Method for preparing conjugated compound having phenoxathiin and electron donating group of conjugated aromatic unit, and OLED device having the conjugated compound

Patent metadata

Field	Value
Publication number	US-9634260-B2
Application number	US-201514763827-A
Country	US
Kind code	B2
Filing date	May 22, 2015
Priority date	Apr 29, 2015
Publication date	Apr 25, 2017
Grant date	Apr 25, 2017

Abstract

The disclosure provides a conjugated compound having phenoxathiinl, method for preparing the same and OLED. The conjugated compound has one of the following formulas:

Different kinds of electron-rich conjugated aromatic units are reacted with intermediate having phenoxathiinl by Suzuki coupling, Buchwald-Hartwig coupling, or Cu-catalyzed amination of halogenated aromatic hydrocarbons for forming the conjugated compound having phenoxathiin. The prepared novel compound is fluorescent, so that it can be used as the material of light emitting layer of OLED devices.

First claim

What is claimed is:

1. A method for preparing a conjugated compound having phenoxathiin, wherein the method comprises:
preparing an intermediate having phenoxathiin; and
reacting the intermediate having phenoxathiin with a compound having an electron-rich conjugated aromatic unit by Suzuki coupling, Buchwald-Hartwig coupling, or Cu-catalyzed amination of halogenated aromatic hydrocarbons for forming the conjugated compound having phenoxathiin,
wherein the conjugated compound has one of the following formula:

in the Formula 1 and the Formula 2, at least one of R 1 -R 8 is an electron donating group of conjugated aromatic unit, alkyl-substituted aromatic unit, alkoxyl-substituted aromatic unit, alkyl- and alkoxyl-substituted aromatic unit, the aromatic unit is selected from one or more from the group constituted of an aromatic ring formed by vinylene group, ethynylene group, C and H atoms, an aromatic heterocyclic group formed by C, N and H atoms, an aromatic heterocyclic group formed by C, N, O and H atoms, an aromatic heterocyclic group formed by C, S and H atoms, and an aromatic heterocyclic group formed by C, Si and H atoms.

2. The method for preparing the conjugated compound having phenoxathiin according to claim 1 , wherein the intermediate having phenoxathiin is compound M1, M2, M3 or M4, and the structural formulas of M1, M2, M3 or M4 are:

3. The method for preparing the conjugated compound having phenoxathiin according to claim 2 , wherein the method and the reactions for preparing the intermediate having phenoxathiin of M1 and M2 are:

the method for preparing the intermediate having phenoxathiin of M1 is:
3 g of 2-hydroxy-benzenethiol and 120 mL of anhydrous N,N-dimethyl formamide being incorporated into a 250 mL three-necked flask and being stirred under Ar, with the protection of air, 5.47 g of potassium tert-butoxide being incorporated, after stirring for 0.5 hour, 7.01 g of 2,5-dibromo nitrobenzene being slowly incorporated, after stirring for 20 minutes, being heated under reflux overnight, after most of the anhydrous N,N-dimethyl formamide being vaporized by a rotary concentrator, the product being extracted by deionized water and dichloromethane and being separated by silica gel chromatography for obtaining a white solid of the intermediate of M1;
the method for preparing the intermediate having phenoxathiin of M2 is:
4.2 g of M1 and 50 mL of glacial acetic acid being incorporated into a 100 mL three-necked flask, after stirring, 10 mL of 30% hydrogen peroxide being incorporated, then, being heated under reflux overnight, after cooling, alcohol being incorporated, then, being vacuum filtrated, after drying, a white solid of the intermediate of M2 being obtained.

4. The method for preparing the conjugated compound having phenoxathiin according to claim 2 , wherein the method and the reactions for preparing the intermediate having phenoxathiin of M3 and M4 are:

the method for preparing the intermediate having phenoxathiin of M3 is:
5 g of 5-bromo-2-hydroxy-benzenethiol and 120 mL of anhydrous N,N-dimethyl formamide being incorporated into a 250 mL three-necked flask and being stirred under Ar, with the protection of air, 5.47 g of potassium tert-butoxide being slowly incorporated, after stirring for 0.5 hour, 7.01 g of 2,5-dibromo nitrobenzne being incorporated, after stirring for 20 minutes, being heated under reflux overnight, after most of the anhydrous N,N-dimethyl formamide being vaporized by a rotary concentrator, being extracted by deionized water and dichloromethane and being separated by silica gel chromatography for obtaining a white solid of the intermediate of M3; and
the method for preparing the intermediate having phenoxathiin of M4 is:
4.6 g of the intermediate of M3 and 50 mL of glacial acetic acid being incorporated into a 100 mL three-necked flask, after stirring, 10 mL of 30% hydrogen peroxide being incorporated, being heated under reflux overnight, after cooling, alcohol being incorporated, being vacuum filtrated, after drying, a white solid of the intermediate of M4 being obtained.

5. The method for preparing the conjugated compound having phenoxathiin according to claim 1 , wherein the electron-rich conjugated aromatic unit is N,N-dimethyl vinyl urea, 9,10-dihydro-9,9-dimethyl-acridine, N,N-diphenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxa pentaborane-2-yl) aniline, bis-(4-tert-butylphenyl) amine, phenothiazine, 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxa pentaborane 2-yl) carbazole, phenoxazine or N,N-dimethyl vinyl urea.

6. An organic light-emitting diode device, comprising a substrate, an anode, a hole injection layer, a hole transfer layer, a light emitting layer, an electron transfer layer and a cathode disposed in sequence from the bottom to the top, characterized by, the light emitting layer including a conjugated compound having phenoxathiin,
wherein the conjugated compound has one of the following formula:

in the Formula 1 and the Formula 2, at least one of R 1 -R 8 is an electron donating group of conjugated aromatic unit, alkyl-substituted aromatic unit, alkoxyl-substituted aromatic unit, alkyl- and alkoxyl-substituted aromatic unit, the aromatic unit is selected from one or more from the group constituted of an aromatic ring formed by vinylene group, ethynylene group, C and H atoms, an aromatic heterocyclic group formed by C, N and H atoms, an aromatic heterocyclic group formed by C, N, O and H atoms, an aromatic heterocyclic group formed by C, S and H atoms, and an aromatic heterocyclic group formed by C, Si and H atoms.

7. The organic light-emitting diode device according to claim 6 , wherein the light emitting layer is formed by vacuum vapor deposition or solution coating.

8. The organic light-emitting diode device according to claim 6 , wherein the substrate is a glass substrate, the material of the anode is indium tin oxide, and the cathode is a bilayer composite structure constituted by a LiF layer and an Al layer.

9. The organic light-emitting diode device according to claim 6 , wherein the material of the hole injection layer is HAT-CN, the material of the hole transfer layer is NPB and TCTA, the material of the electron transfer layer is TPBI, the structural formulas of HAT-CN, NPB, TCTA and TPBI are:

Assignees

• Shenzhen China Star Optoelect

Inventors

• Li Xianjie
• Wu Yuanchun
• Su Shijian
• Liu Ming
• Liu Kunkun

Classifications

• C07D411/04 Primary

  directly linked by a ring-member-to-ring-member bond · CPC title

• H01L51/0071 Primary

  Electricity · mapped topic

• C07D417/14

  containing three or more hetero rings · CPC title

• C09K2211/1029

  containing one nitrogen atom as the heteroatom · CPC title

• H01L51/0058

  Electricity · mapped topic