CN111704623B - Organic electroluminescent red light material and preparation method and application thereof - Google Patents
Organic electroluminescent red light material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an organic light-emitting material, in particular to an organic electroluminescent red light material and a preparation method and application thereof. The organic electroluminescent red light material contains benzo [1,2-b:4,5-b' ] dithiophene and quinoxaline, the material compound is a compound capable of emitting red light, has more red shift of wavelength in a polar solvent, has better electronic transmission capability, has better application value in the field of photoelectric function, and in addition, the adopted preparation method is simple to operate and easy to synthesize.
Description
Technical Field
The invention relates to an organic light-emitting material, in particular to an organic electroluminescent red light material and a preparation method and application thereof.
Background
In recent decades, Organic Light Emitting Diodes (OLEDs) have been rapidly developed in the field of full color displays. The organic semiconductor material has great application prospect in the aspect of electroluminescent devices due to the characteristics of simple preparation, low cost, easy adjustment of functional structures and the like. Red, one of the three primary colors, plays a large role in the field of full-color organic light emission. However, compared with green and blue materials, the red material has poor fluorescence efficiency and color purity, which are determined by the properties of the material itself. Therefore, the development of organic small molecule red light emitting materials with high luminescence quantum efficiency, long lifetime and high color purity is urgently needed. Because small molecule red light materials generally have larger dipole moment and conjugated structure, molecules have strong charge transfer characteristics, and fluorescence quenching is caused by concentration quenching effect at larger concentration, so that the luminous efficiency of the small molecule red light materials is influenced. Based on this, it is the object of the present invention to combine benzo [1,2-b:4,5-b' ] dithiophene (BDT) with electron-withdrawing Quinoxaline (QT) to obtain a new red light material DCAQB with a lower band gap by using the D-A strategy and to apply it in the display field.
Disclosure of Invention
The invention aims to provide a luminescent material containing benzo [1,2-b:4,5-b' ] dithiophene and quinoxaline, a preparation method and photoelectric application thereof. The material compound is a compound capable of emitting red light, can be applied to the field of photoelectric functional material display, and is simple to operate and easy to synthesize.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic electroluminescent red light material contains benzo [1,2-b:4,5-b' ] dithiophene and quinoxaline, and the structural formula is as follows:
a preparation method of an organic electroluminescent red light material comprises the following steps:
step 1, mixing 5- (8- (5-bromothien-2-yl) -2, 3-dihexylquinoxalin-5-yl) thiophene-2-formaldehyde, 2-ethylhexyl 2-cyanoacetate, chloroform and piperidine, reacting under the protection of nitrogen, directly extracting a reaction product with water and dichloromethane after the reaction is finished, drying an organic phase with anhydrous sodium sulfate, spin-drying, and separating by column chromatography to obtain red solid 2-ethylhexyl (E) -3- (5- (8- (5-bromothien-2-yl) -2, 3-dihexylquinoxalin-5-yl) thien-2-yl) -2-cyanoacrylate (compound 1);
step 2, mixing 2-ethylhexyl (E) -3- (5- (8- (5-bromothiophene-2-yl) -2, 3-dihexylquinoxaline-5-yl) thiophene-2-yl) -2-cyanoacrylate, 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thiophene-2-) -benzodithiophene, a palladium catalyst and toluene, reacting under protection of nitrogen and keeping out of light, quenching the reaction by using a potassium fluoride solution after the reaction is finished, drying the toluene, extracting the reaction product by using water and dichloromethane, drying an organic phase by using anhydrous sodium sulfate, drying, and separating by using column chromatography to obtain a purple black solid bis (2-ethylhexyl) 3,3' - ((((((4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo (1, 2-b:4,5-b ') dithien-2, 6-diyl) bis (thiophen-5, 2-diyl)) bis (2, 3-dihexylquinoxalin-8, 5-diyl)) bis (thiophen-5, 2-diyl)) (2E, 2' E) -bis (2-cyanoacrylate) (QTBQT).
Further, 5- (8- (5-bromothien-2-yl) -2, 3-dihexylquinoxalin-5-yl) thiophene-2-carbaldehyde in said step 1 can be prepared according to the literature (Macromol. chem. Phys.,2014,215, 1388-.
Further, in the step 1, the molar ratio of 5- (8- (5-bromothiophene-2-yl) -2, 3-dihexylquinoxaline-5-yl) thiophene-2-formaldehyde, 2-ethylhexyl 2-cyanoacetate and piperidine is 1: 3-5: 0.1-0.3.
Further, the reaction temperature in the step 1 is 60-65 ℃, and the reaction time is 30-45 h.
Further, the column chromatography in the step 1 comprises dichloromethane and petroleum ether, and the volume ratio of the dichloromethane to the petroleum ether is 1: 2.
Still further, in the step 2, the molar ratio of 2-ethylhexyl (E) -3- (5- (8- (5-bromothien-2-yl) -2, 3-dihexylquinoxalin-5-yl) thien-2-yl) -2-cyanoacrylate, 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thien-2-yl) -benzodithiophene and palladium catalyst is 2-2.5: 1: 0.1-0.15, wherein the palladium catalyst is palladium tetratriphenylphosphine.
And further, the temperature of the light-shielding reaction in the step 2 is 100-110 ℃, and the time of the light-shielding reaction is 20-30 hours.
Furthermore, the concentration of the potassium fluoride solution in the step 2 is 1-5 mol/L.
Furthermore, the column chromatography in step 2 comprises dichloromethane and petroleum ether, and the volume ratio of dichloromethane to petroleum ether is 3: 1.
An application of organic electroluminescent red light material, which is used as photoelectric functional material in the field of display.
Compared with the prior art, the invention has the following advantages:
the material containing benzo [1,2-b:4,5-b' ] dithiophene and quinoxaline obtained by the invention is a red light material, has higher luminous efficiency and brightness, and is an ideal red light luminescent material. The luminescent material can be used as a photoelectric functional material in the field of displays. The adopted preparation method has simple reaction operation and easy synthesis.
Drawings
FIG. 1 is a diagram showing an ultraviolet absorption spectrum of a luminescent material in chloroform according to example 1 of the present invention;
FIG. 2 is a fluorescence emission spectrum of the luminescent material of example 1 of the present invention in chloroform;
FIG. 3 is a theoretical calculation of a luminescent material simulation of example 1 of the present invention;
FIG. 4 shows the emission wavelengths of the luminescent material of example 1 of the present invention in different solvents;
FIG. 5 shows a luminescent material and C in embodiment 1 of the present invention70Fluorescence spectra of the interaction in toluene solution;
fig. 6 is a fluorescence spectrum of the interaction between the luminescent material of example 1 of the present invention and the carbon nanotube in the toluene solution.
Detailed Description
Example 1
Step 1, 5- (8- (5-bromothien-2-yl) -2, 3-dihexylquinoxalin-5-yl) thiophene-2-carbaldehyde (100mg,0.176mmoL), 2-ethylhexyl 2-cyanoacetate (174mg,0.88mmoL), piperidine (4. mu.L, 0.035mmoL) was added to a three-necked round bottom flask containing 30mL of a chloroform solution, and reacted at 65 ℃ under reflux for 40 hours under nitrogen. After the reaction is finished, the reaction is directly extracted by water and dichloromethane, and the organic phase is dried by anhydrous sodium sulfate and then is dried by spinning. Column chromatography (dichloromethane: petroleum ether ═ 1:2) gave 110mg of compound 1 (red solid, 84%).
1H NMR(600MHz,CDCl3):δ8.34(s,1H),8.12(d,1H),8.04(d,1H),7.93(d,1H),7.89(d,1H),7.57(d,1H),7.14(d,1H),4.25(t,2H),3.14-3.10(m,4H),1.77(m,1H),1.54-1.49(m,6H),1.43-1.35(m,18H),0.97(m,12H)HRMS-ESI for C40H50BrN3O2S2(m/z)747.8[M]
Step 2, compound 1(80mg,0.107mmoL) and 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thienyl-2-) -benzodithiophene (40.4mg,0.044mmoL) were added to a 15mL pressure bottle. 6mL of toluene was added via syringe and the palladium catalyst, palladium tetrakistriphenylphosphine (5mg,0.0044mmol), was added to the reaction flask under nitrogen. The reaction is carried out for 20 hours at 100 ℃ under the protection of nitrogen and in the dark. After the reaction is finished, quenching the reaction by using 1mL of 5mol/L potassium fluoride solution, spin-drying the toluene, extracting the reaction by using water and dichloromethane, and drying an organic phase by using anhydrous sodium sulfate and spin-drying. Column chromatography (dichloromethane: petroleum ether ═ 3:1) isolated 75mg QTBQT (purple black solid, 89.2%).
1H NMR(600MHz,CDCl3):δ8.26(s,2H),8.06(d,2H),7.97(d,2H),7.83(d,2H),7.79(d,2H),7.74(t,2H),7.67(t,2H),7.34(t,2H),7.25(d,2H),6.96(d,2H),4.21(t,4H),2.94(d,4H),2.13-1.92(m,8H),1.82-1.66(m,2H),1.69-1.31(m,66H),1.03(t,6H),0.93(t,18H),0.86(t,12H)MODI-TOF MS for C114H140N6O4S8(m/z)1914.22[M]
Example 2
A preparation method of an organic electroluminescent red light material comprises the following steps:
step 1, 5- (8- (5-bromothien-2-yl) -2, 3-dihexylquinoxalin-5-yl) thiophene-2-carbaldehyde (100mg,0.176mmoL), 2-ethylhexyl 2-cyanoacetate (138mg,0.704mmoL), piperidine (4. mu.L, 0.035mmoL) were added to a three-necked round bottom flask containing 30mL of a chloroform solution, and reacted at 60 ℃ under reflux for 45 hours under nitrogen. After the reaction is finished, the reaction is directly extracted by water and dichloromethane, and the organic phase is dried by anhydrous sodium sulfate and then is dried by spinning. Column chromatography (dichloromethane: petroleum ether ═ 1:2) isolated 105mg of compound 1 (red solid, 80.7%).
1H NMR(600MHz,CDCl3):δ8.34(s,1H),8.12(d,1H),8.04(d,1H),7.93(d,1H),7.89(d,1H),7.57(d,1H),7.14(d,1H),4.25(t,2H),3.14-3.10(m,4H),1.77(m,1H),1.54-1.49(m,6H),1.43-1.35(m,18H),0.97(m,12H)HRMS-ESI for C40H50BrN3O2S2(m/z)747.8[M]
Step 2, compound 1(82mg,0.11mmoL) and 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thienyl-2-) -benzodithiophene (40.4mg,0.044mmoL) were added to a 15mL pressure bottle. 6mL of toluene was added via syringe and the palladium catalyst, tetrakis triphenylphosphine palladium (7.5mg,0.0066mmol), was added to the reaction flask under nitrogen. The reaction is carried out for 20 hours at 100 ℃ under the protection of nitrogen and in the dark. After the reaction is finished, quenching the reaction by using a small amount of 3mol/L potassium fluoride solution, spin-drying the toluene, extracting the reaction by using water and dichloromethane, and drying an organic phase by using anhydrous sodium sulfate and spin-drying. Column chromatography (dichloromethane: petroleum ether ═ 3:1) isolated 70mg QTBQT (purple black solid, 83.3%).
1H NMR(600MHz,CDCl3):δ8.26(s,2H),8.06(d,2H),7.97(d,2H),7.83(d,2H),7.79(d,2H),7.74(t,2H),7.67(t,2H),7.34(t,2H),7.25(d,2H),6.96(d,2H),4.21(t,4H),2.94(d,4H),2.13-1.92(m,8H),1.82-1.66(m,2H),1.69-1.31(m,66H),1.03(t,6H),0.93(t,18H),0.86(t,12H)MODI-TOF MS for C114H140N6O4S8(m/z)1914.22[M]
Example 3
A preparation method of an organic electroluminescent red light material comprises the following steps:
step 1, 5- (8- (5-bromothien-2-yl) -2, 3-dihexylquinoxalin-5-yl) thiophene-2-carbaldehyde (100mg,0.176mmoL), 2-ethylhexyl 2-cyanoacetate (174mg,0.88mmoL), piperidine (6. mu.L, 0.528mmoL) were added to a three-necked round-bottomed flask containing 30mL of a chloroform solution, and reacted at 65 ℃ under reflux for 40 hours under nitrogen. After the reaction is finished, the reaction is directly extracted by water and dichloromethane, and the organic phase is dried by anhydrous sodium sulfate and then is dried by spinning. Column chromatography (dichloromethane: petroleum ether ═ 1:2) gave 115mg of compound 1 (red solid, 88.5%).
1H NMR(600MHz,CDCl3):δ8.34(s,1H),8.12(d,1H),8.04(d,1H),7.93(d,1H),7.89(d,1H),7.57(d,1H),7.14(d,1H),4.25(t,2H),3.14-3.10(m,4H),1.77(m,1H),1.54-1.49(m,6H),1.43-1.35(m,18H),0.97(m,12H)HRMS-ESI for C40H50BrN3O2S2(m/z)747.8[M]
Step 2, compound 1(80mg,0.107mmoL) and 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thienyl-2-) -benzodithiophene (40.4mg,0.044mmoL) were added to a 15mL pressure bottle. 6mL of toluene was added via syringe and the palladium catalyst, palladium tetrakistriphenylphosphine (5mg,0.0044mmol), was added to the reaction flask under nitrogen. The reaction is carried out for 25h under the protection of nitrogen and at 105 ℃ in the dark. After the reaction is finished, quenching the reaction by using 1mL of 4mol/L potassium fluoride solution, spin-drying the toluene, extracting the reaction by using water and dichloromethane, and drying an organic phase by using anhydrous sodium sulfate and then spin-drying. Column chromatography (dichloromethane: petroleum ether ═ 3:1) isolated 75mg QTBQT (purple black solid, 89.2%).
1H NMR(600MHz,CDCl3):δ8.26(s,2H),8.06(d,2H),7.97(d,2H),7.83(d,2H),7.79(d,2H),7.74(t,2H),7.67(t,2H),7.34(t,2H),7.25(d,2H),6.96(d,2H),4.21(t,4H),2.94(d,4H),2.13-1.92(m,8H),1.82-1.66(m,2H),1.69-1.31(m,66H),1.03(t,6H),0.93(t,18H),0.86(t,12H)MODI-TOF MS for C114H140N6O4S8(m/z)1914.22[M]
Example 4
A preparation method of an organic electroluminescent red light material comprises the following steps:
step 1, 5- (8- (5-bromothien-2-yl) -2, 3-dihexylquinoxalin-5-yl) thiophene-2-carbaldehyde (100mg,0.176mmoL), 2-ethylhexyl 2-cyanoacetate (104mg,0.528mmoL), piperidine (2. mu.L, 0.0176mmoL) were added to a three-necked round-bottomed flask containing 30mL of a chloroform solution, and the reaction was refluxed at 62 ℃ for 30 hours under nitrogen. After the reaction is finished, the reaction is directly extracted by water and dichloromethane, and the organic phase is dried by anhydrous sodium sulfate and then is dried by spinning. Column chromatography (dichloromethane: petroleum ether ═ 1:2) gave 98mg of compound 1 (red solid, 75.3%).
1H NMR(600MHz,CDCl3):δ8.34(s,1H),8.12(d,1H),8.04(d,1H),7.93(d,1H),7.89(d,1H),7.57(d,1H),7.14(d,1H),4.25(t,2H),3.14-3.10(m,4H),1.77(m,1H),1.54-1.49(m,6H),1.43-1.35(m,18H),0.97(m,12H)HRMS-ESI for C40H50BrN3O2S2(m/z)747.8[M]
Step 2, compound 1(65mg,0.088mmoL) and 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thienyl-2-) -benzodithiophene (40.4mg,0.044mmoL) were added to a 15mL pressure bottle. 6mL of toluene was added via syringe and the palladium catalyst tetrakistriphenylphosphine palladium (6.3mg0.0055mmoL) was added to the reaction flask under nitrogen. The reaction is carried out for 25h under the protection of nitrogen and at 110 ℃ in the dark. After the reaction is finished, quenching the reaction by using 1mL of 1mol/L potassium fluoride solution, spin-drying the toluene, extracting the reaction by using water and dichloromethane, and drying an organic phase by using anhydrous sodium sulfate and then spin-drying. Column chromatography (dichloromethane: petroleum ether ═ 3:1) isolated 78mg qtbqt (purple black solid, 92.8%).
1H NMR(600MHz,CDCl3):δ8.26(s,2H),8.06(d,2H),7.97(d,2H),7.83(d,2H),7.79(d,2H),7.74(t,2H),7.67(t,2H),7.34(t,2H),7.25(d,2H),6.96(d,2H),4.21(t,4H),2.94(d,4H),2.13-1.92(m,8H),1.82-1.66(m,2H),1.69-1.31(m,66H),1.03(t,6H),0.93(t,18H),0.86(t,12H)MODI-TOF MS for C114H140N6O4S8(m/z)1914.22[M]
Example 5
5mL of trichloromethane solution of 50 mu g/mL of luminescent material QTBQT is prepared. Accurately, 2.0mL of the sample was transferred to a cuvette and then measured on a HITACHI UH5300 ultraviolet absorption apparatus to obtain an absorption peak of 535 nm. The test results are shown in fig. 1. After that, 2.0mL of the solution was accurately transferred again and added to the fluorescence cell, and then measured on a HITACHI F-4600 fluorometer, the excitation slit widths were all 5nm, and the emission slit width was 5 nm. The excitation wavelength was 535nm and the maximum emission wavelength was 654nm, and the test was carried out at room temperature and at ambient atmospheric pressure. The test results are shown in fig. 2.
Example 6
The QTBQT is theoretically calculated under the DFT/B3LYP/6-31G (d) group by using Gaussian 09 software, and the geometric configuration and the electron distribution of the material are shown in figure 3. QTBQT has a HOMO level of-5 eV, an electron density predominantly distributed on benzo [1,2-b:4,5-b' ] dithiophene, a LUMO level of-2.8 eV, and an electron density predominantly distributed on quinoxaline.
Example 7
Preparing 1mg/mL QTBQT chloroform solution, respectively adding 20 mu L of the chloroform solution into different solvents to ensure that the final volume is 2mL, and obtaining 50 mu g/mL QTBQT solution with different solvents. These solutions were removed from the cuvette and the emission wavelength was measured on a HITACHI F-4600 fluorometer and the curves were normalized as shown in FIG. 4. The results show that the emission wavelength of QTBQT gradually shifts in red with increasing polarity of the solvent, indicating that it has better intermolecular charge transfer capability in polar solvents.
Example 8
Preparing 50 mu g/mL toluene solution of luminescent material QTBQT and 1mg/mL C70In toluene, and C70The solution is mixed with QTBQT solution to obtain mixed solution with a certain concentration gradient. And the fluorescence emission of these mixed solutions was measured in a HITACHIF-4600 fluorometer, and the results are shown in FIG. 5. The results show that with C70The concentration of (a) gradually increases, and the fluorescence of the QTBQT is gradually quenched. Description of QTBQT and C70The QTBQT has certain electronic transmission capability because of the interaction between the QTBQT and the other QTBQT.
Example 9
Preparing 50 mu g/mL toluene solution of luminescent material QTBQT and 2mg/mL toluene solution of carbon nano tube, and mixing the carbon nano tube solution and the QTBQT solution to obtain a mixed solution with a certain concentration gradient. And the fluorescence emission of these mixed solutions was measured in a HITACHI F-4600 fluorometer, and the results are shown in FIG. 6. The results show that the fluorescence of QTBQT is gradually quenched as the concentration of carbon nanotubes is gradually increased. Therefore, the QTBQT has a certain electronic transmission capability.
Claims (10)
1. An organic electroluminescent material is characterized by containing benzo [1,2-b:4,5-b' ] dithiophene and quinoxaline, and the structural formula is as follows:
2. the method for preparing an organic electroluminescent red light material as claimed in claim 1, comprising the steps of:
step 1, mixing 5- (8- (5-bromothiophene-2-yl) -2, 3-dihexylquinoxaline-5-yl) thiophene-2-formaldehyde, 2-ethylhexyl 2-cyanoacetate, chloroform and piperidine, reacting under the protection of nitrogen, directly extracting a reaction product with water and dichloromethane after the reaction is finished, drying an organic phase with anhydrous sodium sulfate, spin-drying, and separating by column chromatography to obtain red solid 2-ethylhexyl (E) -3- (5- (8- (5-bromothiophene-2-yl) -2, 3-dihexylquinoxaline-5-yl) thiophene-2-yl) -2-cyanoacrylate;
step 2, mixing 2-ethylhexyl (E) -3- (5- (8- (5-bromothiophene-2-yl) -2, 3-dihexylquinoxaline-5-yl) thiophene-2-yl) -2-cyanoacrylate, 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thiophene-2-) -benzodithiophene, a palladium catalyst and toluene, reacting under protection of nitrogen and keeping out of light, quenching the reaction by using a potassium fluoride solution after the reaction is finished, drying the toluene, extracting the reaction product by using water and dichloromethane, drying an organic phase by using anhydrous sodium sulfate, drying, and separating by using column chromatography to obtain a purple black solid bis (2-ethylhexyl) 3,3' - ((((((4, 8-bis (5- (2-ethylhexyl) thiophen-2-yl) benzo (1, 2-b:4,5-b ') dithien-2, 6-diyl) bis (thiophen-5, 2-diyl)) bis (2, 3-dihexylquinoxalin-8, 5-diyl)) bis (thiophen-5, 2-diyl)) (2E, 2' E) -bis (2-cyanoacrylate).
3. The method for preparing an organic electroluminescent red material according to claim 2, wherein the molar ratio of 5- (8- (5-bromothien-2-yl) -2, 3-dihexylquinoxalin-5-yl) thiophene-2-carbaldehyde, 2-ethylhexyl 2-cyanoacetate and piperidine in step 1 is 1:3 to 5:0.1 to 0.3.
4. The method for preparing an organic electroluminescent red light material according to claim 2, wherein the reaction temperature in the step 1 is 60-65 ℃ and the reaction time is 30-45 h.
5. The method for preparing an organic electroluminescent red material according to claim 2, wherein the components separated by column chromatography in step 1 are dichloromethane and petroleum ether, and the volume ratio of dichloromethane to petroleum ether is 1: 2.
6. The method for preparing an organic electroluminescent red material according to claim 2, wherein the molar ratio of 2-ethylhexyl (E) -3- (5- (8- (5-bromothien-2-yl) -2, 3-dihexylquinoxalin-5-yl) thien-2-yl) -2-cyanoacrylate, 2, 6-bis (trimethyltin) -4, 8-bis (5- (2-ethylhexyl) thien-2-) -benzodithiophene and palladium catalyst in step 2 is 2-2.5: 1: 0.1-0.15, wherein the palladium catalyst is palladium tetratriphenylphosphine.
7. The method for preparing an organic electroluminescent red material according to claim 2, wherein the temperature of the reaction in the step 2 is 100-110 ℃ away from light, and the reaction time in the step 2 is 20-30 h away from light.
8. The method for preparing an organic electroluminescent red light material according to claim 2, wherein the concentration of the potassium fluoride solution in the step 2 is 1-5 mol/L.
9. The method for preparing an organic electroluminescent red material according to claim 2, wherein the components separated by column chromatography in step 2 are dichloromethane and petroleum ether, and the volume ratio of dichloromethane to petroleum ether is 3: 1.
10. The use of an organic electroluminescent red material according to claim 1 as an electro-optical functional material in the field of displays.
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