the post-treatment to obtain a compound J, wherein the total yield is 75.0-95.0% and the HP L C is more than or equal to 99.5%.

d. Under the protection of inert gas, uniformly mixing the compound J, pinacol ester diboron borate, potassium acetate and dioxane, adding diphenylphosphine palladium dichloride, keeping the temperature for 2-20 h, completely reacting, performing post-treatment, hydrolyzing, extracting, washing with water, decoloring, passing through a column, and recrystallizing to obtain the compound K, wherein the total yield is 65.0-85.0%, and the total yield of HP L C is more than or equal to 99.0%.

e. Under the protection of inert gas, uniformly mixing a compound 3-mercapto-2-bromonitrobenzene, potassium carbonate, water and toluene, adding palladium acetate and tricyclohexylphosphine, dropwise adding a THF solution of a compound K at a controlled temperature, keeping the temperature for 2-20 h to completely react, carrying out aftertreatment, washing with water, passing through a column, and recrystallizing to obtain a compound L, wherein the total yield is 40.0-60.0%, and the HP L C is more than or equal to 99.0%.

f. Under the protection of inert gas, uniformly mixing the compound L, triphenylphosphine and o-dichlorobenzene, keeping the temperature for 2-20 h, and completely reacting, washing the mixture with water, passing through a column, and recrystallizing to obtain the compound M, wherein the total yield is 75.0-95.0%, and the HP L C is not less than 99.5%.

g. Under the protection of inert gas, the compound M, DMSO is uniformly mixed, palladium dichloride is added, the temperature is kept for 2-20 hours, the reaction is complete, two compounds with main structure are obtained through post-treatment, extraction, water washing, column chromatography and recrystallization, the total yield is 20.0-40.0%, and the HP L C is more than or equal to 99.5%.

The invention also discloses an application of the organic electroluminescent material taking the seven-membered heterocycle as a main body, which comprises the following steps: the organic electroluminescent material with seven-membered heterocycle as the main body is applied to organic electroluminescent devices.

Furthermore, the organic electroluminescent material with the seven-membered heterocycle as the main body is applied to a light-emitting layer of an organic electroluminescent device, and the organic electroluminescent material with the seven-membered heterocycle as the main body is used as a light-emitting main body material.

Furthermore, the organic electroluminescent material with the seven-membered heterocycle as the main body is applied to a hole transport layer of an organic electroluminescent device, and the organic electroluminescent material with the seven-membered heterocycle as the main body is used as a hole transport material.

Compared with the known compounds in commercial application, the organic electroluminescent material taking the seven-membered heterocycle as the main body shows better thermal stability, better color purity, better luminous efficiency, higher external quantum efficiency, lower driving voltage and especially longer service life when being applied to an organic electroluminescent device.

Drawings

FIG. 1 is a schematic structural view of an organic electroluminescent device described in the examples;

in the figure, 1 a transparent substrate layer, 2 a transparent electrode layer, 3 a hole injection layer, 4 a hole transport layer, 5 a light emitting layer, 6 an electron transport layer, 7 an electron injection layer, 8 a cathode reflection electrode layer.

Detailed Description

The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.