CN113683498A - Green light material based on 9-fluorenone structural framework and preparation method and application thereof - Google Patents
Green light material based on 9-fluorenone structural framework and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a green light material based on a 9-fluorenone structural framework, which has a general structural formula
The material takes 9-fluorenone as a material mother nucleus, and a green material is obtained by introducing mono-substituted or multi-substituted aryl to 3, 6-positions of the 9-fluorenone. By means of electron pushing effect of the methoxyl group and electron effect and space effect generated by different substitution positions, the injection and transmission of material carriers are more balanced, and the improvement of the performance of the device is facilitated. Meanwhile, the material has a specific space torsion angle due to large steric hindrance, and the fluorescent quantum efficiency of the solid film is improved, so that the material can emit green light efficiently in an organic solvent. The invention also discloses a preparation method of the green light material, and the method has the advantages of low raw material cost, mild reaction conditions, simple operation, high yield and the like. The invention also discloses the application of the green light material in an organic electroluminescent device or an intelligent material, and the green light material has a good application prospect.
Description
Technical Field
The invention belongs to the field of synthesis of organic green-light luminescent materials, and relates to a green-light material based on a 9-fluorenone structural framework, and a preparation method and application thereof.
Background
The flexible, light, low-cost and high-efficiency display screen is always the target of people, and the display screen greatly changes the daily life of people and improves the information interaction capability of people. Organic Light Emitting Diodes (OLEDs) have become the next generation of display lighting technology after LEDs, and compared with other display technologies, OLEDs have the remarkable advantages of wide viewing angle, low energy consumption, fast response speed, ultra-thin, ultra-light, simple and convenient molding and processing, and the like, can prepare fully cured thin film devices, can realize flexible display, and have received extensive attention and intensive research of people.
Fluorescence usually occurs in molecules with rigid planes and pi-electron conjugated systems, and the degree of intramolecular conjugation is the main influence factor of the fluorescence performance of the material, so that the degree of pi-electron conjugation in the molecules is improved, and the fluorescence luminous efficiency of the molecules can be effectively improved. Fluorene and fluorenone have rigid plane biphenyl structure and contain relatively large conjugated system in the molecule, and fluorenone material has relatively high heat stability, high fluorescent quantum effect and relatively wide band gap energy, and is one important kind of fluorescent material. However, due to the influence of the structures of fluorene and fluorenone, excimer formation and long-wave emission are easily caused, which may affect the chromaticity and color stability of the overall emitted light in the device. Therefore, the improvement of the color purity and stability of fluorenone materials is of great importance to the development of the OLED industry.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a green light material based on a 9-fluorenone structural framework, which has the characteristics of good luminescence property, high thermal stability and high color purity.
The second purpose of the present invention is to provide a preparation method of the green light material based on the 9-fluorenone structural skeleton.
The invention also aims to provide application of the green light material based on the 9-fluorenone structural framework.
One of the purposes of the invention is realized by adopting the following technical scheme:
a green light material based on 9-fluorenone structure skeleton, which has a general structural formula A
Wherein R is
R1、R2、R3Each independently selected from methoxy or hydrogen.
Further, the green light material based on the 9-fluorenone structural framework has the structure that:
the second purpose of the invention is realized by adopting the following technical scheme:
the preparation method of the green light material based on the 9-fluorenone structural framework comprises the following steps:
under the protection of nitrogen, 3, 6-dibromo-9H-fluorene-9-ketone, boric acid derivative corresponding to R, tetrakis (triphenylphosphine) palladium and an alkaline substance are mixed, and a mixed solution of tetrahydrofuran and water is added to the mixture to react to obtain a final product A.
Further, the molar ratio of the 3, 6-dibromo-9H-fluorene-9-one, the boric acid derivative corresponding to R, the tetrakis (triphenylphosphine) palladium and the alkaline substance is 1 (2-5): (0.006-0.016): (0.8-2).
Further, the boric acid derivative corresponding to R is selected from one of 4-methoxyphenylboronic acid, 3, 4-dimethoxyphenylboronic acid, 3, 5-dimethoxyphenylboronic acid, 2, 4-dimethoxyphenylboronic acid, 6-methoxy-2-naphthylboronic acid and benzo [ d ] [1,3] dioxa-5-ylboronic acid.
Further, the alkaline substance is selected from one of potassium carbonate and sodium hydroxide.
Furthermore, the adding ratio of the tetrahydrofuran, the water and the 3, 6-dibromo-9H-fluorene-9-ketone is (10-1) mL and 1mL, and the adding ratio is (225.3-22.5) mg.
Further, the reaction temperature is 100 ℃, and the reaction time is 24-36 hours.
The second purpose of the invention is realized by adopting the following technical scheme:
the green light material based on the 9-fluorenone structural framework is applied to an organic electroluminescent device or an intelligent material.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a green light material based on a 9-fluorenone structural framework, which has the characteristics of good luminous performance, high thermal stability and high color purity. The material takes 9-fluorenone as a material mother nucleus, and a green material is obtained by introducing mono-substituted or multi-substituted aryl to 3, 6-positions of the 9-fluorenone. By means of electron pushing effect of the methoxyl group and electronic effect and space effect generated by different substitution positions, the injection and transmission of material carriers are more balanced, and the performance of the device is improved. Meanwhile, the material has a specific space torsion angle due to large steric hindrance, and the fluorescent quantum efficiency of the solid film is improved, so that the material can emit green light efficiently in an organic solvent. The invention also provides a preparation method of the green light material, and the method has the advantages of low raw material cost, mild reaction conditions, simple operation, high yield and the like. The invention also provides the application of the green light material in an organic electroluminescent device or an intelligent material, the material is a pure organic small-molecule green light material, the defects of low thermal stability of the existing electroluminescent material and heavy metal pollution of a waste luminescent device can be effectively overcome, and the application prospect is good.
Drawings
FIG. 1 is a synthetic scheme of examples 1 to 6 of the present invention;
FIG. 2 shows the product obtained in example 1 of the present invention1H NMR chart;
FIG. 3 shows the product obtained in example 1 of the present invention13C NMR chart;
FIG. 4 shows the product obtained in example 2 of the present invention1H NMR chart;
FIG. 5 shows the product obtained in example 2 of the present invention13C NMR chart;
FIG. 6 shows the product obtained in example 3 of the present invention1H NMR chart;
FIG. 7 shows the product obtained in example 3 of the present invention13C NMR chart;
FIG. 8 shows the product obtained in example 4 of the present invention1H NMR chart;
FIG. 9 shows the product obtained in example 4 of the present invention13C NMR chart;
FIG. 10 shows the product obtained in example 5 of the present invention1H NMR chart;
FIG. 11 shows the product obtained in example 5 of the present invention13C NMR chart;
FIG. 12 shows the product obtained in example 6 of the present invention1H NMR chart;
FIG. 13 shows the product obtained in example 6 of the present invention13C NMR chart;
FIG. 14 is a graph showing an emission spectrum of a product obtained in example 1 of the present invention;
FIG. 15 is a graph showing an emission spectrum of a product obtained in example 2 of the present invention;
FIG. 16 is a graph showing an emission spectrum of a product obtained in example 3 of the present invention;
FIG. 17 is a graph showing an emission spectrum of a product obtained in example 4 of the present invention;
FIG. 18 is a graph showing an emission spectrum of a product obtained in example 5 of the present invention;
FIG. 19 is a graph showing an emission spectrum of a product obtained in example 6 of the present invention;
FIG. 20 is a thermogravimetric analysis of the product obtained in example 5 of the present invention;
FIG. 21 is a thermogravimetric analysis of the product obtained in example 6 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and the detailed description, and it should be noted that any combination of the embodiments or technical features described below can be used to form a new embodiment without conflict.
The synthetic routes for the compounds of examples 1 to 6 are shown in figure 1.
Example 1
Synthesis of 3, 6-bis (4-methoxyphenyl) -9H-fluoren-9-one:
3, 6-dibromo-9H-fluoren-9-one (67.6mg,0.2mmol), 4-methoxyphenylboronic acid (91.2mg,0.6mmol), tetrakis (triphenylphosphine) palladium (11.6mg,0.01mmol), and potassium carbonate (165.8mg,1.2mmol) were added to a Schlenk tube. Under nitrogen protection, 3mL of tetrahydrofuran were added: the solution was mixed 3:1 with water and heated to 100 ℃ for 36 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a saturated NaCl solution was slowly added to the reaction mixture, followed by extraction with 3X 10mL of dichloromethane. The organic phases were combined and anhydrous Na was added2SO4Drying, filtering to remove Na2SO4The organic solvent was evaporated to dryness under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether: dichloromethane ═ 1:5) to give 3, 6-bis (4-methoxyphenyl) -9H-fluoren-9-one i in 85% yield. Process for preparing 3, 6-bis (4-methoxyphenyl) -9H-fluoren-9-one I1H NMR chart,13The C NMR charts are shown in FIG. 2 and FIG. 3, respectively.
1H NMR(400MHz,CDCl3)δ7.74(d,J＝1.5Hz,2H),7.70(d,J＝7.7Hz,2H),7.66–7.58(m,4H),7.48(dd,J＝7.7,1.5Hz,2H),7.05–6.99(m,4H),3.88(s,6H).13C NMR(100MHz,CDCl3)δ193.2,160.1,147.3,144.9,133.1,132.6,128.4,127.4,124.7,118.6,114.4,55.4.
Example 2
Synthesis of 3, 6-bis (3, 4-dimethoxyphenyl) -9H-fluoren-9-one:
3, 6-dibromo-9H-fluoren-9-one (67.6mg,0.2mmol), 3, 4-dimethoxyphenylboronic acid (109.2mg,0.6mmol), tetrakis (triphenylphosphine) palladium (11.6mg,0.01mmol), and sodium hydroxide (48mg,1.2mmol) were added to a Schlenk tube. Under nitrogen protection, 3mL of tetrahydrofuran were added: the solution was mixed 3:1 with water and heated to 100 ℃ for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a saturated NaCl solution was slowly added to the reaction mixture, followed by extraction with 3X 10mL of dichloromethane. The organic phases were combined and anhydrous Na was added2SO4Drying, filtering to remove Na2SO4The organic solvent was evaporated to dryness under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether: dichloromethane ═ 1:5) to give 3, 6-bis (3, 4-dimethoxyphenyl) -9H-fluoren-9-one ii in 91% yield. Process for preparing 3, 6-bis (3, 4-dimethoxyphenyl) -9H-fluoren-9-one II1H NMR chart,13The C NMR charts are shown in FIG. 4 and FIG. 5, respectively.
1H NMR(400MHz,CDCl3)δ7.75(s,2H),7.72(d,J＝7.6Hz,2H),7.49(d,J＝7.7Hz,2H),7.25(d,J＝8.8Hz,2H),7.17(s,2H),6.99(d,J＝8.2Hz,2H),4.00(s,6H),3.95(s,6H).13C NMR(100MHz,CDCl3)δ193.2,149.7,149.4,147.7,145.0,133.3,133.2,127.7,124.8,120.0,118.9,111.5,110.4,56.24,56.16.
Example 3
Synthesis of 3, 6-bis (3, 5-dimethoxyphenyl) -9H-fluoren-9-one:
3, 6-dibromo-9H-fluoren-9-one (67.6mg,0.2mmol), 3, 5-dimethoxyphenylboronic acid (109.2mg,0.6mmol), tetrakis (triphenylphosphine) palladium (11.6mg,0.0 mmol), and a reaction solution thereof were added to a reaction solution1mmol), sodium hydroxide (48mg,1.2mmol) were added to a Schlenk tube. Under nitrogen protection, 3mL of tetrahydrofuran were added: the solution was mixed 3:1 with water and heated to 100 ℃ for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a saturated NaCl solution was slowly added to the reaction mixture, followed by extraction with 3X 10mL of dichloromethane. The organic phases were combined and anhydrous Na was added2SO4Drying, filtering to remove Na2SO4The organic solvent was evaporated to dryness under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether: dichloromethane ═ 1:5) to give 3, 6-bis (3, 5-dimethoxyphenyl) -9H-fluoren-9-one iii in 88% yield. Process for preparing 3, 6-bis (3, 5-dimethoxyphenyl) -9H-fluoren-9-one III1H NMR chart,13The C NMR charts are shown in FIG. 6 and FIG. 7, respectively.
1H NMR(400MHz,CDCl3)δ7.75(s,2H),7.72(d,J＝7.6Hz,2H),7.51(d,J＝7.5Hz,2H),6.79(s,4H),6.53(s,2H),3.88(s,12H).13C NMR(100MHz,CDCl3)δ193.2,161.3,147.9,144.9,142.5,133.9,128.3,124.8,119.4,105.6,100.4,55.7.
Example 4
Synthesis of 3, 6-bis (2, 4-dimethoxyphenyl) -9H-fluoren-9-one:
3, 6-dibromo-9H-fluoren-9-one (67.6mg,0.2mmol), 2, 4-dimethoxyphenylboronic acid (109.2mg,0.6mmol), tetrakis (triphenylphosphine) palladium (11.6mg,0.01mmol), and sodium hydroxide (48mg,1.2mmol) were added to a Schlenk tube. Under nitrogen protection, 3mL of tetrahydrofuran were added: the solution was mixed 3:1 with water and heated to 100 ℃ for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a saturated NaCl solution was slowly added to the reaction mixture, followed by extraction with 3X 10mL of dichloromethane. The organic phases were combined and anhydrous Na was added2SO4Drying, filtering to remove Na2SO4The organic solvent was evaporated to dryness under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether: dichloromethane ═ 1:5) to give 3, 6-bis (2, 4-dimethoxyphenyl) -9H-fluoren-9-one iv in 84% yield. Process for preparing 3, 6-bis (2, 4-dimethoxyphenyl) -9H-fluoren-9-one IV1H NMR chart,13The C NMR charts are shown in FIG. 8 and FIG. 9, respectively.
1H NMR(400MHz,CDCl3)δ7.72–7.61(m,4H),7.41(d,J＝7.6Hz,2H),7.31(d,J＝8.1Hz,2H),6.69–6.46(m,4H),3.87(s,6H),3.83(s,6H).13C NMR(100MHz,CDCl3)δ193.7,161.2,157.7,145.2,144.5,133.0,131.3,130.1,124.0,122.8,121.7,104.9,99.2,55.8,55.6.
Example 5
Synthesis of 3, 6-bis (6-methoxynaphthalen-2-yl) -9H-fluoren-9-one:
3, 6-dibromo-9H-fluoren-9-one (67.6mg,0.2mmol), 6-methoxy-2-naphthylboronic acid (121.2mg,0.6mmol), tetrakis (triphenylphosphine) palladium (11.6mg,0.01mmol), and sodium hydroxide (48mg,1.2mmol) were added to a Schlenk tube. Under nitrogen protection, 3mL of tetrahydrofuran were added: the solution was mixed 3:1 with water and heated to 100 ℃ for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a saturated NaCl solution was slowly added to the reaction mixture, followed by extraction with 3X 10mL of dichloromethane. The organic phases were combined and anhydrous Na was added2SO4Drying, filtering to remove Na2SO4The organic solvent was evaporated to dryness under reduced pressure, and the crude product was purified by silica gel column chromatography (petroleum ether: dichloromethane ═ 1:5) to give 3, 6-bis (6-methoxynaphthalen-2-yl) -9H-fluoren-9-one v, yield 76%. Process for preparing 3, 6-bis (6-methoxynaphthalen-2-yl) -9H-fluoren-9-one V1H NMR chart,13The C NMR charts are shown in FIG. 10 and FIG. 11, respectively.
1H NMR(400MHz,CDCl3)δ8.09(s,2H),7.95(s,2H),7.85(t,J＝8.0Hz,4H),7.79(d,J＝8.0Hz,4H),7.66(d,J＝7.7Hz,2H),7.24–7.16(m,4H),3.96(s,6H).13C NMR(100MHz,CDCl3)δ193.2,158.3,147.8,145.0,135.3,134.4,133.4,129.9,129.0,128.1,127.6,126.2,125.6,124.8,119.6,119.2,105.6,55.4.
Example 6
Synthesis of 3, 6-bis (benzo [ d ] [1,3] dioxa-5-yl) -9H-fluoren-9-one:
3, 6-dibromo-9H-fluoren-9-one (67.6mg,0.2mmol), benzo [ d][1,3]Dioxa-5-ylboronic acid (99.5mg,0.6mmol), tetrakis (triphenylphosphine) palladium (11.6mg,0.01mmol), sodium hydroxide (48mg,1.2mmol) were added to a Schlenk tube. Under nitrogen protection, 3mL of tetrahydrofuran were added: the solution was mixed 3:1 with water and heated to 100 ℃ for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and a saturated NaCl solution was slowly added to the reaction mixture, followed by extraction with 3X 10mL of dichloromethane. The organic phases were combined and anhydrous Na was added2SO4Drying, filtering to remove Na2SO4Evaporating the organic solvent under reduced pressure, and performing silica gel column chromatography (petroleum ether: dichloromethane: 1:5) on the crude product to obtain the product 3, 6-bis (benzo [ d)][1,3]Dioxa-5-yl) -9H-fluoren-9-one VI in a yield of 92%. 3, 6-bis (benzo [ d ]][1,3]Process for dioxa-5-yl) -9H-fluoren-9-one VI1H NMR chart,13The C NMR charts are shown in FIG. 12 and FIG. 13, respectively.
1H NMR(400MHz,CDCl3)δ7.71(dd,J＝7.3,1.8Hz,4H),7.45(d,J＝7.7Hz,2H),7.19–7.10(m,4H),6.93(d,J＝7.8Hz,2H),6.05(s,4H).13C NMR(100MHz,CDCl3)δ193.1,148.5,148.2,147.6,145.0,134.6,133.4,127.8,124.8,121.3,119.0,108.9,107.7,101.6.
Examples of the experiments
And (3) emission spectrum detection:
using the compounds prepared in examples 1 to 6, 10 was prepared in a volumetric flask-4A dichloromethane standard solution of mol/L. Emission spectra of the compounds prepared in examples 1 to 6 were measured, and the results are shown in fig. 14 to 19. It can be seen from the graph that the peak wavelength of the luminescence of the compounds prepared in examples 1 to 6 is about 510nm, corresponding to the green region.
Thermogravimetric analysis:
compound V3.620 mg and Compound VI 3.867mg prepared in example 5 and example 6 were weighed out separately and analyzed by thermogravimetry on a model STA409PC thermal analyzer. Set maximum temperature 1050 ℃, test temperature range: and testing the compound at the temperature of between 30 and 1050 ℃ under the protection of argon. The results are shown in fig. 20 and 21: when the temperature is increased from room temperature to the final detection temperature of 963.5 ℃, the weight loss of the compound V and the compound VI is 35.12 percent and 23.17 percent respectively, which shows that the compound prepared by the invention has the characteristic of high thermal stability at higher temperature.
The invention provides a green light material based on a 9-fluorenone structure framework, which takes 9-fluorenone as a material mother nucleus and obtains the green light material by introducing mono-substituted or multi-substituted aryl to 3, 6-positions of the 9-fluorenone. By means of electron pushing effect of the methoxyl group and electronic effect and space effect generated by different substitution positions, the injection and transmission of material carriers are more balanced, and the performance of the device is improved. Meanwhile, the material has a specific space torsion angle due to large steric hindrance, and the fluorescent quantum efficiency of the solid film is improved, so that the material can emit green light efficiently in an organic solvent. The invention also provides a preparation method of the green light material, and the method has the advantages of low raw material cost, mild reaction conditions, simple operation, high yield and the like. The invention also provides the application of the green light material in an organic electroluminescent device or an intelligent material, the material is a pure organic small molecular green light material, has the characteristic of high color purity, can effectively overcome the defects of low thermal stability of the existing electroluminescent material and heavy metal pollution of a waste luminescent device, and has good application prospect.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (9)
1. A green light material based on a 9-fluorenone structural framework is characterized by having a structural general formula A
Wherein R is
R1、R2、R3Each independently selected from methoxy or hydrogen, R3Is methoxy.
2. The green light material based on the 9-fluorenone structural skeleton as claimed in claim 1, wherein the structure is as follows:
3. the method for preparing the green light material based on the 9-fluorenone structural skeleton according to claim 1 or 2, comprising the following steps:
under the protection of nitrogen, 3, 6-dibromo-9H-fluorene-9-ketone, boric acid derivative corresponding to R, tetrakis (triphenylphosphine) palladium and an alkaline substance are mixed, and a mixed solution of tetrahydrofuran and water is added to the mixture to react to obtain a final product A.
4. The method for preparing the green light material based on the 9-fluorenone structural framework, according to claim 3, wherein the molar ratio of the 3, 6-dibromo-9H-fluoren-9-one, the boric acid derivative corresponding to R, tetrakis (triphenylphosphine) palladium and the alkaline substance is 1 (2-5): (0.006-0.016): (0.8-2).
5. The method of claim 4, wherein the boronic acid derivative corresponding to R is one selected from the group consisting of 4-methoxyphenylboronic acid, 3, 4-dimethoxyphenylboronic acid, 3, 5-dimethoxyphenylboronic acid, 2, 4-dimethoxyphenylboronic acid, 6-methoxy-2-naphthylboronic acid, and benzo [ d ] [1,3] dioxa-5-ylboronic acid.
6. The method for preparing a green light material based on a 9-fluorenone structural framework according to claim 3, wherein the alkaline substance is one selected from potassium carbonate and sodium hydroxide.
7. The method for preparing the green light material based on the 9-fluorenone structural framework, according to claim 3, wherein the addition ratio of tetrahydrofuran, water and 3, 6-dibromo-9H-fluoren-9-one is (10-1) mL:1mL (225.3-22.5) mg.
8. The method for preparing the green light material based on the 9-fluorenone structural framework according to claim 3, wherein the reaction temperature is 100 ℃ and the reaction time is 24-36 h.
9. The use of the green material based on 9-fluorenone structural skeleton according to claim 1 or 2 in organic electroluminescent devices or smart materials.
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