CN111440187A - Thermal excitation blue light delaying material and preparation method and application thereof - Google Patents

Thermal excitation blue light delaying material and preparation method and application thereof Download PDF

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CN111440187A
CN111440187A CN201911268332.7A CN201911268332A CN111440187A CN 111440187 A CN111440187 A CN 111440187A CN 201911268332 A CN201911268332 A CN 201911268332A CN 111440187 A CN111440187 A CN 111440187A
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benzofuran
blue light
thieno
light material
benzothiophene
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CN111440187B (en
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孟鸿
施明
孙越
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Peking University Shenzhen Graduate School
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Abstract

The invention relates to a thermal excitation blue light delaying material and a preparation method and application thereof. The invention takes benzo [4,5] thieno [3,2-b ] benzofuran 10, 10-dioxide as an electron acceptor, and compared with the traditional electron acceptor such as sulfone or ketone group, the invention has a rigid plane structure, thereby being beneficial to not only fluorescence and stability, but also the migration of carriers; meanwhile, the difference between the triplet state energy level and the singlet state energy level of the molecule is small, and TADF molecules can be constructed beneficially. The prepared thermal excitation delayed blue light material has the advantages of high luminous efficiency and stable performance.

Description

Thermal excitation blue light delaying material and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic luminescent materials, in particular to a thermal excitation delay blue light material and a preparation method and application thereof.
Background
Since the discovery of organic light emitting diodes (O L ED), organic light emitting devices mainly use organic light emitting small molecules and high molecular polymers as light emitting materials, and are prepared by evaporation or spin coating, however, due to the poor solubility of organic light emitting small molecules, the light emitting efficiency of fluorescent materials is low (the traditional fluorescent efficiency is not more than 25%), phosphorescent light emitting materials generally contain precious metals (iridium, platinum, etc.), and the conditions required by the evaporation process are severe, so that the manufacturing process cost of organic light emitting devices is extremely high.
The Adachi group designs and synthesizes a series of organic light-emitting small molecular materials of deep blue light based on a TADF (thermally excited delayed fluorescence) mechanism, the External Quantum Efficiency (EQE) of a device prepared from the materials can exceed 20 percent, and the blue purity and the EQE of the device are higher than those of the commercialized materials.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a thermal excitation delayed blue light material, a preparation method and an application thereof, and aims to solve the problems of poor luminous purity and poor stability of the existing TADF blue light material.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a thermal excitation delayed blue light material has a molecular structural formula as follows:
Figure BDA0002313480020000021
wherein R is1、R2、R3Is an aromatic system unit.
The thermal excitation delayed blue light material, wherein R1、R2、R3Each independently is any one of the following aromatic system units:
Figure BDA0002313480020000022
the thermal excitation delayed blue light material has a molecular structural formula of any one of the following molecular formulas:
Figure BDA0002313480020000031
Figure BDA0002313480020000041
Figure BDA0002313480020000051
Figure BDA0002313480020000061
a method for preparing a thermally-excited delayed blue light material, wherein the method comprises the steps of:
dissolving [1] benzothiophene [3,2-b ] [1] benzofuran in chloroform, dropwise adding a chloroform solution of liquid bromine into the chloroform solution, reacting, adding a saturated sodium thiosulfate aqueous solution, washing, and drying to obtain 2, 7-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran;
dissolving the 2, 7-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran in acetic acid, adding 30% hydrogen peroxide, refluxing at a first preset temperature, pouring into water after the reaction is finished, and performing suction filtration and separation to obtain 2, 7-dibromo [4,5] thieno [3,2-b ] benzofuran 10, 10-dioxide;
dissolving the 2, 7-dibromobenzo [4,5] thieno [3,2-b ] benzofuran 10, 10-dioxide and an aromatic system unit in toluene, adding a catalyst, heating to a second preset temperature under the protection of inert gas, washing, drying, concentrating and carrying out column chromatography treatment after the reaction is finished to obtain the 2, 7-arylamine substituted benzo [4,5] thieno [3,2-b ] benzofuran 10, 10-dioxide.
A method for preparing a thermally-excited delayed blue light material, wherein the method comprises the steps of:
dissolving [1] benzothiophene [3,2-b ] [1] benzofuran in chloroform, dropwise adding a chloroform solution of liquid bromine with the same molar mass at 0 ℃, adding a saturated sodium thiosulfate aqueous solution, washing, and drying to obtain 2-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran;
dissolving the 2-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran in acetic acid, adding 30% hydrogen peroxide, refluxing at a first preset temperature, pouring into water after the reaction is finished, and performing suction filtration and separation to obtain 2-dibromo-benzo [4,5] thieno [3,2-b ] benzofuran 10, 10-dioxide;
2-dibromobenzo [4,5]]Thieno [3,2-b]Dissolving benzofuran 10, 10-dioxide and aromatic system unit in toluene, and adding Pd (PPh)3)4And potassium carbonate, heating to a second preset temperature under the protection of inert gas, washing, drying, concentrating and carrying out column chromatography treatment after the reaction is finished to obtain 2-arylamine substituted benzo [4,5]]Thieno [3,2-b]Benzofuran 10, 10-dioxides.
The preparation method of the thermal excitation delayed blue light material comprises the following steps that the first preset temperature is 80-100 ℃, and the second preset temperature is 100-120 ℃.
The preparation method of the thermal excitation blue light delaying material is characterized in that the reflux time is 5-8 h.
The preparation method of the thermal excitation blue light delaying material is characterized in that the catalyst is Pd2(dba)3，HF4P(t-Bu)3And potassium tert-butoxide.
The preparation method of the thermal excitation delayed blue light material is characterized in that the aromatic system unit is any one of the following organic molecules:
Figure BDA0002313480020000071
Figure BDA0002313480020000081
a light-emitting device comprises a cathode, a light-emitting layer and an anode from top to bottom in sequence, wherein the light-emitting layer is made of the thermal excitation delayed blue light material.
Drawings
FIG. 1 is a thermogravimetric analysis curve of a thermally-excited delayed blue light material in example 1 of the present invention.
FIG. 2 is a fluorescence emission spectrum of a thermally-excited delayed blue material in an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The thermal excitation delayed blue light material provided by the embodiment of the invention has the following molecular structural formula:
Figure BDA0002313480020000082
wherein R is1、R2、R3Is an aromatic system unit. Benzo [4,5] in the molecular structural formula]Thieno [3,2-b ]]The benzofuran 10, 10-dioxide has excellent fluorescence property, has a rigid plane structure compared with a traditional electron acceptor such as sulfone or ketone, is favorable for fluorescence and stability, is favorable for carrier migration, and simultaneously has good electron and hole transport capacity.
In particular, R1、R2、R3Wherein R is1、R2May be the same or different, R1、 R2、R3Each independently is any one of the following aromatic system units:
Figure BDA0002313480020000091
the aromatic system unit is selected as an electron donor, and the aromatic group in the aromatic system unit can provide abundant electrons for an electron acceptor, so that the obtained thermally-excited delayed blue light material has high stability in structure.
In one or more embodiments, the molecular formula of the thermally-excited delayed blue light material of the present invention may be any one of the following molecular formulas:
Figure BDA0002313480020000092
Figure BDA0002313480020000101
Figure BDA0002313480020000111
Figure BDA0002313480020000121
Figure BDA0002313480020000131
based on the same inventive concept, the invention also provides a preparation method of the thermal excitation blue light delaying material, which comprises the following preparation steps:
dissolving [1] benzothiophene [3,2-b ] [1] benzofuran in chloroform, dripping chloroform solution of liquid bromine at low temperature (about 0 ℃) until the raw materials react completely, and adding saturated sodium thiosulfate water solution to reduce excessive liquid bromine. Washing the organic phase with saturated sodium bicarbonate water solution, drying and purifying to obtain 2, 7-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran for later use.
Dissolving 2, 7-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran in acetic acid, adding 30% hydrogen peroxide, and heating and refluxing for 6 h. Pouring into water after the reaction is finished, separating out solid, performing suction filtration separation, recrystallizing by using chloroform and petroleum ether, and purifying to obtain the 2, 7-dibromobenzo [4,5] thieno [3,2-b ] benzofuran 10, 10-dioxide.
Buchward coupling: the bromobenzo [4,5] obtained above is subjected to]Thieno [3,2-b]Benzofuran 10, 10-dioxide and aromatic electron donor are dissolved in toluene, and after oxygen in the system is removed, a catalytic amount of Pd is added2(dba)3，HF4P(t-Bu)3Heating and reacting with potassium tert-butoxide under the protection of inert gas until the reaction of the raw materials is finished; cooling to room temperature, washing with saturated saline and water, drying with anhydrous sodium sulfate, concentrating, and subjecting the residue to column chromatography with petroleum ether and dichloromethane as eluent to obtain 2, 7-arylamine substituted benzo [4,5]]Thieno [3,2-b]Benzofuran 10, 10-dioxides.
The specific synthetic route is as follows:
Figure BDA0002313480020000141
in another embodiment, the method for preparing the thermally-excited delayed blue light material comprises the following steps:
dissolving [1] benzothiophene [3,2-b ] [1] benzofuran in chloroform, dripping a chloroform solution of liquid bromine with the same molar mass at low temperature until the raw materials completely react, and adding a saturated sodium thiosulfate aqueous solution to reduce the excessive liquid bromine. Washing the organic phase with saturated sodium bicarbonate water solution, drying and purifying to obtain 2-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran for later use.
Dissolving 2-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran in acetic acid, adding 30% hydrogen peroxide, and heating and refluxing for 6 h. Pouring into water after the reaction is finished, separating out solids, performing suction filtration and separation, recrystallizing by using chloroform and petroleum ether, and purifying to obtain the 2-dibromobenzo [4,5] thieno [3,2-b ] benzofuran 10, 10-dioxide.
Suzuki coupling: the bromobenzo [4,5] obtained above is subjected to]Thieno [3,2-b]Benzofuran 10, 10-dioxide, aromatic electron donating borate group are dissolved in toluene, and after removing oxygen in the system, catalytic amount of Pd (PPh) is added3)4And potassium carbonate, heating and reacting under the protection of inert gas until the reaction of the raw materials is finished; cooling to room temperature, washing with saturated saline and water, drying with anhydrous sodium sulfate, concentrating, and subjecting the residue to column chromatography with petroleum ether and dichloromethane to obtain 2-substituted benzo [4,5]]Thieno [3,2-b]Benzofuran 10, 10-dioxides.
The specific synthetic route is as follows:
Figure RE-GDA0002534548390000231
the embodiment of the invention also provides application of the thermal excitation delayed blue light material, and the material has good fluorescence and stability, and the difference between the triplet state energy level and the singlet state energy level of molecules is small, so that the material can be used as a light-emitting layer of an O L ED light-emitting device.
The present invention is explained in detail below by way of specific examples.
Example 1
Figure BDA0002313480020000152
The bromobenzo [4,5] obtained above is subjected to]Thieno [3,2-b]Benzofuran 10, 10-dioxide (2.07g,5mmol) and 1, 8-dimethylcarbazole (1.95g,10mmol) were dissolved in 60 ml of toluene, and after removing oxygen in the system, Pd was added2(dba)3(3％-5％)，HF4P(t-Bu)3(10% -15%) and potassium tert-butoxide (1.68g,15mmol) under the protection of inert gas, and heating to react until the reaction of the raw materials is finished; cooling to room temperature, washing with saturated saline and water, drying with anhydrous sodium sulfate, concentrating, and subjecting the residue to column chromatography with petroleum ether and dichloromethane as eluentCompound 1 was obtained in 83% yield.
Performance testing
As shown in FIG. 1, Compound 1 is excellent in thermal stability and has a thermal decomposition temperature exceeding 530 ℃. The powder fluorescence quantum yield of compound 1 was tested by integrating sphere and was 75%.
As can be seen from FIG. 2, the fluorescence spectra of the undoped and doped thin films were measured for a thin film having a thickness of 50nm by vacuum evaporation, and the undoped thin film had an emission peak of 453nm and a half-width of 60nm, and the thin film doped with DPEPO had an emission peak of 420nm and a half-width of 50 nm.
In summary, the present invention provides a thermally-excited delayed blue light material, and a preparation method and an application thereof. The invention takes benzo [4,5] thieno [3,2-b ] benzofuran 10, 10-dioxide as an electron acceptor, and compared with the traditional electron acceptor such as sulfone or ketone group, the invention has a rigid plane structure, thereby being beneficial to not only fluorescence and stability, but also the migration of carrier; meanwhile, the difference between the triplet state energy level and the singlet state energy level of the molecule is small, and the TADF molecule is favorably constructed. The prepared thermal excitation delayed blue light material has the advantages of high luminous efficiency and stable performance.
Meanwhile, the material can also be used as a transmission layer of an organic photoelectric device due to good carrier transmission characteristics.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (10)

1. A thermal excitation delayed blue light material is characterized in that the molecular structural formula is as follows:
Figure FDA0002313480010000011
wherein R is1、R2、R3Is an aromatic system unit.
2. A thermally-activated delayed blue light material as claimed in claim 1, wherein R is1、R2、R3Each independently is any one of the following aromatic system units:
Figure FDA0002313480010000012
3. a thermally-excited delayed blue light material as claimed in claim 1, wherein the molecular structural formula is any one of the following formulas:
Figure FDA0002313480010000013
Figure FDA0002313480010000021
Figure FDA0002313480010000031
Figure FDA0002313480010000041
4. a method of making a thermally-activated delayed blue light material, the method comprising the steps of:
dissolving [1] benzothiophene [3,2-b ] [1] benzofuran in chloroform, dropwise adding a chloroform solution of liquid bromine into the chloroform solution to react, adding a saturated sodium thiosulfate aqueous solution, washing and drying to obtain 2, 7-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran;
dissolving the 2, 7-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran in acetic acid, adding 30% hydrogen peroxide, refluxing at a first preset temperature, pouring into water after the reaction is finished, and performing suction filtration and separation to obtain 2, 7-dibromo [4,5] thieno [3,2-b ] benzofuran 10, 10-dioxide;
dissolving the 2, 7-dibromobenzo [4,5] thieno [3,2-b ] benzofuran 10, 10-dioxide and an aromatic system unit in toluene, adding a catalyst, heating to a second preset temperature under the protection of inert gas, washing, drying, concentrating and carrying out column chromatography treatment after the reaction is finished to obtain the 2, 7-arylamine substituted benzo [4,5] thieno [3,2-b ] benzofuran 10, 10-dioxide.
5. A method of making a thermally-activated delayed blue light material, the method comprising the steps of:
dissolving [1] benzothiophene [3,2-b ] [1] benzofuran in chloroform, dropwise adding a chloroform solution of liquid bromine with the same molar mass at 0 ℃, adding a saturated sodium thiosulfate aqueous solution, washing, and drying to obtain 2-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran;
dissolving the 2-dibromo [1] benzothiophene [3,2-b ] [1] benzofuran in acetic acid, adding 30% hydrogen peroxide, refluxing at a first preset temperature, pouring into water after the reaction is finished, and performing suction filtration and separation to obtain 2-dibromo-benzo [4,5] thieno [3,2-b ] benzofuran 10, 10-dioxide;
2-dibromobenzo [4,5]]Thieno [3,2-b]The benzofuran 10, 10-dioxide and aromatic system unit are dissolved in toluene, and Pd (PPh) is added3)4And potassium carbonate, heating to a second preset temperature under the protection of inert gas, washing, drying, concentrating and carrying out column chromatography treatment after the reaction is finished to obtain 2-arylamine substituted benzo [4,5]]Thieno [3,2-b]Benzofuran 10, 10-dioxides.
6. The method as claimed in claim 4 or 5, wherein the first predetermined temperature is 80-100 ℃ and the second predetermined temperature is 100-120 ℃.
7. A method for preparing a thermally-excited delayed blue light material as claimed in claim 4 or 5, wherein the reflow time is 5-8 h.
8. The method of claim 4, wherein the catalyst is Pd2(dba)3，HF4P(t-Bu)3And potassium tert-butoxide.
9. The method for preparing a thermal excitation delayed blue light material as claimed in claim 4 or 5, wherein the aromatic system unit is any one of the following organic molecules:
Figure FDA0002313480010000061
Figure FDA0002313480010000071
10. a light-emitting device comprising, in order from top to bottom, a cathode, a light-emitting layer and an anode, wherein the light-emitting layer is made of the thermally-excited delayed blue light material according to any one of claims 1 to 3.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110452226A (en) * 2019-08-05 2019-11-15 北京大学深圳研究生院 A kind of organic blue-light fluorescent material and blue-light device based on azole derivatives

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