阅读说明：本技术 一种芘类蓝色荧光掺杂物质，包含此物质的有机电致发光器件 (Pyrene blue fluorescence doping substance and organic electroluminescent device containing pyrene blue fluorescence doping substance ) 是由 钱超 许军 于 2019-04-29 设计创作，主要内容包括：本发明公开了一种芘类蓝色荧光掺杂物质,包含此物质的有机电致发光器件,该化合物结构式如式I所示：<Image he="607" wi="453" file="DDA0002045180740000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>该类化合物能够作为有机电致发光材料应用。与对比技术相比,该技术设计发明的材料在发光效率、寿命、色纯度、材料的热稳定性及使用范围上有极大的改善及提高。有效的解决了现有技术中寿命短,效率低、良率低等问题。(The invention discloses a pyrene blue fluorescence doping substance, an organic electroluminescent device containing the substance, and the structural formula of the compound is shown as the formula I: the compounds can be used as organic electroluminescent materials. Compared with the comparative technology, the technology designs the material of the invention to have luminous efficiency, service life and colorThe purity, the thermal stability and the application range of the material are greatly improved. The problems of short service life, low efficiency, low yield and the like in the prior art are effectively solved.)

1. An organic electroluminescent compound, the structural formula of which is shown in formula (I):

wherein Ar1, Ar2, Ar3 and Ar4 are respectively and independently substituted or unsubstituted silane groups or silicon derivative groups, substituted or unsubstituted C1-C40 straight-chain or branched-chain alkyl groups, substituted or unsubstituted C3-C40 cycloalkyl groups, substituted or unsubstituted C1-C40 heteroalkyl groups, substituted or unsubstituted C2-C40 alkenyl groups, substituted or unsubstituted C2-C40 alkynyl groups, substituted or unsubstituted C6-C60 aromatic hydrocarbon groups and substituted or unsubstituted C5-C60 aromatic heterohydrocarbon groups;

r1, R2, R3 and R4 are respectively and independently selected from cyano, CF3, substituted or unsubstituted silane groups or silicon derivative groups, substituted or unsubstituted C1-C40 straight-chain or branched alkyl groups, substituted or unsubstituted C3-C40 cycloalkyl groups, substituted or unsubstituted C1-C40 heteroalkyl groups, substituted or unsubstituted C2-C40 alkenyl groups, substituted or unsubstituted C2-C40 alkynyl groups, substituted or unsubstituted C6-C60 aromatic hydrocarbon groups and substituted or unsubstituted C5-C60 heteroaromatic hydrocarbon groups.

2. The organic electroluminescent compound according to claim 1,

wherein, Ar1, Ar2, Ar3, Ar4 are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted 3, 5-diphenylphenyl group, a substituted or unsubstituted 1, 2-diphenylphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted 9, 9-spirobifluorene group, a substituted or unsubstituted 9, 9-dimethylfluorene group, a substituted or unsubstituted carbazolyl group and a derivative group thereof, a substituted or unsubstituted furan group and a derivative group thereof, a substituted or unsubstituted thiophene group and a derivative group thereof, a substituted or unsubstituted naphthalene group and a derivative group thereof;

R1, R2, R3, R4 are each independently selected from the group consisting of methyl, methyl wherein one or more hydrogens are replaced with deuterium (D) or are unsubstituted, ethyl, hexyl wherein one or more hydrogens are replaced with deuterium (D) or are unsubstituted, isopropyl wherein one or more hydrogens are replaced with deuterium (D) or are unsubstituted, tert-butyl, tert-butyl groups in which one or more hydrogens are replaced by deuterohydrogen (D), substituted or unsubstituted silane groups or silicon derivative groups, substituted or substituted phenyl groups, substituted or unsubstituted tolyl groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted terphenyl groups, substituted or unsubstituted fluorene derivative groups, substituted or unsubstituted carbazole and its derivative groups, substituted or unsubstituted furan and its derivative groups, and substituted or unsubstituted thiophene and its derivative groups.

3. The organic electroluminescent compound according to claim 1 or 2,

wherein Ar1, Ar2, Ar3 and Ar4 are each independently phenyl, methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, pentafluorophenyl, 4-fluorophenyl, 4-cyanophenyl, biphenyl, 1-naphthyl, 2-naphthyl, dibenzofuranyl, 4-methyldibenzofuranyl, 4-ethyldibenzofuranyl, 4-isopropyldibenzofuranyl, 4-tert-butyldibenzofuranyl, carbazolyl or dibenzothiophenyl;

R1, R2, R3 and R4 are each independently selected from the group consisting of methyl, monodeomethyl, dideuteromethyl, trideuteromethyl, ethyl, monodeoethyl, dideuteroethyl, trideuteroethyl, tetradeuteroethyl, pentadeoethyl, isopropyl, monodeoisopropyl, dideuteroisopropyl, trideeoisopropyl, tetradeuteroisopropyl, pentadeoisopropyl, hexadeuteroisopropyl, heptadeuteroisopropyl, tert-butyl, monodeotert-butyl, dideuter-tert-butyl, trideuter-tert-butyl, tetradeuterotert-butyl, pentadeotert-butyl, hexadeuterotert-butyl, heptadeuterotert-butyl, octadeuterotert-butyl, nonadeuterotert-butyl, phenyl, tolyl, 4-fluorophenyl, 4-cyanophenyl, pentafluorophenyl, biphenyl, terphenyl, 4-trifluoromethylphenyl, 3, 5-diphenylphenyl, 1, 2-diphenylphenyl and the like, A hexadeuterated 9, 9-dimethylfluorene group, a 9, 9-diphenylfluorene group, and a 9, 9-spirobifluorene group.

4. The organic electroluminescent compound according to claim 3,

wherein Ar1, Ar2, Ar3 and Ar4 are each independently phenyl, methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, pentafluorophenyl, 4-fluorophenyl, 4-cyanophenyl, biphenyl, 1-naphthyl, 2-naphthyl, dibenzofuranyl, 4-methyldibenzofuranyl, 4-ethyldibenzofuranyl, 4-isopropyldibenzofuranyl, 4-tert-butyldibenzofuranyl or dibenzothiophenyl;

R1, R2, R3 and R4 are each independently selected from methyl, trideuteromethyl, ethyl, dideuteroethyl, pentaduteroethyl, isopropyl, monoduteroisopropyl, heptadeuteroisopropyl, tert-butyl, nonadeuterotert-butyl, phenyl, tolyl, 4-fluorophenyl, 4-cyanophenyl, pentafluorophenyl, biphenyl, terphenyl, 4-trifluoromethylphenyl, 3, 5-diphenylphenyl, 1, 2-diphenylphenyl, hexadeutero-9, 9-dimethylfluorene group, 9-diphenylfluorene group and 9, 9-spirobifluorene group.

5. The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound is any one of compounds G1 to G228:

。

6. an organic electroluminescent device comprising the organic electroluminescent compound as claimed in any one of claims 1 to 5.

7. The organic electroluminescent device according to claim 6, wherein the organic electroluminescent device comprises:

a structure in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially stacked;

wherein an electron blocking layer is arranged between the anode and the luminescent layer;

a hole blocking layer is arranged between the cathode and the luminescent layer;

The surface of the cathode is also provided with a covering layer.

8. The organic electroluminescent device according to claim 7, wherein at least one of the hole transport layer, the electron blocking layer, the hole blocking layer, the electron transport layer, the light emitting layer material, or the cover layer comprises the organic electroluminescent compound according to any one of claims 1 to 5.

9. An organic electroluminescent display device comprising the organic electroluminescent device according to any one of claims 6 to 8.

10. Use of a compound according to any one of claims 1 to 5 as an organic electroluminescent material.

Technical Field

The invention belongs to the technical field of organic electroluminescent materials, and particularly relates to an organic electroluminescent compound and a preparation method and application thereof.

Background

Organic Light-emitting Devices (OLEDs) are spontaneous Light-emitting Devices that utilize the following principle: when an electric field is applied, the fluorescent substance emits light by recombination of holes injected from the positive electrode and electrons injected from the negative electrode. The self-luminous device has the characteristics of low voltage, high brightness, wide viewing angle, quick response, good temperature adaptability and the like, is ultrathin, can be manufactured on a flexible panel and the like, and is widely applied to the fields of mobile phones, tablet computers, televisions, illumination and the like.

The organic electroluminescent device is like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers or recommended by a user, and the different functional materials are mutually overlapped together according to the purpose to form the organic electroluminescent device. When the organic electroluminescent device is used as a current device, voltage is applied to two end electrodes of the organic electroluminescent device, positive and negative charges are generated in the organic layer functional material film layer under the action of an electric field, the positive and negative charges are further compounded in the light emitting layer to generate light, and the process is electroluminescence.

The research on the improvement of the performance of the organic electroluminescent device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the organic electroluminescent device, not only the innovation of the structure and the manufacturing process of the organic electroluminescent device is required, but also the continuous research and innovation of the organic electro-photoelectric functional material are required, and the organic electroluminescent functional material with higher performance is created.

In terms of the actual demand of the current organic electroluminescent industry, the development of the current organic electroluminescent materials is far from enough and lags behind the requirements of panel manufacturing enterprises.

Compared with the current prior art 2015110294947, the material designed by the invention has higher efficiency, higher color purity and longer service life. The blue light doped material of the prior art 2015110294947 has a fluorescence emission wavelength between 468-490nm, and has an emission color from light blue to sky blue. The blue fluorescent compound designed by the invention has the fluorescence emission wavelength of 440-460 and the color of dark blue, and the higher color purity is more favorable for improving the color saturation, the luminous efficiency and the service life of the luminescent device. Compared with 2015110294947 in the prior art, due to the change of the molecular structure of the core structure, the planarity of the core structure is reduced, the crystallinity of the product is reduced, the lower crystallinity can effectively prevent the material from generating cracks in the evaporation process, the yield of device preparation is improved, the changed core structure has better thermal stability, and the application range and the application of the material are increased.

Disclosure of Invention

The purpose of the invention is as follows: in order to solve the technical problems, the invention provides an organic electroluminescent compound, a preparation method and application thereof, wherein the compound can be used as a Blue dopant (Blue dopant).

In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:

an organic electroluminescent compound, the structural formula of which is shown in formula (I):

wherein Ar1, Ar2, Ar3 and Ar4 are respectively and independently substituted or unsubstituted silane groups or silicon derivative groups, substituted or unsubstituted C1-C40 straight-chain or branched-chain alkyl groups, substituted or unsubstituted C3-C40 cycloalkyl groups, substituted or unsubstituted C1-C40 heteroalkyl groups, substituted or unsubstituted C2-C40 alkenyl groups, substituted or unsubstituted C2-C40 alkynyl groups, substituted or unsubstituted C6-C60 aromatic hydrocarbon groups and substituted or unsubstituted C5-C60 aromatic heterohydrocarbon groups;

r1, R2, R3 and R4 are respectively and independently selected from cyano, CF3, substituted or unsubstituted silane groups or silicon derivative groups, substituted or unsubstituted C1-C40 straight-chain or branched alkyl groups, substituted or unsubstituted C3-C40 cycloalkyl groups, substituted or unsubstituted C1-C40 heteroalkyl groups, substituted or unsubstituted C2-C40 alkenyl groups, substituted or unsubstituted C2-C40 alkynyl groups, substituted or unsubstituted C6-C60 aromatic hydrocarbon groups and substituted or unsubstituted C5-C60 heteroaromatic hydrocarbon groups.

The further preferable technical scheme of the invention is as follows:

Wherein, Ar1, Ar2, Ar3, Ar4 are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted 3, 5-diphenylphenyl group, a substituted or unsubstituted 1, 2-diphenylphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted 9, 9-spirobifluorene group, a substituted or unsubstituted 9, 9-dimethylfluorene group, a substituted or unsubstituted carbazolyl group and a derivative group thereof, a substituted or unsubstituted furan group and a derivative group thereof, a substituted or unsubstituted thiophene group and a derivative group thereof, a substituted or unsubstituted naphthalene group and a derivative group thereof;

r1, R2, R3, R4 are each independently selected from the group consisting of methyl, methyl wherein one or more hydrogens are replaced with deuterium (D) or are unsubstituted, ethyl, hexyl wherein one or more hydrogens are replaced with deuterium (D) or are unsubstituted, isopropyl wherein one or more hydrogens are replaced with deuterium (D) or are unsubstituted, tert-butyl, tert-butyl groups in which one or more hydrogens are replaced by deuterohydrogen (D), substituted or unsubstituted silane groups or silicon derivative groups, substituted or substituted phenyl groups, substituted or unsubstituted tolyl groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted terphenyl groups, substituted or unsubstituted fluorene derivative groups, substituted or unsubstituted carbazole and its derivative groups, substituted or unsubstituted furan and its derivative groups, and substituted or unsubstituted thiophene and its derivative groups.

The further preferable technical scheme of the invention is as follows:

wherein Ar1, Ar2, Ar3 and Ar4 are each independently phenyl, methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, pentafluorophenyl, o-fluorophenyl, m-fluorophenyl, 4-cyanophenyl, biphenyl, 1-naphthyl, 2-naphthyl, dibenzofuranyl, 4-methyldibenzofuranyl, 4-ethyldibenzofuranyl, 4-isopropyldibenzofuranyl, 4-tert-butyldibenzofuranyl, carbazolyl, 3-phenylcarbazolyl, 3-biphenylcarbazolyl, 9-phenylcarbazolyl or dibenzothiophenyl;

r1, R2, R3 and R4 are each independently selected from the group consisting of methyl, monodeomethyl, dideuteromethyl, trideuteromethyl, ethyl, monodeoethyl, dideuteroethyl, trideuteroethyl, tetradeuteroethyl, pentadeoethyl, isopropyl, monodeoisopropyl, dideuteroisopropyl, trideeoisopropyl, tetradeuteroisopropyl, pentadeoisopropyl, hexadeuteroisopropyl, heptadeuteroisopropyl, tert-butyl, monodeotert-butyl, dideuter-tert-butyl, trideuter-tert-butyl, tetradeuterotert-butyl, pentadeotert-butyl, hexadeuterotert-butyl, heptadeuterotert-butyl, octadeuterotert-butyl, nonadeuterotert-butyl, phenyl, tolyl, 4-fluorophenyl, 4-cyanophenyl, pentafluorophenyl, biphenyl, terphenyl, 4-trifluoromethylphenyl, 3, 5-diphenylphenyl, 1, 2-diphenylphenyl and the like, A hexadeuterated 9, 9-dimethylfluorene group, a 9, 9-diphenylfluorene group, and a 9, 9-spirobifluorene group.

The further preferable technical scheme of the invention is as follows:

wherein Ar1, Ar2, Ar3 and Ar4 are each independently phenyl, methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, pentafluorophenyl, 4-fluorophenyl, 4-cyanophenyl, biphenyl (o-biphenyl, m-biphenyl, p-biphenyl), 1-naphthyl, 2-naphthyl, dibenzofuranyl, 4-methyldibenzofuranyl, 4-ethyldibenzofuranyl, 4-isopropyldibenzofuranyl, 4-tert-butyldibenzofuranyl, dibenzothiophenyl, carbazolyl;

r1, R2, R3 and R4 are independently selected from methyl, trideuteromethyl, ethyl, dideuteroethyl, pentaduteroethyl, isopropyl, monoduteroisopropyl, heptadeuteroisopropyl, tert-butyl, nonadeuterotert-butyl, phenyl, tolyl, 4-fluorophenyl, 4-cyanophenyl, pentafluorophenyl, biphenyl, terphenyl, 4-trifluoromethylphenyl, 3, 5-diphenylphenyl, 1, 2-diphenylphenyl, hexadeutero-9, 9-dimethylfluorene, 9-diphenylfluorene, 9-spirobifluorene, carbazolyl, 9-phenylcarbazolyl, 3-biphenylcarbazolyl and 3, 6-diphenylcarbazolyl.

The organic electroluminescent compound of the present invention is specifically any one of compounds G1 to G228:

An organic electroluminescent device comprising the organic electroluminescent compound.

Preferably, the organic electroluminescent device includes:

a structure in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially stacked;

wherein an electron blocking layer is arranged between the anode and the luminescent layer;

a hole blocking layer is arranged between the cathode and the luminescent layer;

the surface of the cathode is also provided with a covering layer.

At least one of the hole transport layer, the electron blocking layer, the hole blocking layer, the electron transport layer, the light emitting layer material, or the cover layer contains the organic electroluminescent compound.

An organic electroluminescent display device comprising the above organic electroluminescent device.

The application of the compound in serving as an organic electroluminescent material.

The invention has the beneficial effects that:

in comparison to current prior art 2015110294947, I designed the material of the invention to have higher efficiency, higher color purity, and longer life. The blue light doped material of the prior art 2015110294947 has a fluorescence emission wavelength between 468-490nm, and has an emission color from light blue to sky blue. The blue fluorescent compound designed by the invention of the technology has the fluorescence emission wavelength of 440-460 and the color of deep blue, and the higher color purity of the blue fluorescent compound is more favorable for improving the color saturation, the luminous efficiency and the service life of a luminescent device. Compared with 2015110294947 in the prior art, due to the change of the molecular structure of the core structure, the planarity of the core structure is reduced, the crystallinity of the product is reduced, the lower crystallinity can effectively prevent the material from generating cracks in the evaporation process, the yield of device preparation is improved (by using the technology, the yield of the device is improved to 80% from the previous 10%), the changed core structure has better thermal stability, and the application range and the application of the material are increased. Compared with the prior art, the material designed and invented by the technology has greatly improved luminous efficiency, service life, color purity, thermal stability and application range. The problems of short service life, low efficiency, low yield and the like in the prior art are effectively solved.

Detailed Description