阅读说明：本技术 一种二苯并噻吩衍生物及其有机发光器件 (Dibenzothiophene derivative and organic light-emitting device thereof ) 是由 韩春雪 周雯庭 孙月 于 2020-08-18 设计创作，主要内容包括：本发明提供一种二苯并噻吩衍生物及其有机发光器件,涉及有机光电材料技术领域。本发明以二苯并噻吩基连苯基芴基作为取代基团与三芳胺类结构连接,进一步增强了化合物的给电子能力,使得化合物具有良好的空穴传输性能,是良好的空穴传输材料；本发明所述二苯并噻吩衍生物具有特殊的刚性稠环结构,可以使基团整体的运动相对受限,显著降低材料的聚集态荧光淬灭现象,提高化合物的稳定性,且本发明提供的二苯并噻吩衍生物成膜性好,合成简单易操作,可广泛应用于面板显示、照明光源、有机太阳能电池、有机感光体或有机薄膜晶体管等领域。(The invention provides a dibenzothiophene derivative and an organic light-emitting device thereof, and relates to the technical field of organic photoelectric materials. According to the invention, dibenzothiophene-phenyl fluorenyl is used as a substituent group to be connected with a triarylamine structure, so that the electron donating capability of the compound is further enhanced, and the compound has good hole transport performance and is a good hole transport material; the dibenzothiophene derivative provided by the invention has a special rigid condensed ring structure, can relatively limit the movement of the whole group, remarkably reduces the aggregation state fluorescence quenching phenomenon of materials, and improves the stability of compounds.)

1. A dibenzothiophene derivative is characterized in that the molecular structural general formula is shown as formula I:

wherein, L is selected from one of single bond, substituted or unsubstituted C6-C25 arylene, substituted or unsubstituted C2-C20 heteroarylene;

Ar₁、Ar₂independently selected from one of substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl;

L₀one selected from single bond, substituted or unsubstituted C6-C25 arylene, substituted or unsubstituted C2-C20 heteroarylene;

R₁、R₂independently selected from one of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, acridinyl, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, pyrenyl, indolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl;

p and q are independently selected from integers of 0 to 4, and when p is greater than 1, each R₁Identical or different, or adjacent R₁Can be connected into a ring; when q is greater than 1, each R₂Identical or different, or adjacent R₂Can be connected into a ring.

2. The dibenzothiophene derivative according to claim 1, wherein formula i is selected from the group consisting of those represented by formulae i-a to i-m:

3. the dibenzothiophene derivative according to claim 1, whereinCharacterized in that Ar is₁、Ar₂Independently selected from one of the following groups:

wherein R is₁₂One selected from methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, phenyl, tolyl, biphenyl and naphthyl;

R₁₃one selected from deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, acridine, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, pyrenyl, indolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl;

L₁one selected from the group consisting of formulas (1) to (14):

a is selected from an integer of 0 to 3;

c is an integer from 0 to 4;

b is an integer from 0 to 5;

d is an integer from 0 to 7;

f is an integer from 0 to 9.

4. The dibenzothiophene derivative according to claim 1, wherein Ar is Ar₁One selected from the group shown below:

5. the dibenzothiophene derivative according to claim 1, wherein Ar is Ar₂Is selected from methylPhenyl, biphenyl, terphenyl, naphthyl, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl, dibenzofuranyl.

6. The dibenzothiophene derivative according to claim 1, wherein said L, L is₀Independently selected from one of single bond, phenylene, naphthylene, biphenylene, terphenylene, tolylene, dimethylphenylene and anthrylene.

7. The dibenzothiophene derivative according to claim 1, wherein said L, L is₀Independently selected from a single bond or any one of the following groups:

8. the dibenzothiophene derivative according to claim 1, wherein the dibenzothiophene derivative is selected from any one of the following chemical structures:

。

9. an organic light-emitting device comprising a cathode, an anode, and one or more organic layers disposed between and outside the cathode and the anode, wherein the organic layers comprise at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a capping layer; the organic layer contains any one or a combination of at least two of the dibenzothiophene derivatives according to any one of claims 1 to 8.

10. An organic light-emitting device according to claim 9, wherein the organic layer comprises a hole transport layer containing any one or a combination of at least two of the dibenzothiophene derivatives of any one of claims 1 to 8.

Technical Field

The invention relates to the technical field of organic photoelectric materials, in particular to a dibenzothiophene derivative and an organic light-emitting device thereof.

Background

The OLED is called as an organic light emitting diode or an organic light emitting display screen, and has the following characteristics as a new application technology in the display field: the material adopts organic matter/macromolecule, so the material selection range is wide, and the display of any color from red light to blue light can be realized; compared with flat panel displays such as field emission displays, plasma display devices and liquid crystal displays, the display panel has the characteristic of low driving voltage, and only needs 3-12V direct current voltage; the luminous brightness and luminous efficiency are high; the luminous visual angle is wide, and the response speed is high; the light-emitting diode is ultrathin, light in weight and capable of emitting light in a fully-cured active mode; the device can be made on a flexible substrate, and the device can be bent; the working temperature range is wide; the molding process is relatively simple, can directly form complex images and perform large-scale large-area production by using an ink-jet printing technology and the like, does not require expensive production lines and equipment, is easy to integrate with other products, and has excellent cost performance. In recent years, OLEDs have been increasingly used in the display market, and are currently the most promising panel display technology.

According to the difference of the organic light-emitting materials, the devices made of organic small molecules as the light-emitting materials are called organic light-emitting devices, abbreviated as OLEDs; a device made of polymer as an electroluminescent material is called a polymer electroluminescent device, abbreviated as PLED. Organic/polymer LEDs are display technologies based on organic semiconductor materials, and the realization and excellent performance of full color display thereof are determined by the properties of the materials, so that the materials are very important for the research of OLEDs. The most basic requirements as qualified organic light emitting materials are: (1) in solid or liquid state, the fluorescence has high efficiency in visible light region; (2) the conductive film has higher conductivity and shows good semiconductor characteristics; (3) the film has good film forming property, and basically has no pinholes in films of hundreds of nanometers or even dozens of nanometers; (4) has strong stability and generally has good mechanical processing performance. And can be further classified into a light emitting material, a hole transporting material, an electron transporting material, and the like according to the difference in function.

The hole transport layer has the basic functions of improving the transport efficiency of holes in the device and effectively blocking electrons in the light emitting layer to realize the maximum recombination of current carriers; meanwhile, the energy barrier of the holes in the injection process is reduced, and the injection efficiency of the holes is improved, so that the brightness, the efficiency and the service life of the device are improved. The hole transport material should have the following properties: a) the hole mobility is good, so that good hole transmission performance is guaranteed; b) capable of forming a uniform amorphous film free of pinholes; c) the formed amorphous film has good thermal stability; d) have suitable HOMO orbital levels to ensure efficient injection and transport of holes between the electrode/organic layer and the organic layer/organic layer interface.

Since the device is operating to generate joule heat, this heat often causes recrystallization of the material. Crystallization can destroy the uniformity of the film and also destroy the good interfacial contact between the hole transport layer and the anode and the organic layer, resulting in reduced efficiency and lifetime of the device. And the injection of holes and electrons is unbalanced due to the low mobility of the holes, and the holes and the electrons cannot be effectively combined in the light-emitting layer, so that the light-emitting efficiency of the organic light-emitting device is reduced. Therefore, the research on the organic hole transport material focuses on improving the thermal stability and hole mobility of the material.

In general, in the future, the OLED is developed to be a white light device and a full color display device with high efficiency, long lifetime and low cost, but the industrialization process of the technology still faces many key problems, and how to design a material with better performance for adjustment is a problem that needs to be solved by those skilled in the art.

Disclosure of Invention

The present invention is directed to a dibenzothiophene derivative and an organic light emitting device using the same, which have excellent light emitting efficiency.

The invention provides a dibenzothiophene derivative which is used as a main component of a hole transport layer in an organic light-emitting device and solves the problems, and the molecular structural general formula of the dibenzothiophene derivative is shown as the formula I:

wherein, L is selected from one of single bond, substituted or unsubstituted C6-C25 arylene, substituted or unsubstituted C2-C20 heteroarylene;

Ar₁、Ar₂independently selected from one of substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl;

L₀one selected from single bond, substituted or unsubstituted C6-C25 arylene, substituted or unsubstituted C2-C20 heteroarylene;

R₁、R₂independently selected from one of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, acridinyl, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, pyrenyl, indolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl;

p and q are independently selected from integers of 0 to 4, and when p is greater than 1, each R₁Identical or different, or adjacent R₁Can be connected into a ring; when q is greater than 1, each R₂Identical or different, or adjacent R₂Can be connected into a ring.

Preferably, the formula I is selected from one of the groups shown in the following formulas I-a to I-m:

preferably, Ar is₁、Ar₂Independently selected from one of the following groups:

wherein R is₁₂Selected from methyl, ethyl, n-propylOne of n-butyl, isopropyl, tert-butyl, phenyl, tolyl, biphenyl and naphthyl;

R₁₃one selected from deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, acridine, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, pyrenyl, indolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl;

L₁one selected from the group consisting of formulas (1) to (14):

a is selected from an integer of 0 to 3;

c is an integer from 0 to 4;

b is an integer from 0 to 5;

d is an integer from 0 to 7;

f is an integer from 0 to 9.

Preferably, Ar is₁One selected from the group shown below:

preferably, Ar is₂One selected from methyl, phenyl, biphenyl, terphenyl, naphthyl, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl and dibenzofuranyl.

Preferably, said L, L₀Independently selected from one of single bond, phenylene, naphthylene, biphenylene, terphenylene, tolylene, dimethylphenylene and anthrylene.

Preferably, said L, L₀Independently selected from a single bond or any one of the following groups:

the invention also provides an organic light-emitting device which comprises a cathode, an anode and one or more organic layers arranged between and outside the cathode and the anode, wherein the organic layer comprises at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a covering layer; the organic layer contains any one or a combination of at least two of any one of the dibenzothiophene derivatives described in the present invention.

Preferably, the organic layer according to the present invention includes a hole transport layer containing any one or a combination of at least two of the dibenzothiophene derivatives according to the present invention.

The invention has the beneficial effects that:

the invention provides a dibenzothiophene derivative and an organic light-emitting device thereof, wherein dibenzothiophene-phenyl fluorenyl is used as a substituent group to be connected with a triarylamine structure, so that the electron donating capability of the compound is further enhanced, and the compound has good hole transport performance and is a good hole transport material; the dibenzothiophene derivative provided by the invention has a special rigid condensed ring structure, so that the movement of the whole group is relatively limited, the aggregation state fluorescence quenching phenomenon of the material is obviously reduced, and the stability of the compound is improved.

The dibenzothiophene derivative provided by the invention is applied to an organic light-emitting device, and the organic light-emitting device prepared by using the dibenzothiophene derivative as a hole transport layer material has the advantage of high light-emitting efficiency.

Drawings

FIG. 1 is a drawing showing Compound 1 of the present invention¹H NMR chart; FIG. 2 shows Compound 2 of the present invention¹H NMR chart;

FIG. 3 is a drawing of Compound 15 of the present invention¹H NMR chart; FIG. 4 is a drawing showing Compound 17 of the present invention¹H NMR chart;

FIG. 5 is a drawing showing Compound 46 of the present invention¹H NMR chart; FIG. 6 is a drawing showing a scheme for preparing a compound 65 of the present invention¹H NMR chart;

FIG. 7 is a drawing showing a preparation of Compound 75 of the present invention¹H NMR chart; FIG. 8 is a drawing showing Compound 77 of the present invention¹H NMR chart;

FIG. 9 is a drawing showing a scheme of preparation of compound 109 of the present invention¹H NMR chart; FIG. 10 is a photograph of Compound 173 of the present invention¹H NMR chart.

Detailed Description

The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of the present invention.

The alkyl group in the present invention refers to a hydrocarbon group formed by dropping one hydrogen atom from an alkane molecule, and may be a straight-chain alkyl group, a branched-chain alkyl group, or a cyclic alkyl group, and preferably has 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The straight chain alkyl group includes methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like, but is not limited thereto; the branched alkyl group includes, but is not limited to, an isomeric group of isopropyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, an isomeric group of n-hexyl, an isomeric group of n-heptyl, an isomeric group of n-octyl, an isomeric group of n-nonyl, an isomeric group of n-decyl, etc.; the cycloalkyl group includes cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, and the like, but is not limited thereto. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group or a 2-adamantyl group.

The aryl group in the present invention refers to a general term of monovalent group remaining after one hydrogen atom is removed from an aromatic nucleus carbon of an aromatic compound molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 14 carbon atoms. The monocyclic aryl group means an aryl group having only one aromatic ring in the molecule, for example, phenyl group and the like, but is not limited thereto; the polycyclic aromatic group means an aromatic group having two or more independent aromatic rings in the molecule, for example, biphenyl group, terphenyl group and the like, but is not limited thereto; the fused ring aryl group refers to an aryl group in which two or more aromatic rings are contained in a molecule and are fused together by sharing two adjacent carbon atoms, and examples thereof include, but are not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylene, fluoranthenyl, spirobifluorenyl, and the like. The above aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group (preferably a 2-naphthyl group), an anthryl group (preferably a 2-anthryl group), a phenanthryl group, a pyrenyl group, a perylenyl group, a fluorenyl group, a benzofluorenyl group, a triphenylene group, or a spirobifluorenyl group.

The heteroaryl group in the present invention refers to a general term of a group obtained by replacing one or more aromatic nucleus carbon atoms in an aryl group with a heteroatom, including but not limited to oxygen, sulfur, nitrogen or phosphorus atom, preferably having 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 3 to 15 carbon atoms, wherein the attachment site of the heteroaryl group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a fused ring heteroaryl group. The monocyclic heteroaryl group includes pyridyl, pyrimidyl, triazinyl, furyl, thienyl, pyrrolyl, imidazolyl and the like, but is not limited thereto; the polycyclic heteroaryl group includes bipyridyl, phenylpyridyl, and the like, but is not limited thereto; the fused ring heteroaryl group includes quinolyl, isoquinolyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiyl and the like, but is not limited thereto. The heteroaryl group is preferably a pyridyl group, a pyrimidyl group, a thienyl group, a furyl group, a benzothienyl group, a benzofuryl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuryl group, a dibenzothienyl group, a dibenzofuryl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group or a phenoxathiyl group.

The arylene group in the present invention refers to a general term of a divalent group remaining after two hydrogen atoms are removed from an aromatic core carbon of an aromatic compound molecule, and may be a monocyclic arylene group, a polycyclic arylene group or a condensed ring arylene group, and preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 14 carbon atoms. The monocyclic arylene group includes phenylene group and the like, but is not limited thereto; the polycyclic arylene group includes, but is not limited to, biphenylene, terphenylene, and the like; the condensed ring arylene group includes naphthylene, anthrylene, phenanthrylene, fluorenylene, pyrenylene, triphenylene, fluoranthenylene, phenylfluorenylene, and the like, but is not limited thereto. The arylene group is preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a fluorenylene group, or a phenylfluorenylene group.

Heteroarylene as used herein refers to the generic term for groups in which one or more of the aromatic core carbons in the arylene group is replaced with a heteroatom, including, but not limited to, oxygen, sulfur, nitrogen, or phosphorus atoms. Preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 15 carbon atoms, and the linking site of the heteroarylene group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom, and the heteroarylene group may be a monocyclic heteroarylene group, a polycyclic heteroarylene group, or a fused ring heteroarylene group. The monocyclic heteroarylene group includes a pyridylene group, a pyrimidylene group, a triazinylene group, a furanylene group, a thiophenylene group and the like, but is not limited thereto; the polycyclic heteroarylene group includes bipyridyl idene, phenylpyridyl, etc., but is not limited thereto; the fused ring heteroarylene group includes, but is not limited to, a quinolylene group, an isoquinolylene group, an indolyl group, a benzothiophene group, a benzofuranylene group, a benzoxazolyl group, a benzimidazolylene group, a benzothiazolyl group, a dibenzofuranylene group, a dibenzothiophenylene group, a carbazolyl group, a benzocarbazolyl group, an acridinylene group, a 9, 10-dihydroacridine group, a phenoxazinyl group, a phenothiazinylene group, a phenoxathiin group and the like. The heteroaryl group is preferably a pyridylene group, pyrimidylene group, thienylene group, furylene group, benzothienylene group, benzofuranylene group, benzoxazolyl group, benzimidazolylene group, benzothiazolyl group, dibenzofuranylene group, dibenzothiophenylene group, dibenzofuranylene group, carbazolyl group, acridinylene group, phenoxazinyl group, phenothiazinylene group, phenoxathiin group.

The substituted group such as substituted alkyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene means mono-or poly-substituted with a group independently selected from deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C15 heteroaryl, substituted or unsubstituted amine, etc., but not limited thereto, preferably with a group selected from deuterium, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, perylenyl, pyrenyl, benzyl, fluorenyl, 9-dimethylfluorenyl, dianilinyl, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furyl, thienyl, benzofuranyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, diarylide, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, thienyl, benzofuranyl, benzothienyl, and the like, Mono-or polysubstitution of dibenzofuranyl, dibenzothienyl, phenothiazinyl, phenoxazinyl, indolyl groups.

The term "integer selected from 0 to M" as used herein means any one of the integers having a value selected from 0 to M, including 0,1, 2 … M-2, M-1, M. For example, "p is selected from an integer of 0 to 4" means that p is selected from 0,1, 2,3, 4; "q is an integer selected from 0 to 4" means that a is selected from 0,1, 2,3, 4; and so on.

The linking to form a ring as described herein means that two groups are linked to each other by a chemical bond. As exemplified below:

in the present invention, the ring connected to the ring may be a five-membered ring or a six-membered ring or a fused ring, such as phenyl, naphthyl, cyclopentenyl, cyclopentyl, cyclohexanophenyl, fluorenyl, but not limited thereto.

The invention provides a dibenzothiophene derivative, the molecular structural general formula of which is shown as formula I:

wherein, L is selected from one of single bond, substituted or unsubstituted C6-C25 arylene, substituted or unsubstituted C2-C20 heteroarylene;

Ar₁、Ar₂independently selected from one of substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl;

L₀one selected from single bond, substituted or unsubstituted C6-C25 arylene, substituted or unsubstituted C2-C20 heteroarylene;

R₁、R₂independently selected from one of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, acridinyl, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, pyrenyl, indolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl;

p and q are independently selected from integers of 0 to 4, and when p is greater than 1, each R₁Identical or different, or adjacent R₁Can be connected into a ring; when q is greater than 1, each R₂Identical or different, or adjacent R₂Can be connected into a ring.

Preferably, the formula I is selected from one of the groups shown in the following formulas I-a to I-m:

preferably, Ar is₁、Ar₂Independently selected from one of the following groups:

wherein R is₁₂One selected from methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, phenyl, tolyl, biphenyl and naphthyl;

R₁₃one selected from deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, phenyl, tolyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, acridine, spirobifluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, pyrenyl, indolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl;

L₁one selected from the group consisting of formulas (1) to (14):

a is selected from an integer of 0 to 3; c is an integer from 0 to 4; b is an integer from 0 to 5; d is an integer from 0 to 7; f is an integer from 0 to 9.

Preferably, Ar is₁One selected from the group shown below:

preferably, Ar is₂One selected from methyl, phenyl, biphenyl, terphenyl, naphthyl, triphenylene, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-phenylcarbazolyl, dibenzothienyl and dibenzofuranyl.

Preferably, said L, L₀Independently selected from single bond, phenyleneNaphthalene group, biphenylene group, terphenylene group, tolylene group, dimethylphenylene group, and anthracenylene group.

Preferably, said L, L₀Independently selected from a single bond or any one of the following groups:

more preferably, the dibenzothiophene derivative of the present invention is selected from any one of the following chemical structures:

the dibenzothiophene derivative shown in the formula I is obtained through the following synthetic route:

the intermediate product and the dibenzothiophene derivative shown in the chemical formula I can be obtained through a Buchwald reaction and a Suzuki coupling reaction, namely, the intermediate product and the dibenzothiophene derivative are obtained by adding raw materials, a catalyst, alkali, a ligand and a solution in a nitrogen atmosphere and reacting at corresponding temperature.

The present invention is not particularly limited in terms of the source of the raw materials used in the above-mentioned reactions, and the dibenzothiophene derivatives according to the present invention can be obtained using commercially available raw materials or by preparation methods known to those skilled in the art.

The present invention is not particularly limited to the above-mentioned reaction, and a conventional reaction known to those skilled in the art may be used.

The invention also provides an organic light-emitting device which comprises a cathode, an anode and one or more organic layers arranged between and outside the cathode and the anode, wherein the organic layer comprises at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a covering layer; the organic layer contains any one or a combination of at least two of any one of the dibenzothiophene derivatives described in the present invention.

Preferably, the organic layer according to the present invention includes a hole transport layer containing any one or a combination of at least two of the dibenzothiophene derivatives according to the present invention.

The light emitting device of the present invention is generally formed on a substrate. The substrate may be any substrate as long as it does not change when forming an electrode or an organic layer, for example, a substrate of glass, plastic, a polymer film, silicon, or the like. When the substrate is opaque, the electrode opposite thereto is preferably transparent or translucent.

In the light-emitting device of the present invention, at least one of the anode and the cathode is transparent or translucent, and preferably, the cathode is transparent or translucent.

The anode material is preferably a material having a large work function so that holes are smoothly injected into the organic material layer, and a conductive metal oxide film, a translucent metal thin film, or the like is often used. Examples of the method for producing the film include a film (NESA or the like) made of a conductive inorganic compound containing indium oxide, zinc oxide, tin oxide, and a composite thereof, such as indium tin oxide (abbreviated as ITO) or indium zinc oxide (abbreviated as IZO), and a method using gold, platinum, silver, copper, or the like. As the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof, or the like can be used. The anode may have a multilayer structure of 2 or more layers, and preferably, an ITO-Ag-ITO substrate is used as the anode in the present invention.

The hole injection layer is to improve the efficiency of hole injection from the anode into the hole transport layer and the light emitting layer. The hole injection material of the present invention may be a metal oxide such as molybdenum oxide, silver oxide, vanadium oxide, tungsten oxide, ruthenium oxide, nickel oxide, copper oxide, or titanium oxide, or a low molecular weight organic compound such as a phthalocyanine-based compound or a polycyano group-containing conjugated organic material, but is not limited thereto. Preferably, the hole injection layer of the present invention is selected from 4,4 '-tris [ 2-naphthylphenylamino ] triphenylamine (abbreviated as 2T-NATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylamine (abbreviated as HAT-CN), 4' -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), 4 '-tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (abbreviated as MTDATA), copper (II) phthalocyanine (abbreviated as CuPc), N' -bis [4- [ bis (3-methylphenyl) amino ] phenyl ] -N, N '-diphenyl-biphenyl-4, 4' -diamine (abbreviated as DNTPD), etc., it may be a single structure made of a single substance, or a single-layer structure or a multi-layer structure made of different substances.

The hole transport layer is a layer having a function of transporting holes. The hole transport material of the present invention is preferably a material having a good hole transport property, and may be selected from small molecular materials such as aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyldiamine derivatives, styrene compounds, butadiene compounds, and the like, and polymeric materials such as poly-p-phenylene derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, and the like, and a dibenzothiophene derivative provided by the present invention, but is not limited thereto. Preferably, the hole transport layer of the present invention is selected from the group consisting of N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (abbreviated as NPB), N '-di (naphthalene-1-yl) -N, N' -di (phenyl) -2,2 '-dimethylbenzidine (abbreviated as. alpha. -NPD), N' -diphenyl-N, N '-di (3-methylphenyl) -1,1' -biphenyl-4, 4 '-diamine (abbreviated as TPD), 4' -cyclohexyldi [ N, N-di (4-methylphenyl) aniline ] (abbreviated as TAPC), 2,7, 7-tetra (diphenylamino) -9, the 9-spirobifluorene (short for Spiro-TAD) and the dibenzothiophene derivative provided by the invention can be of a single structure formed by a single substance, or of a single-layer structure or a multi-layer structure formed by different substances.

The electron-blocking layer is a layer which transports holes and blocks electrons, and is preferably selected from N, N ' -bis (naphthalen-1-yl) -N, N ' -bis (phenyl) -2,2' -dimethylbenzidine (abbreviated as. alpha. -NPD), 4' -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (abbreviated as TPD), 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (abbreviated as TAPC), 2,7, 7-tetrakis (diphenylamino) -9, 9-spirobifluorene (abbreviated as Spiro-TAD), and the like, it may be a single structure made of a single substance, or a single-layer structure or a multi-layer structure made of different substances.

The light-emitting layer is a layer having a light-emitting function. The light emitting layer material comprises a light emitting layer host material AND a light emitting layer guest material, preferably, the host material of the present invention is selected from 4,4 '-bis (9-carbazole) biphenyl (CBP for short), 9, 10-bis (2-naphthyl) anthracene (ADN for short), 4-bis (9-carbazolyl) biphenyl (CPB for short), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP for short), 4 '-tris (carbazol-9-yl) triphenylamine (TCTA for short), 9, 10-bis (1-naphthyl) anthracene (alpha-AND for short), N' -bis- (1-naphthyl) -N, N '-diphenyl- [1,1':4', 1':4', 1' -tetrabiphenyl ] -4,4' -diamino (4P-NPB for short), 1,3, 5-tri (9-carbazolyl) benzene (TCP for short) and the like, which can be a single-layer structure formed by a single substance or a single-layer structure or a multi-layer structure formed by different substances.

The guest material of the light-emitting layer of the present invention may include one material or a mixture of two or more materials, and the light-emitting material is classified into a blue light-emitting material, a green light-emitting material, and a red light-emitting material. Preferably, the luminescent material of the invention is a green luminescent material, and the blue luminescence isThe layer guest is selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyren-1-amine) (DPAP-DPPA), 2,5,8, 11-tetra-tert-butylperylene (TBPe), 4' -bis [4- (diphenylamino) styryl]Biphenyl (BDAVBi for short), 4' -di [4- (di-p-tolylamino) styryl]Biphenyl (DPAVBi for short), bis (2-hydroxyphenyl pyridine) beryllium (Bepp for short)₂) Bis (4, 6-difluorophenylpyridine-C2, N) picolinoyiridium (FIrpic).

The doping ratio of the host material and the guest material of the light-emitting layer is preferably varied depending on the materials used, and the doping film thickness ratio of the guest material of the light-emitting layer is usually 0.01 to 20%, preferably 0.1 to 15%, more preferably 1 to 10%.

The hole blocking layer is a layer that transports electrons and blocks holes, and is preferably selected from 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (abbreviated as BCP), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (abbreviated as TPBi), and tris (8-hydroxyquinoline) aluminum (III) (abbreviated as Alq)₃) 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), and the like, which may be a single structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.

The electron transport layer is a layer having a function of transporting electrons, and functions to inject electrons and balance carriers. The electron transport material of the present invention may be selected from known oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenoquinone derivatives, and metal complexes of 8-hydroxyquinoline and its derivatives, and preferably, the electron transport layer is selected from 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), and tris (8-hydroxyquinoline) aluminum (III) (Alq)₃) 1,3, 5-tris [ (3-pyridyl) -3-phenyl)]Benzene (abbreviated as TMPYPB), 8-hydroxyquinoline-lithium (abbreviated as Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylbenzenePhenol) aluminum (III) (BAlq for short), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-triazole (TAZ for short), and the like, which may be a single structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.

The electron injection layer material is a material that assists the injection of electrons from the cathode into the organic layer. The best choice of material is usually a corrosion resistant high work function metal as the cathode, with Al and Ag being common materials. Electron injection materials have been developed to date and include two types; one type is an alkali metal compound, such as lithium oxide (Li)₂O), lithium boron oxide (LiBO)₂) Cesium carbonate (Cs)₂CO₃) Potassium silicate (K)₂SiO₃) And the optimal thickness is generally 0.3-1.0 nm, and the device formed by the compound can reduce the driving voltage and improve the efficiency of the device. In addition, acetate compounds of alkali metals (CH)₃COOM, where M is Li, Na, K, Rb, Cs) also have similar effects. Another class is alkali metal fluorides (MF, where M is Li, Na, K, Rb, Cs), and if Al is used as the cathode material, the optimum thickness of these materials is typically less than 1.0 nm. Preferably, the electron injection layer according to the present invention may be selected from LiF.

In the cathode material, a metal material having a small work function is generally preferable in order to inject electrons into the electron injection/transport layer or the light-emitting layer. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like, alloys of 2 or more of these metals, or alloys of 1 or more of these metals and 1 or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite, or graphite intercalation compounds, and the like can be used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy. The cathode may have a laminated structure of 2 or more layers. The cathode can be prepared by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Among them, when light emission of the light-emitting layer is extracted from the cathode, the light transmittance of the cathode is preferably more than 10%. It is also preferable that the sheet resistivity of the cathode is several hundred Ω/□ or less, and the film thickness is usually 10nm to 1 μm, preferably 50 to 200 nm.

The covering layer material is used for reducing the total emission loss and waveguide loss in the OLED device and improving the light extraction efficiency. Alq may be used as the cover layer material of the present invention₃TPBi or a compound shown as follows:

preferably, the cathode of the invention uses Ag or Mg-Ag alloy or thin Al.

Preferably, the hole transport layer material of the present invention is selected from any one or a combination of at least two of any one of the dibenzothiophene derivatives described in the present invention.

The film thicknesses of the hole transporting layer and the electron transporting layer may be selected as appropriate depending on the materials used, and may be selected so as to achieve appropriate values of the driving voltage and the light emission efficiency. Therefore, the film thicknesses of the hole transporting layer and the electron transporting layer are, for example, 1nm to 1um, preferably 2nm to 500nm, and more preferably 5nm to 200 nm.

The order and number of layers to be stacked and the thickness of each layer can be appropriately selected in consideration of the light emission efficiency and the lifetime of the device.

The organic light-emitting device of the present invention preferably has a structure in which: substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode. However, the structure of the organic light emitting device is not limited thereto. The organic light-emitting device can be selected and combined according to the parameter requirements of the device and the characteristics of materials, and part of organic layers can be added or omitted.

The method for forming each layer in the organic light-emitting device is not particularly limited, and any one of vacuum evaporation, spin coating, vapor deposition, blade coating, laser thermal transfer, electrospray, slit coating, and dip coating may be used, and in the present invention, vacuum evaporation is preferably used.

The organic light-emitting device can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps and the like.

The invention is explained in more detail by the following examples, without wishing to restrict the invention accordingly. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue inventive effort.

Preparation and characterization of the Compounds

Description of raw materials, reagents and characterization equipment:

the raw materials used in the following examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art.

The mass spectrum was analyzed by matrix-assisted laser desorption ionization (AXIMA-CFR plus) from Kratos Analytical, Inc. of Shimadzu corporation, U.K., using chloroform as a solvent;

the element analysis uses a Vario EL cube type organic element analyzer of Germany Elementar company, and the mass of a sample is 5-10 mg;

nuclear magnetic resonance (1H NMR Spectroscopy) A nuclear magnetic resonance spectrometer model Bruker-510 (Bruker, Germany), 600MHz, CDCl, was used₃As solvent, TMS as internal standard.

EXAMPLE 1 Synthesis of Compound 1

Step 1: synthesis of intermediate A-1

To a 1L reaction flask were added toluene (600mL), a-1 (benzidine) (35.54g, 0.21mol), b-1(67.46g, 0.21mol), palladium acetate (0.61g, 0.0027mol), sodium tert-butoxide (33.7g, 0.351mol), and tri-tert-butylphosphine (10.8mL of a 1.0M solution in toluene, 0.0108mol) in that order under nitrogen. And reacted under reflux for 2 hours. After the reaction is stopped, the mixture is cooled to room temperature, filtered by using kieselguhr, the filtrate is concentrated, recrystallized by using methanol, filtered by suction and rinsed by using methanol to obtain a recrystallized solid, and the intermediate A-1(67.08g, the yield is about 78%) is obtained, and the purity of the solid is not less than 98.4% by HPLC (high performance liquid chromatography).

Step 2: synthesis of intermediate B-1

Under nitrogen protection, a 1L reaction flask was charged with toluene solvent (600ml), c-1(42.03g, 108mmol), intermediate A-1(49.14g, 120mmol), and Pd in that order₂(dba)₃(3.98g, 4.35mol), BINAP (2.02g, 3.25mmol) and sodium tert-butoxide (16.61g, 172.8mmol), dissolved with stirring, and reacted under reflux under a nitrogen atmosphere for 24 hours, after completion of the reaction, the reaction solution was washed with dichloromethane and distilled water, and subjected to extraction by separation. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed, followed by washing with cyclohexane: and (3) separating, purifying and refining ethyl acetate 10:1 by column chromatography as an eluent to finally obtain a solid intermediate B-1(55.77g, the yield is 77%), and the solid purity is not less than 99.1% by HPLC (high performance liquid chromatography).

Step 3: synthesis of intermediate C-1

Intermediate B-1(50.43g, 75.2mmol) was dissolved in tetrahydrofuran (280mL), and after dropwise addition of a hexane solvent and n-butyllithium (36mL, 90.2mmol) at-78 deg.C, the mixture was stirred for 1 hour. Trimethyl borate (26mL, 112.8mmol) was then slowly added dropwise and the mixture was stirred for 2 hours. 2M hydrochloric acid was added dropwise to neutralize and the product was extracted with ethyl acetate and water. Recrystallization from dichloromethane and hexane gave compound C-1(22.46g, 47%) with a solid purity ≧ 99.6% by HPLC.

Step 4: synthesis of Compound 1

To a 1L reaction flask were added, under nitrogen, intermediate C-1(22.25g, 35mmol), b-1(11.24g, 35mmol), palladium tetrakistriphenylphosphine (1.15g, 1mmol) and sodium carbonate (41.4g, 300mmol) in that order, and the weighed reactants were dissolved in a solvent of toluene (1L)/EtOH (200 mL)/distilled water (200mL) and heated at 90 ℃ for 2 hours. The reaction mixture was cooled to room temperature, diluted with toluene and filtered through celite. The filtrate was diluted with water and extracted with toluene, and the organic phases were combined and evaporated under vacuum. The residue was filtered through silica gel and recrystallized. Compound 1(22.72g, 78% yield) is obtained, and the solid purity is ≧ 98.9% by HPLC.

Mass spectrum m/z: 831.37 (theoretical value: 831.30). Theoretical element content (%) C₆₂H₄₁And NS: c, 89.50; h, 4.97; n, 1.68; s, 3.85 measured element content (%): c, 89.52; h, 4.97; n, 1.66; and S, 3.85.¹H NMR(600MHz,CDCl₃)(,ppm)：8.17(d,1H),8.11–8.02(m,4H),7.92–7.89(m,3H),7.85–7.77(m,6H),7.73(td,1H),7.67–7.63(m,3H),7.60–7.56(m,4H),7.54–7.49(m,2H),7.48–7.42(m,6H),7.40–7.38(m,2H),7.34–7.23(m,8H),7.18(td,1H)。¹The H NMR is shown in FIG. 1. The above results confirmed that the obtained product was the objective product.

EXAMPLE 2 Synthesis of Compound 2

Compound 2(20.90g, Step4 yield: 79%) was obtained by replacing a-1 (benzidine) in Step1 of Synthesis example 1 with an equimolar a-2 and carrying out the same procedure, and the purity of the solid was 99.4% or more by HPLC.

Mass spectrum m/z: 755.29 (theoretical value: 755.26). Theoretical element content (%) C₅₆H₃₇And NS: c, 88.97; h, 4.93; n, 1.85; s, 4.24 measured elemental content (%): c, 88.98; h, 4.92; n, 1.84; and S, 4.25.¹H NMR(600MHz,CDCl₃)(,ppm)：8.15(d,1H),8.09–8.02(m,2H),7.99–7.92(m,3H),7.91–7.83(m,4H),7.80(dt,3H),7.78–7.64(m,5H),7.56(td,3H),7.51–7.40(m,6H),7.34–7.21(m,5H),7.12(dd,2H),7.04–7.02(m,3H)。¹The H NMR is shown in FIG. 2. The above results confirmed that the obtained product was the objective product.

EXAMPLE 3 Synthesis of Compound 15

The same procedure was repeated except for changing a-1 (benzidine) to an equimolar a-15 in Step1 of Synthesis example 1 to obtain 15(23.19g, Step4 yield: about 76%), and purity of solid was ≧ 99.5% by HPLC.

Mass spectrum m/z: 871.37 (theoretical value: 871.33). Theoretical element content (%) C₆₅H₄₅And NS: c, 89.52; h, 5.20; n, 1.61; s, 3.68 measured element content (%): c, 89.54; h, 5.18; n, 1.62; and S, 3.67.¹H NMR(600MHz,CDCl₃)(,ppm)：8.30(s,1H),8.16–8.07(m,3H),7.97–7.88(m,6H),7.82(dd,1H),7.79–7.73(m,4H),7.68(d,1H),7.64–7.48(m,12H),7.45–7.37(m,5H),7.32–7.21(m,4H),7.12-7.08(m,2H),1.71(s,3H),1.60(s,3H)。¹The H NMR is shown in FIG. 3. The above results confirmed that the obtained product was the objective product.

EXAMPLE 4 Synthesis of Compound 17

Compound 17(21.62g, Step4 yield: 73%) was obtained by replacing a-1 (benzidine) in Step1 of Synthesis example 1 with an equimolar a-17 and carrying out the same procedure, and the purity of the solid was 99.2% or more by HPLC.

Mass spectrum m/z: 845.33 (theoretical value: 845.28). Theoretical element content (%) C₆₂H₃₉NOS: c, 88.02; h, 4.65; n, 1.66; o, 1.89; s, 3.79 measured elemental content (%): c, 88.04; h, 4.63; n, 1.65; o, 1.89; and S, 3.80.¹H NMR(600MHz,CDCl₃)(,ppm)：8.29(dd,1H),8.17(d,1H),8.08(d,1H),8.03(dd,1H),8.00–7.93(m,5H),7.90–7.83(m,6H),7.82–7.79(m,2H),7.78–7.72(m,2H),7.71–7.64(m,3H),7.59–7.42(m,10H),7.37–7.20(m,7H)。¹The H NMR is shown in FIG. 4. The above results confirmed that the obtained product was the objective product.

EXAMPLE 5 Synthesis of Compound 46

The same procedure was repeated except for changing a-1 (benzidine) to an equimolar a-46 in Step1 of Synthesis example 1 to give 46(22.84g, Step4 yield: about 72%) as a compound having a purity of 99.3% or more by HPLC.

Mass spectrum m/z: 905.36 (theoretical value: 905.31). Theoretical element content (%) C₆₈H₄₃And NS: c, 90.13; h, 4.78; n, 1.55; s, 3.54 measured element content (%): c, 90.14; h, 4.77; n, 1.55; and S, 3.54.¹H NMR(600MHz,CDCl₃)(,ppm)：9.08(dd,1H),8.95(d,1H),8.67(dd,1H),8.50(d,1H),8.33(dd,1H),8.15–8.03(m,5H),8.00–7.89(m,5H),7.84(d,1H),7.79(d,1H),7.72–7.49(m,19H),7.38(dd,1H),7.33–7.21(m,4H),6.91(d,1H),6.64(dd,1H)。¹The H NMR is shown in FIG. 5. The above results confirmed that the obtained product was the objective product.

EXAMPLE 6 Synthesis of Compound 65

The compound 65(22.92g, about 75% yield of Step 4) was obtained by replacing a-1 (benzidine) in Step1 of Synthesis example 1 with an equimolar a-65, and the purity of the solid was ≧ 99.8% by HPLC.

Mass spectrum m/z: 872.33 (theoretical value: 872.29). Theoretical element content (%) C₆₃H₄₀N₂And OS: c, 86.67; h, 4.62; n, 3.21; o, 1.83; s, 3.67 measured elemental content (%): c, 86.68; h, 4.61; n, 3.22; o, 1.83; and S, 3.66.¹H NMR(600MHz,CDCl₃)(,ppm)：8.20(d,1H),8.06–8.01(m,2H),7.99–7.93(m,3H),7.89–7.82(m,3H),7.81–7.74(m,6H),7.68(dd,1H),7.65–7.59(m,6H),7.56–7.53(m,2H),7.50–7.38(m,12H),7.32–7.20(m,4H)。¹The H NMR is shown in FIG. 6. The above results confirmed that the obtained product was the objective product.

EXAMPLE 7 Synthesis of Compound 75

Compound 75(22.27g, Step4 yield about 76%) was obtained by replacing a-1 (benzidine) in Synthesis example 1, Step1, with an equimolar amount of a-75 and b-1 with an equimolar amount of b-75 in the same manner as in the previous Step, and the purity of the solid was 99.3% by HPLC.

Mass spectrum m/z: 836.37 (theoretical value: 836.33). Theoretical element content (%) C₆₂H₃₆D₅And NS: c, 88.96; h, 5.54; n, 1.67; s, 3.83 measured element content (%): c, 88.94; h, 5.57; n, 1.66; and S, 3.83.¹H NMR(600MHz,CDCl₃)(,ppm)：7.87–7.84(m,5H),7.68(d,1H),7.59(d,1H),7.57–7.51(m,9H),7.39(td,4H),7.28–7.20(m,7H),7.15–7.12(m,2H),7.11–7.06(m,7H)。¹The H NMR is shown in FIG. 7. The above results confirmed that the obtained product was the objective product.

EXAMPLE 8 Synthesis of Compound 77

Compound 77(23.20g, Step4 yield: 73%) was obtained by replacing b-1 in Step1 of Synthesis example 1 with equimolar b-75 and carrying out the same procedure, and the purity of the solid was ≧ 98.8% by HPLC.

Mass spectrum m/z: 907.37 (theoretical value: 907.33). Theoretical element content (%) C₆₈H₄₅And NS: c, 89.93; h, 4.99; n, 1.54; s, 3.53 measured elemental content (%): c, 89.95; h, 4.99; n, 1.52; and S, 3.53.¹H NMR(600MHz,CDCl₃)(,ppm)：8.29–8.21(m,2H),7.97–7.90(m,8H),7.88–7.86(m,3H),7.81(d,1H),7.73(dd,1H),7.64–7.56(m,10H),7.55–7.46(m,8H),7.44(t,2H),7.35–7.31(m,1H),7.29–7.21(m,7H),7.19–7.13(m,2H)。¹The H NMR is shown in FIG. 8. The above results confirmed that the obtained product was the objective product.

EXAMPLE 9 Synthesis of Compound 109

Compound 109(22.57g, Step4 yield: 71%) was obtained by replacing b-1 in Step1 of Synthesis example 1 with equimolar b-75 and c-1 with equimolar c-109 in the same manner as above, and the purity of the solid was ≧ 99.2% by HPLC.

Mass spectrum m/z: 907.37 (theoretical value: 907.33). Theoretical element content (%) C₆₈H₄₅And NS: c, 89.93; h, 4.99; n, 1.54; s, 3.53 measured elemental content (%): c, 89.94; h, 4.99; n, 1.53; and S, 3.53.¹H NMR(600MHz,CDCl₃)(,ppm)：8.38–8.29(m,2H),8.11(d,1H),8.05–7.99(m,2H),7.97(dd,1H),7.94–7.86(m,7H),7.80(d,1H),7.74–7.68(m,2H),7.63–7.56(m,8H),7.55–7.47(m,10H),7.45–7.43(m,2H),7.40–7.38(m,1H),7.35–7.31(m,1H),7.29–7.20(m,6H),6.49(dd,1H)。¹The H NMR is shown in FIG. 9. The above results confirmed that the obtained product was the objective product.

EXAMPLE 10 Synthesis of Compound 173

Step 1: synthesis of Compound b-173

After 2-bromodibenzofuran (54.20g, 206mmol) and 340mL of tetrahydrofuran were introduced into the reaction vessel, the vessel was cooled to-78 ℃ under a nitrogen atmosphere. 33mL of n-butyllithium (2.5M, 82mmol) were then slowly added dropwise to the mixture. After stirring the mixture at-78 ℃ for 2 hours, 9H-fluoren-9-one (37.12g, 206mmol) dissolved in 340mL of tetrahydrofuran was slowly added dropwise to the mixture. After the addition, the reaction temperature was slowly warmed to room temperature, and the mixture was stirred for 30 minutes. Then, an aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, and the mixture was extracted with ethyl acetate. The extracted organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining material was then purified by column chromatography to obtain compound b-173(56.34g, yield about 64%), and purity ≧ 99.5% by HPLC.

Compound 173(22.51g, 76% yield) was obtained by replacing b-1 in Step1 of Synthesis example 1 with equimolar b-173, and the purity of the solid was ≧ 99.0% by HPLC.

Mass spectrum m/z: 845.33 (theoretical value: 845.28). Theoretical element content (%) C₆₂H₃₉NOS: c, 88.02; h, 4.65; n, 1.66; o, 1.89; s, 3.79 measured elemental content (%): c, 88.03; h, 4.64; n, 1.65; o, 1.89; and S, 3.80.¹H NMR(600MHz,CDCl₃)(,ppm)：8.53(d,1H),8.15(d,1H),8.12–8.06(m,2H),8.04(dd,1H),8.00(dd,1H),7.98–7.91(m,3H),7.91–7.84(m,4H),7.79(dd,2H),7.75–7.65(m,4H),7.59–7.52(m,7H),7.51–7.42(m,3H),7.36–7.33(m,2H),7.29–7.20(m,3H),7.16–7.10(m,4H),7.07–7.00(m,1H)。¹The H NMR is shown in FIG. 10. The above results confirmed that the obtained product was the objective product.

[ comparative examples 1 to 4]

Device preparation example:

the organic light-emitting device is prepared by a vacuum thermal evaporation method. The experimental steps are as follows: repeatedly washing the ITO-Ag-ITO substrate with a glass cleaning agent, then washing the ITO-Ag-ITO substrate in distilled water for 2 times, ultrasonically washing for 15 minutes, after the washing with the distilled water is finished, ultrasonically washing solvents such as isopropanol, acetone and methanol in sequence, drying at 120 ℃, and conveying to an evaporation plating machine.

Evaporating a hole injection layer 2-TNATA/45nm, evaporating a hole transport layer NPB/40nm, and evaporating a light emitting layer (main body CBP: doped Ir (ppy))₃8% mixture)/30 nm, then evaporating an electron transport layer TMPYPB/40nm, an electron injection layer LiF/1nm, a cathode Mg-Ag (Mg: Ag doping ratio is 9:1)/20nm, and then evaporating a cover material CP-1/60nm on the cathode layer. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is as follows:

comparative example 2: a comparative organic light emitting device 2 was obtained by replacing the hole transport layer material NPB of comparative example 1 with the compound HT-1, and the other steps were the same.

Comparative example 3: a comparative organic light emitting device 3 was obtained by replacing the hole transport layer material NPB of comparative example 1 with the compound HT-2, and the other steps were the same.

Comparative example 4: the hole transport layer material NPB in comparative example 1 was replaced with the compound HT-3, and the other steps were the same, to obtain a comparative organic light-emitting device 4.

[ application examples 1 to 10]

Application examples 1 to 10: the hole transport layer material of the organic light emitting device was changed to compound 1, compound 2, compound 15, compound 17, compound 46, compound 65, compound 75, compound 77, compound 109, compound 173 of the present invention in this order, and the other steps were the same as in comparative example 1.

The test software, computer, K2400 digital source meter manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by photressearch corporation, usa were combined into a combined IVL test system to test the luminous efficiency and CIE color coordinates of the organic light emitting device.

The results of the light emission characteristic test of the obtained organic light emitting device are shown in table 1. Table 1 shows the results of the test of the light emitting characteristics of the light emitting devices prepared by the compounds prepared in the examples of the present invention and the comparative materials.

Table 1 test of light emitting characteristics of light emitting device

As can be seen from the results in table 1, the dibenzothiophene derivatives of the present invention, when applied to an organic light emitting device, particularly as a hole transport layer material, exhibited an advantage of higher light emission efficiency compared to comparative examples 1-2, and were organic light emitting materials with good performance.

It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.