CN112209936A - Novel AIE material based on seven-membered cyclic imide, preparation method thereof and method for preparing organic electroluminescent device - Google Patents

Novel AIE material based on seven-membered cyclic imide, preparation method thereof and method for preparing organic electroluminescent device Download PDF

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CN112209936A
CN112209936A CN202010970658.0A CN202010970658A CN112209936A CN 112209936 A CN112209936 A CN 112209936A CN 202010970658 A CN202010970658 A CN 202010970658A CN 112209936 A CN112209936 A CN 112209936A
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赵祖金
王之君
何刚
唐本忠
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South China University of Technology SCUT
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Abstract

The invention discloses a novel AIE material based on seven-membered cyclic imide, a preparation method thereof and a method for preparing an organic electroluminescent device. Based on the receptor micromolecules with active sites, donors are introduced through coupling reaction such as Suzuki and the like, and a series of novel D-A-D type luminescent materials with AIE characteristics are synthesized. The invention designs and synthesizes D-A-D type benzimide/diimide with AIE characteristics for the first time, and the unique twisted structure of the benzimide/diimide shows unique photoelectric property and thermal activation delayed fluorescence property. The preparation method of the imide compound is simple and convenient to operate and mild in reaction condition; the prepared electroluminescent device has higher external quantum efficiency and high brightness, and is a guest material with excellent performance in organic electroluminescent small molecular materials. The invention not only makes up the defects of the structural variety of the imide materials, but also widens the application of the imide materials in organic electroluminescent devices.

Description

Novel AIE material based on seven-membered cyclic imide, preparation method thereof and method for preparing organic electroluminescent device
Technical Field
The invention belongs to the technical field of preparation of luminescent compounds and preparation of electroluminescent devices thereof, and particularly relates to a novel AIE material based on heptacyclic imide, a preparation method of the novel AIE material and a method for preparing an organic electroluminescent device.
Background
Organic optoelectronics is a new cross-discipline across chemistry, materials, physics, information as an emerging research field, and has received widespread attention in academia and industry in recent years. At present, rapid development of organic photoelectric devices such as organic electroluminescent diodes, organic field effect transistors, organic photovoltaic cells, organic sensors and the like has embodied incomparable advantages of inorganic semiconductor devices. Compared with inorganic materials, organic luminescent materials have a wide variety, rich colors, flexible design and good controllability, and have attracted extensive attention and research of researchers. In the field of Organic Light-Emitting Diodes (OLEDs), scientists have been devoted to designing and developing OLED devices with high efficiency and high color purity. However, the conventional light emitting materials often have problems of insufficient efficiency and severe roll-off when applied to OLED devices. To solve this problem, doping is often used to mitigate the roll-off in efficiency due to concentration quenching during device fabrication. However, the doping method is limited and troublesome to operate, and is not beneficial to the application in future industrial production, so how to design the light-emitting material of the OLED device with good device efficiency and without doping is a difficult problem to solve urgently, and is very important for the industrial production of the OLED device.
Common organic light-emitting molecules are mostly planar conjugated structures, and although the molecules emit light strongly in a solution state, in an Aggregation state, fluorescence Quenching occurs due to pi-pi interaction between strong planes, and the phenomenon is called Aggregation-induced fluorescence Quenching (ACQ). Since the light emitting layer of the electroluminescent device is made of a thin-film aggregate fluorescent material, the ACQ phenomenon is very disadvantageous for the application of the electroluminescent device in the OLED device. In 2001, the tangkunzhi group found that the silole derivative 1-methyl-1,2,3,4, 5-pentaphenylsilole (1-methyl-1,2,3,4, 5-pentaphenylsilole, MPPS) hardly emitted light in the solution state, but emitted light significantly increased in the aggregate state, and this unique light emitting property different from the ACQ phenomenon was called Aggregation-Induced Emission (AIE). Since the AIE concept was proposed, researchers have conducted extensive studies on the mechanism and molecular design of this phenomenon, and applications in the fields of organic electroluminescent devices, fluorescent molecular probes, chemical sensors, and the like have also been explored.
Due to good thermal stability and unique photophysical characteristics, imide molecules are widely applied to organic photoelectric devices such as organic field effect transistors, organic photovoltaic cells and organic sensors as a good acceptor material. However, in many five-membered ring and six-membered ring imide compounds which are widely used, due to inherent plane rigidity of molecular structures and strong pi-pi interaction among molecules, intramolecular rotation is limited, so that the compounds emit light weakly or not in a solid state, show obvious ACQ properties, and greatly limit the application prospect of the compounds in organic electroluminescent devices. Recently reported luminescent materials taking planar NDI with six-membered rings as a main body structure have serious molecular accumulation, so that the solid-state luminescence is extremely poor, and the maximum EQE of a TADF doped device taking the NDI as a luminescent layer main body is 2.4%, which greatly limits the application of the luminescent materials in organic electroluminescent devices. (J.Mater.chem.C 2018,6,8219-8225.) it is therefore of great importance to develop novel imide-based luminescent materials with AIE properties.
Disclosure of Invention
The invention aims to provide a novel AIE material based on seven-membered cyclic imide, a preparation method thereof and a method for preparing an organic electroluminescent device.
The invention is realized by the following technical scheme:
the invention discloses a seven-membered cyclic imide micromolecule, which has the following structure;
Figure BDA0002683898330000021
Figure BDA0002683898330000031
the invention also discloses a synthetic method of the seven-membered cyclic imide micromolecule, which comprises the following steps:
preparation of novel AIE Material 1
1) Preparation of Compound A
Under the protection of argon, dropwise adding amine into a dichloromethane solution of 2,2 ', 6, 6' -biphenyltetracarboxylic anhydride, and stirring and reacting for 8-16 hours at room temperature; removing the solvent, adding sodium acetate into the residual solid, carrying out reflux reaction in acetic anhydride for 3-6 hours, and then cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and performing column chromatography with dichloromethane-n-hexane system to obtain compound A;
wherein, the structure of the compound A is as follows:
Figure BDA0002683898330000032
2) preparation of small molecule 1 containing seven-membered ring imide
Under the protection of argon, sequentially adding a compound A, a compound B, tetrakis (triphenylphosphine) palladium and a potassium carbonate aqueous solution into toluene, uniformly stirring, heating to 110 ℃, reacting at a constant temperature for 12-48 hours, naturally cooling to room temperature, removing the solvent, and performing column chromatography separation by using a dichloromethane-n-hexane system to obtain a micromolecule containing heptacyclic imide;
the structure of the imide-containing micromolecule is as follows;
Figure BDA0002683898330000033
wherein the compound B is
Figure BDA0002683898330000034
Preferably, in the step 1), the molar ratio of the 2,2 ', 6, 6' -biphenyltetracarboxylic anhydride to the amine is 1:3, and the volume ratio of the dichloromethane to the n-hexane is 1: 2;
preferably, in the step 2), the molar ratio of the compounds A, B and the tetrakis (triphenylphosphine) palladium is 1: 2.2-3: 0.01-0.05, and the volume ratio of the dichloromethane-n-hexane is 1:1.
Preparation of novel AIE Material 2
1) Preparation of Compound C
Stirring a sodium acetate solution of 2,2 ', 6, 6' -biphenyltetracarboxylic anhydride in DMF at 120 ℃ for 10-30 minutes under the protection of argon; then adding amine with the same equivalent weight, stirring at 120 ℃ for reaction for 3-6 hours, and cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and performing column chromatography with dichloromethane-methanol system to obtain compound C;
wherein, the structure of the compound C is as follows:
Figure BDA0002683898330000041
2) preparation of small molecule 2 containing seven-membered cyclic imide
Under the protection of argon, sequentially adding a compound C, a compound B, tetrakis (triphenylphosphine) palladium and a potassium carbonate aqueous solution into toluene, uniformly stirring, heating to 110 ℃, reacting at a constant temperature for 12-36 hours, naturally cooling to room temperature, removing the solvent, and performing column chromatography separation by using a dichloromethane-methanol system to obtain a micromolecule 2 containing the heptatomic cyclic imide;
the structure of the imide-containing micromolecule is as follows;
Figure BDA0002683898330000042
wherein the compound B is
Figure BDA0002683898330000043
Preferably, in the step 1), the molar ratio of the 2,2 ', 6, 6' -biphenyltetracarboxylic anhydride to the amine is 1:1.2, and the volume ratio of the dichloromethane to the methanol is 5: 1;
preferably, in the step 2), the molar ratio of the compound C, the compound B and the tetrakis (triphenylphosphine) palladium is 1: 1-1.2: 0.02, and the volume ratio of dichloromethane-methanol is 10: 1.
Preparation of novel AIE Material 3
1) Preparation of Compound D
Adding 2,2 ', 6, 6' -biphenyltetracarboxylic acid into absolute methanol, stirring and dissolving, then dropwise adding a small amount of concentrated sulfuric acid, reacting at room temperature for 12-36h, washing with water, filtering, drying to obtain a white solid, and separating and purifying the solid by column chromatography to obtain a compound D;
wherein, the structure of the compound D is as follows:
Figure BDA0002683898330000051
2) preparation of Compound E
Adding a compound D, a compound F, cesium carbonate, palladium acetate and triphenylphosphine into dry toluene under the condition of argon, heating and refluxing for 24-48h, cooling to room temperature after the reaction is finished, extracting with dichloromethane, collecting an organic phase, and purifying by using dichloromethane-n-hexane column chromatography to obtain a compound E;
wherein, the structure of the compound E is as follows:
Figure BDA0002683898330000052
the compound F is R1H
3) Preparation of seven-membered cyclic imide Small molecule 3
Under the protection of argon, dissolving the compound F in a methanol/tetrahydrofuran/sodium hydroxide aqueous solution, refluxing and stirring for reaction for 10-16 hours, removing the solvent under reduced pressure, dissolving residual solids in water, and then adding a solid intermediate product acidified by hydrochloric acid; drying, refluxing in acetic anhydride for 3-6 hr, removing solvent under reduced pressure after reaction, dissolving solid in tetrahydrofuran, adding amine, and stirring at room temperature for 8-16 hr; removing the solvent, adding sodium acetate into the residual solid, carrying out reflux reaction in acetic anhydride for 5-8 hours, and then cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and separating with dichloromethane-n-hexane system by column chromatography to obtain target product, i.e. small molecule 3 containing heptatomic cyclic imide.
The structure of the imide-containing micromolecule is as follows;
Figure BDA0002683898330000061
preferably, in the step 1), the molar ratio of 2,2 ', 6, 6' -biphenyltetracarboxylic acid to anhydrous methanol to concentrated sulfuric acid is 1: 10-20: 0.01 to 0.05; in the step 2), the molar ratio of the compound D, the compound F, cesium carbonate, palladium acetate and triphenylphosphine is 1: 2.2-3: 4:0.1:0.3, and the volume ratio of dichloromethane-n-hexane is 2: 1;
preferably, the volume ratio of methanol/tetrahydrofuran/aqueous sodium hydroxide solution in step 3) is 3:1: 2.
Preparation of novel AIE Material 4
1) Preparation of compound E the same procedure as for the above novel AIE material 3;
2) preparation of seven-membered cyclic imide Small molecule 4
Under the protection of argon, dissolving the compound E in a methanol/tetrahydrofuran/sodium hydroxide aqueous solution, refluxing and stirring for reaction for 8-16 hours, removing the solvent under reduced pressure, dissolving residual solids in water, and then adding a solid intermediate product acidified by hydrochloric acid; drying, refluxing in acetic anhydride for 3-6 hr, removing solvent under reduced pressure after reaction, dissolving solid in sodium acetate solution of DMF, and stirring at 120 deg.C for 10-30 min; then adding amine with the same equivalent weight, stirring at 120 ℃ for reaction for 6-12 hours, and cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and separating with dichloromethane-methanol system by column chromatography to obtain target product, i.e. small molecule 4 containing heptatomic ring imide.
The structure of the micromolecule containing the seven-membered ring imide is as shown in the following formula;
Figure BDA0002683898330000062
preferably, in the step 1), the molar ratio of 2,2 ', 6, 6' -biphenyltetracarboxylic acid to anhydrous methanol to concentrated sulfuric acid is 1: 10-20: 0.01 to 0.05; in the step 2), the molar ratio of the compound D, the compound F, cesium carbonate, palladium acetate and triphenylphosphine is 1: 2.2-3: 4:0.1:0.3, and the volume ratio of dichloromethane-n-hexane is 2: 1;
preferably, the volume ratio of methanol/tetrahydrofuran/aqueous sodium hydroxide solution in step 3) is 3:1: 2.
The invention also discloses a method for preparing an electroluminescent device by adopting the seven-membered cyclic imide micromolecules, which is characterized by comprising the following steps:
1) preparing a multilayer thin film device by using the novel AIE material through sublimation purification and vacuum evaporation;
2) the novel AIE material is used as a guest material of a luminous layer, and different host materials and doping concentrations are selected to prepare an electroluminescent device with optimal performance;
3) the novel AIE material is used as a luminescent layer, the structure of the device is optimized, and the high-performance non-doped organic electroluminescent device is prepared.
The invention also discloses application of the thin film device prepared by the method as an electroluminescent device.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a benzimide/diimide micromolecule luminescent material containing a seven-membered ring. Based on the receptor micromolecules with active sites, donors are introduced through coupling reaction such as Suzuki and the like, and a series of novel D-A-D type luminescent materials with AIE characteristics are synthesized. In addition, by introducing different donor structures and numbers, the light color of the luminescent material in a solid state is adjusted, and electroluminescent devices with different colors are prepared. The invention designs and synthesizes D-A-D type benzimide/diimide with AIE characteristic for the first time. The novel imide compound shows unique photoelectric property and thermal activation delayed fluorescence property due to the unique distorted structure. Therefore, the small molecules can be used as a light-emitting layer and applied to electroluminescent devices with excellent performance. The preparation method of the imide compound is simple and convenient to operate and mild in reaction condition; the prepared electroluminescent device has higher external quantum efficiency and high brightness, and is a guest material with excellent performance in organic electroluminescent small molecular materials. The invention not only makes up the defects of the structural variety of the imide materials, but also widens the application of the imide materials in organic electroluminescent devices.
Drawings
FIG. 1 is nuclear magnetic hydrogen spectrum of example 1 containing a small molecule 1 of a seven-membered cyclic imide;
FIG. 2 is the nuclear magnetic hydrogen spectrum of example 2 containing a seven-membered cyclic imide small molecule 2;
FIG. 3 is a photoluminescence spectrum of small molecules 1 and 2 containing seven-membered cyclic imide in examples 1 and 2;
FIG. 4a is the AIE spectrum of small molecule 1 containing seven-membered cyclic imide of example 1;
FIG. 4b is the AIE spectrum of the small molecule 2 containing a seven-membered cyclic imide of example 2;
FIG. 5 is the electroluminescence spectra of the small molecules 1 and 2 containing the seven-membered cyclic imide of examples 1 and 2;
FIG. 6 is a graph of external quantum efficiency versus luminance for small seven-membered cyclic imide-containing molecules 1 and 2 of examples 1 and 2;
FIG. 7 is a graph of current density-voltage-luminance for small seven-membered cyclic imide molecules 1 and 2 of examples 1 and 2.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The novel AIE material containing the seven-membered cyclic imide micromolecules can be prepared by the following steps:
1. preparation of seven-membered cyclic imide micromolecule 1
(1) Preparation of Compound A
Under the protection of argon, dissolving 2,2 ', 6, 6' -biphenyltetracarboxylic anhydride in tetrahydrofuran solution, dropwise adding amine, and stirring at room temperature for reaction for 12 hours; removing the solvent under reduced pressure, adding sodium acetate into the residual solid, carrying out reflux reaction in acetic anhydride for 6 hours, and cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and performing column chromatography with dichloromethane-n-hexane system to obtain compound A;
the reaction equation is as follows:
Figure BDA0002683898330000081
2) preparation of small molecule 1 containing seven-membered ring imide
Under the protection of argon, sequentially adding a compound A, a compound B, tetrakis (triphenylphosphine) palladium and a potassium carbonate aqueous solution into toluene, uniformly stirring, heating to 110 ℃, reacting at a constant temperature for 24 hours, naturally cooling to room temperature, removing a solvent, and performing column chromatography separation by using a dichloromethane-n-hexane system to obtain a micromolecule containing heptacyclic imide;
the reaction equation is as follows:
Figure BDA0002683898330000091
2. preparation of seven-membered cyclic imide micromolecule 2
1) Preparation of Compound C
Stirring a sodium acetate solution of 2,2 ', 6, 6' -biphenyltetracarboxylic anhydride in DMF at 120 ℃ for 10 minutes under the protection of argon; then adding amine with the same equivalent weight, stirring at 120 ℃ for reaction for 6 hours, and cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and performing column chromatography with dichloromethane-methanol system to obtain compound C;
the reaction equation is as follows:
Figure BDA0002683898330000092
2) preparation of small molecule 2 containing seven-membered cyclic imide
Under the protection of argon, sequentially adding a compound C, a compound B, tetrakis (triphenylphosphine) palladium and a potassium carbonate aqueous solution into toluene, uniformly stirring, heating to 110 ℃, reacting at a constant temperature for 24 hours, naturally cooling to room temperature, removing a solvent, and performing column chromatography separation by using a dichloromethane-methanol system to obtain a micromolecule 2 containing the heptatomic cyclic imide;
the reaction equation is as follows:
Figure BDA0002683898330000101
3. preparation of seven-membered cyclic imide micromolecule 3
1) Preparation of Compound D
Adding 2,2 ', 6, 6' -biphenyltetracarboxylic acid into absolute methanol, stirring and dissolving, then dropwise adding a small amount of concentrated sulfuric acid, reacting for 24 hours at room temperature, washing with water, filtering, drying to obtain a white solid, and separating and purifying the solid by column chromatography to obtain a compound D;
the reaction equation is as follows:
Figure BDA0002683898330000102
2) preparation of Compound E
Adding a compound D, a compound F, cesium carbonate, palladium acetate and triphenylphosphine into dry toluene under the condition of argon, heating and refluxing for 36h, cooling to room temperature after the reaction is finished, extracting with dichloromethane, collecting an organic phase, and purifying by using dichloromethane-n-hexane column chromatography to obtain a compound E;
the reaction equation is as follows:
Figure BDA0002683898330000111
the compound F is R3H
3) Preparation of seven-membered cyclic imide Small molecule 3
Under the protection of argon, dissolving the compound E in a methanol/tetrahydrofuran/sodium hydroxide aqueous solution, refluxing, stirring and reacting for 12 hours, decompressing and removing the solvent, dissolving residual solid in water, and then adding a solid intermediate product acidified by hydrochloric acid; drying, refluxing in acetic anhydride for 6 hours, removing the solvent under reduced pressure after the reaction is finished, dissolving the solid in tetrahydrofuran, adding amine, and stirring at room temperature for reaction for 12 hours; removing the solvent, adding sodium acetate into the residual solid, carrying out reflux reaction in acetic anhydride for 6 hours, and then cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and separating with dichloromethane-n-hexane system by column chromatography to obtain target product, i.e. small molecule 3 containing heptatomic cyclic imide.
The reaction equation is as follows:
Figure BDA0002683898330000112
4. preparation of seven-membered cyclic imide micromolecule 4
1) The preparation of the compound E is the same as the step of the seven-membered cyclic imide micromolecule 3;
2) preparation of seven-membered cyclic imide Small molecule 4
Under the protection of argon, dissolving the compound E in a methanol/tetrahydrofuran/sodium hydroxide aqueous solution, refluxing, stirring and reacting for 12 hours, decompressing and removing the solvent, dissolving residual solid in water, and then adding a solid intermediate product acidified by hydrochloric acid; drying, refluxing in acetic anhydride for 6 hr, removing solvent under reduced pressure after reaction, dissolving solid in sodium acetate solution of DMF, and stirring at 120 deg.C for 10 min; then adding amine with the same equivalent weight, stirring at 120 ℃ for reaction for 6 hours, and cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and separating with dichloromethane-methanol system by column chromatography to obtain target product, i.e. small molecule 4 containing heptatomic ring imide.
The structure of the micromolecule containing the seven-membered ring imide is as shown in the following formula;
Figure BDA0002683898330000121
5. AIE characteristic test of the seven-membered cyclic imide micromolecules and application of electroluminescent devices
1) Testing the fluorescence spectra of the molecules in different polar solvents, and exploring the AIE characteristics of the molecules;
2) sublimating and purifying the obtained target product, and preparing a multilayer thin film device by a vacuum evaporation method;
3) the obtained target product is used as a guest material of a luminous layer, and different host materials and doping concentrations are selected to prepare an electroluminescent device with optimal performance;
4) the obtained target product is used as a luminous layer, the structure of the device is optimized, and the high-performance undoped electroluminescent device is prepared.
Example 1
1) Preparation of Compound A
Under the protection of argon, 2 ', 6, 6' -biphenyltetracarboxylic anhydride (0.452g,1mmol) is dissolved in tetrahydrofuran (20ml), n-octylamine (0.387g,3mmol) is added dropwise, and the reaction is stirred at room temperature for 12 hours; the solvent was removed under reduced pressure and the residual solid was added to sodium acetate (0.205g, 25mmol) and reacted in acetic anhydride (10ml) under reflux for 6h before cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and performing column chromatography with dichloromethane-n-hexane system to obtain compound A;
the reaction equation is as follows:
Figure BDA0002683898330000131
2) preparation of small molecule 1 containing seven-membered ring imide
Under the protection of argon, sequentially adding a compound A (1mmol), a compound B (2.4mmol), tetrakis (triphenylphosphine) palladium (0.02mmol) and a potassium carbonate aqueous solution (2M,3ml) into 9ml of anhydrous toluene, uniformly stirring, heating to 110 ℃, stirring at constant temperature for reaction for 24 hours, naturally cooling to room temperature, removing a solvent, and performing column chromatography separation by using a dichloromethane-n-hexane system to obtain a micromolecule 1 containing heptacyclic imide;
the reaction equation is as follows:
Figure BDA0002683898330000132
example 2
1) Preparation of Compound C
Under the protection of argon, 2 ', 6, 6' -biphenyltetracarboxylic anhydride (1mmol) is dissolved in 10ml DM, 20mmol sodium acetate is added, and the mixture is stirred for 10 minutes at 120 ℃; then adding 1.1mmol of octylamine, stirring at 120 ℃ for reaction for 6 hours, and cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and performing column chromatography with dichloromethane-methanol system to obtain compound C;
the reaction equation is as follows:
Figure BDA0002683898330000133
2) preparation of small molecule 2 containing seven-membered cyclic imide
Under the protection of argon, sequentially adding a compound C, a compound B, tetrakis (triphenylphosphine) palladium and a potassium carbonate aqueous solution into toluene, uniformly stirring, heating to 110 ℃, reacting at a constant temperature for 24 hours, naturally cooling to room temperature, removing a solvent, and performing column chromatography separation by using a dichloromethane-methanol system to obtain a micromolecule 2 containing the heptatomic cyclic imide;
the reaction equation is as follows:
Figure BDA0002683898330000141
example 3
1) Preparation of Compound D
Adding 2,2 ', 6, 6' -biphenyltetracarboxylic acid (4.52g,10mmol) into anhydrous methanol (60ml), stirring to dissolve, then dropwise adding a small amount of concentrated sulfuric acid, reacting at 80 ℃ for 24h, washing with water, filtering, drying to obtain a white solid, and separating and purifying the solid by column chromatography to obtain a compound D;
the reaction equation is as follows:
Figure BDA0002683898330000142
2) preparation of Compound E
Adding a compound D (0.271g,0.5mmol), phenoxazine (0.30g, 1.5mmol), cesium carbonate (0.650g,2mmol), palladium acetate (0.011g,0.05mmol) and triphenylphosphine (0.039g,0.15mmol) into dried toluene under the condition of argon, heating and refluxing at 120 ℃ for 36h, cooling to room temperature after the reaction is finished, extracting with dichloromethane, collecting an organic phase, and purifying by dichloromethane-n-hexane column chromatography to obtain a compound E;
the reaction equation is as follows:
Figure BDA0002683898330000151
3) preparation of seven-membered cyclic imide Small molecule 3
Dissolving compound E (0.375g,0.5mmol) in methanol/tetrahydrofuran/sodium hydroxide aqueous solution (6ml/18ml/21ml) under the protection of argon, carrying out reflux reaction at 100 ℃ for 12 hours, removing the solvent under reduced pressure, dissolving residual solid in water, and adding hydrochloric acid acidified solid intermediate product; after drying, refluxing in acetic anhydride (5ml) for 6 hours, removing the solvent under reduced pressure after the reaction is finished, dissolving the solid in tetrahydrofuran (10ml), adding octylamine (1.5mmol), and stirring at room temperature for reaction for 12 hours; removing the solvent, adding sodium acetate (10mmol) into the residual solid, refluxing in acetic anhydride (10ml) for 6 hours, and cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and separating with dichloromethane-n-hexane system by column chromatography to obtain target product, i.e. small molecule 3 containing heptatomic cyclic imide.
The reaction equation is as follows:
Figure BDA0002683898330000152
example 4
1) Compound E was prepared in the same manner as in example 3;
2) preparation of seven-membered cyclic imide Small molecule 4
Dissolving compound E (0.5mmol) in methanol/tetrahydrofuran/sodium hydroxide aqueous solution (6ml/18ml/21ml) under the protection of argon, refluxing and stirring for reaction for 12 hours, removing the solvent under reduced pressure, dissolving residual solid in water, and then adding hydrochloric acid acidified solid intermediate product; after drying, refluxing in acetic anhydride (5ml) for 6 hours, after the reaction is finished, removing the solvent under reduced pressure, dissolving the solid in DMF (10ml) solution of sodium acetate (10mmol), and stirring at 120 ℃ for 10 minutes; then adding octylamine with the same equivalent weight, stirring at 120 ℃ for reaction for 6 hours, and cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and separating with dichloromethane-methanol system by column chromatography to obtain target product, i.e. small molecule 4 containing heptatomic ring imide.
The structure of the micromolecule containing the seven-membered ring imide is as shown in the following formula;
Figure BDA0002683898330000161
examples 5 to 8
The preparation method of the embodiment 1-4 is followed, and octylamine is replaced by aniline, and other steps are the same, so that the seven-membered cyclic imide micromolecule 5-8 is prepared.
Figure BDA0002683898330000162
Examples 9 to 12
By the same procedures as in examples 1 to 4 except for replacing octylamine with 4-tert-butylaniline, small heptacyclic imide molecules 9 to 12 were obtained.
Figure BDA0002683898330000163
Examples 13 to 16
According to the preparation method of the embodiment 1-4, the octylamine is replaced by aniline, the phenoxazine phenylboronate is replaced by phenothiazine phenylboronate, the phenoxazine is replaced by phenothiazine with the synthetic compound E, and the other steps are the same, so that the heptatomic cyclic imide micromolecule 13-16 is prepared.
Figure BDA0002683898330000171
Examples 17 to 20
According to the preparation method of the embodiment 1-4, the octylamine is replaced by aniline, the phenoxazine phenylboronate is replaced by selenazine phenylboronate, the phenoxazine is replaced by selenazine in the synthetic compound E, and the other steps are the same, so that the heptatomic cyclic imide micromolecule 17-20 is prepared.
Figure BDA0002683898330000172
Examples 21 to 24
According to the method of the embodiment 1-4, the octylamine is replaced by 4-tert-butylaniline, the phenoxazine phenylboronate is replaced by phenothiazine phenylboronate, the synthetic compound E is replaced by phenoxazine, and other steps are the same, so that the heptacyclic imide micromolecule 13-16 is prepared.
Figure BDA0002683898330000173
Examples 25 to 30
According to the method of the embodiment 1-4, the octylamine is replaced by 4-tert-butylaniline, the phenoxazine phenylboronate is replaced by selenazine phenylboronate, the phenoxazine is replaced by selenazine with the synthetic compound E, and the other steps are the same, so that the heptatomic cyclic imide micromolecule 25-30 is prepared.
Figure BDA0002683898330000181
Examples 31 to 34
According to the preparation method of the embodiment 1-4, the octylamine is replaced by aniline, the phenoxazine phenylboronate is replaced by dimethylacridine phenylboronate, the phenoxazine is replaced by dimethylacridine, and the synthetic compound E is replaced by dimethylacridine, and the other steps are the same, so that the heptatomic cyclic imide micromolecules 31-34 are prepared.
Figure BDA0002683898330000182
Examples 35 to 38
According to the preparation method of the embodiment 1-4, the octylamine is replaced by 4-tert-butylaniline, the phenoxazine phenylboronate is replaced by dimethyl acridine phenylboronate, the phenoxazine is replaced by dimethyl acridine with the synthetic compound E, and the other steps are the same, so that the heptatomic cyclic imide micromolecule 35-38 is prepared.
Figure BDA0002683898330000183
Examples 39 to 40
According to the preparation method of the embodiment 1-2, the octylamine is replaced by aniline, the phenoxazine phenylboronic acid ester is replaced by triphenylamine borate, and other steps are the same, so that the heptatomic cyclic imide micromolecule 39-40 is prepared.
Figure BDA0002683898330000191
Examples 41 to 42
According to the preparation method of the embodiment 1-2, octylamine is replaced by 4-tert-butylaniline, phenoxazine phenylboronate is replaced by triphenylamine borate, and other steps are the same, so that the heptatomic cyclic imide micromolecules 41-42 are prepared.
Figure BDA0002683898330000192
In order to verify the effects of the present invention, the research on the AIE properties of the heptacyclic imide compounds synthesized in examples 1 and 2 and the use thereof in an electroluminescent device were investigated, as shown in the figure.
FIGS. 1 and 2 show nuclear magnetic hydrogen spectra of synthesized compounds 1 and 2, respectively, from which the structure of the compound can be judged as the product synthesized as described above.
FIG. 3 shows the fluorescence spectra of the synthesized compounds 1 and 2, and it can be seen from FIG. 2 that the maximum emission peak of the compound 1 is yellow light around 540nm, and the maximum emission peak of the compound 2 is green light around 490 nm. It can be concluded that products of different light colors can be obtained by adjusting different donor structures.
Wherein FIG. 4a is THF/H of heptacyclic imide small molecule 1 at different volume ratio2Change in fluorescence intensity in O solution. As is evident from the fluorescence spectrum of FIG. 4a, the molecule hardly luminesced with H in THF solution2The increase in the proportion of O gradually aggregates the molecules, accompanied by an increase in the fluorescence intensity. At fw(VH2O/VH2O+THF)>At 70%, the fluorescence intensity increased significantly. Maximum emission at 568nm, with fwFurther increase in (f) the maximum emission peak is blue-shifted when at fwAt 99%, the maximum emission is at 542 nm. Showing a pronounced aggregation-induced emission phenomenon (AIE). FIG. 4b is the THF/H ratio of heptacyclic imide small molecule 2 at different volume ratios2In O solution, the change in fluorescence intensity showed the same aggregation-induced emission phenomenon (AIE) as that of Compound 1.
FIG. 5 shows the electroluminescence spectra of the doped films of the synthesized compounds 1 and 2 as the light-emitting layers, from FIG. 4 it can be seen that the maximum emission peaks of the electroluminescence spectra of the light-emitting layers are 542nm and 492nm, respectively, which are consistent with the photoluminescence spectra of the compounds 1 and 2, and the luminescence of the electroluminescent device is illustrated as coming from the compounds 1 and 2.
Fig. 6 is a graph of luminance versus external quantum efficiency of electroluminescent devices in which the synthesized compounds 1 and 2 were used as light emitting layers, and it can be seen from fig. 6 that the devices exhibited good device characteristics, with maximum EQE of 18.1% and 16.2%, respectively, which are much greater than those of common fluorescent materials (EQE ═ 5%). Meanwhile, the device has high brightness.
Fig. 7 is a graph of luminance-voltage-current density of an electroluminescent device in which the synthesized compounds 1 and 2 are used as a light emitting layer, and as is apparent from fig. 7, the device has a lower lighting voltage of 3.2V, respectively.
The compounds obtained in examples 3-42 have the same properties as described above.
The seven-membered cyclic imide micromolecules have remarkable AIE characteristics and show excellent device performance when used as a light-emitting layer of an electroluminescent device.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (9)

1. A novel AIE material based on seven-membered cyclic imide is characterized in that the structure of the novel AIE material is as follows,
Figure FDA0002683898320000011
wherein the content of the first and second substances,
Figure FDA0002683898320000012
Figure FDA0002683898320000013
Figure FDA0002683898320000021
2. the method of preparing the novel AIE material of claim 1, wherein the preparation of the novel AIE material I comprises the steps of:
1) preparation of Compound A
Under the protection of argon, dropwise adding amine into a dichloromethane solution of 2,2 ', 6, 6' -biphenyltetracarboxylic anhydride, and stirring and reacting for 8-16 hours at room temperature; removing the solvent, adding sodium acetate into the residual solid, carrying out reflux reaction in acetic anhydride for 3-6 hours, and then cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and performing column chromatography with dichloromethane-n-hexane system to obtain compound A;
wherein, the structure of the compound A is as follows:
Figure FDA0002683898320000022
2) preparation of small molecule I containing seven-membered cyclic imide
Under the protection of argon, sequentially adding a compound A, a compound B, tetrakis (triphenylphosphine) palladium and a potassium carbonate aqueous solution into toluene, uniformly stirring, heating to 110 ℃, reacting at a constant temperature for 12-48 hours, naturally cooling to room temperature, removing a solvent, and performing column chromatography separation by using a dichloromethane-n-hexane system to obtain a micromolecule I containing the heptatomic cyclic imide;
the structure of the imide-containing micromolecule is as follows;
Figure FDA0002683898320000023
wherein the compound B is
Figure FDA0002683898320000031
3. The method of preparing the novel AIE material of claim 1, wherein the preparation of the novel AIE material II comprises the steps of:
1) preparation of Compound C
Stirring a sodium acetate solution of 2,2 ', 6, 6' -biphenyltetracarboxylic anhydride in DMF at 120 ℃ for 10-30 minutes under the protection of argon; then adding amine with the same equivalent weight, stirring at 120 ℃ for reaction for 3-6 hours, and cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and performing column chromatography with dichloromethane-methanol system to obtain compound C;
wherein, the structure of the compound C is as follows:
Figure FDA0002683898320000032
2) preparation of small molecule II containing seven-membered cyclic imide
Under the protection of argon, sequentially adding a compound C, a compound B, tetrakis (triphenylphosphine) palladium and a potassium carbonate aqueous solution into toluene, uniformly stirring, heating to 110 ℃, reacting at a constant temperature for 12-36 hours, naturally cooling to room temperature, removing the solvent, and performing column chromatography separation by using a dichloromethane-methanol system to obtain a micromolecule II containing the heptatomic cyclic imide;
the structure of the imide-containing small molecule II is shown as the following formula;
Figure FDA0002683898320000041
wherein the compound B is
Figure FDA0002683898320000042
4. The method of preparing the novel AIE material of claim 1, wherein the preparation of the novel AIE material III comprises the steps of:
1) preparation of Compound D
Adding 2,2 ', 6, 6' -biphenyltetracarboxylic acid into absolute methanol, stirring and dissolving, then dropwise adding a small amount of concentrated sulfuric acid, reacting at room temperature for 12-36h, washing with water, filtering, drying to obtain a white solid, and separating and purifying the solid by column chromatography to obtain a compound D;
wherein, the structure of the compound D is as follows:
Figure FDA0002683898320000043
2) preparation of Compound E
Adding a compound D, a compound F, cesium carbonate, palladium acetate and triphenylphosphine into dry toluene under the condition of argon, heating and refluxing for 24-48 hours, cooling to room temperature after the reaction is finished, extracting with dichloromethane, collecting an organic phase, and purifying by using dichloromethane-n-hexane column chromatography to obtain a compound E;
wherein, the structure of the compound E is as follows:
Figure FDA0002683898320000051
the compound F is R1H
3) Preparation of seven-membered cyclic imide Small molecule III
Under the protection of argon, dissolving the compound E in a methanol/tetrahydrofuran/sodium hydroxide aqueous solution, carrying out reflux stirring reaction for 10-16 hours, removing the solvent under reduced pressure, dissolving residual solids in water, and then adding a solid intermediate product acidified by hydrochloric acid; after drying, refluxing in acetic anhydride for 3-6 hours, removing the solvent under reduced pressure after the reaction is finished, dissolving in tetrahydrofuran solution, then adding amine with the same equivalent weight, reacting at room temperature for 8-16 hours, removing the solvent under reduced pressure after the reaction is finished, dissolving the residual solid in sodium acetate solution of acetic anhydride, refluxing, stirring, reacting for 5-8 hours, and cooling to room temperature; washing with water, extracting with dichloromethane, collecting an organic phase, and performing column chromatography separation with a dichloromethane-n-hexane system to obtain a target product, namely a small molecule III containing heptatomic cyclic imide;
the structure of the micromolecule containing the seven-membered ring imide is as shown in the following formula;
Figure FDA0002683898320000052
5. the method of preparing the novel AIE material of claim 1, wherein the preparation of the novel AIE material IV comprises the steps of:
1) preparation of Compound D
Adding 2,2 ', 6, 6' -biphenyltetracarboxylic acid into absolute methanol, stirring and dissolving, then dropwise adding a small amount of concentrated sulfuric acid, reacting at room temperature for 12-36h, washing with water, filtering, drying to obtain a white solid, and separating and purifying the solid by column chromatography to obtain a compound D;
wherein, the structure of the compound D is as follows:
Figure FDA0002683898320000061
2) preparation of Compound E
Adding a compound D, a compound F, cesium carbonate, palladium acetate and triphenylphosphine into dry toluene under the condition of argon, heating and refluxing for 24-48h, cooling to room temperature after the reaction is finished, extracting with dichloromethane, collecting an organic phase, and purifying by using dichloromethane-n-hexane column chromatography to obtain a compound E;
wherein, the structure of the compound E is as follows:
Figure FDA0002683898320000062
the compound F is R1H；
3) Preparation of seven-membered cyclic imide Small molecule IV
Under the protection of argon, dissolving the compound E in a methanol/tetrahydrofuran/sodium hydroxide aqueous solution, refluxing and stirring for reaction for 8-16 hours, removing the solvent under reduced pressure, dissolving residual solids in water, and then adding a solid intermediate product acidified by hydrochloric acid; after drying, refluxing in acetic anhydride for 3-6 hours, removing the solvent under reduced pressure after the reaction is finished, dissolving the solid in a sodium acetate solution of DMF, and heating and stirring for 10-30 minutes; then adding amine with the same equivalent weight, heating, stirring, reacting for 6-12 hours, and cooling to room temperature; washing with water, extracting with dichloromethane, collecting organic phase, and separating with dichloromethane-methanol system by column chromatography to obtain target product, i.e. small molecule IV containing heptatomic ring imide.
The structure of the micromolecule containing the seven-membered ring imide is as shown in the following formula;
Figure FDA0002683898320000071
6. the method of claim 2, wherein in step 1), the molar ratio of 2,2 ', 6, 6' -biphenyltetracarboxylic anhydride to amine is 1:3, and the volume ratio of dichloromethane to n-hexane is 1: 2; in the step 2), the molar ratio of the compounds A and B to the tetrakis (triphenylphosphine) palladium is 1: 2.2-3: 0.01-0.05, wherein the volume ratio of dichloromethane to n-hexane is 1:1.
7. The method of claim 3, wherein in step 1), the molar ratio of 2,2 ', 6, 6' -biphenyltetracarboxylic anhydride to amine is 1:1.2, and the volume ratio of dichloromethane to methanol is 5: 1; in the step 2), the molar ratio of the compound C, the compound B and the tetrakis (triphenylphosphine) palladium is 1: 1-1.2: 0.01-0.05, wherein the volume ratio of dichloromethane to methanol is 10: 1.
8. The method for preparing a novel AIE material according to claim 4 or 5, wherein in the step 1), the molar ratio of 2,2 ', 6, 6' -biphenyltetracarboxylic acid to anhydrous methanol to concentrated sulfuric acid is 1: 10-20: 0.01 to 0.05; in the step 2), the molar ratio of the compound D to the compound F to cesium carbonate to palladium acetate to triphenylphosphine is 1: 2.2-3: 4:0.1:0.3, and the volume ratio of dichloromethane to n-hexane is 2: 1; the volume ratio of methanol/tetrahydrofuran/sodium hydroxide aqueous solution in the step 3) is 3:1: 2.
9. A method for preparing an organic electroluminescent device using the novel AIE material of claim 1, comprising the steps of,
1) preparing a multilayer thin film device by using the novel AIE material through sublimation purification and vacuum evaporation;
2) the novel AIE material is used as a guest material of a luminescent layer, and different host materials and doping concentrations are selected to prepare an electroluminescent device with optimal performance;
3) the novel AIE material is used as a luminescent layer, the structure of the device is optimized, and a high-performance undoped electroluminescent device is prepared.
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