CN117683027A - An organic hole injection material and its application - Google Patents
An organic hole injection material and its application Download PDFInfo
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- CN117683027A CN117683027A CN202211054115.XA CN202211054115A CN117683027A CN 117683027 A CN117683027 A CN 117683027A CN 202211054115 A CN202211054115 A CN 202211054115A CN 117683027 A CN117683027 A CN 117683027A
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Abstract
本发明涉及一种有机空穴注入材料，化学通式如下：本发明的空穴注入材料，结构含氮杂芴烯类衍生物与环状缺电子基团两个单元等。此类材料相比以前的空穴注入材料具有以下优势：材料的合成较为简单，有利于大规模生产；材料的HOMO与LUMO能级结构合适，有利于载流子的注入；材料以氮杂芴烯类衍生物与缺电子基团为核心，有利于载流子在有机层中传输；材料具有较高的LUMO/HOMO能级，有利于将空穴从阳极ITO传输到空穴传输层中。
The invention relates to an organic hole injection material, the general chemical formula of which is as follows: The hole injection material of the present invention has a structure containing two units: a nitrogen heterofluorene derivative and a cyclic electron-deficient group. This type of material has the following advantages compared with previous hole injection materials: the synthesis of the material is relatively simple, which is conducive to mass production; the HOMO and LUMO energy level structure of the material is suitable, which is conducive to the injection of carriers; the material is based on azafluorene Alkene derivatives and electron-deficient groups are at the core, which is conducive to carrier transport in the organic layer; the material has a high LUMO/HOMO energy level, which is conducive to transporting holes from the anode ITO to the hole transport layer.
Description
Technical Field
The invention relates to the field of organic photoelectricity, in particular to a hole injection material, an organic light-emitting diode and a perovskite solar cell.
Background
Organic Light-emitting Diodes (OLEDs) are a new generation of display technology, and are becoming an important component in the current display technology due to their advantages of self-luminescence, flexibility, high contrast, power saving, etc., and have been widely paid attention to in academia and industry. In OLEDs devices, the hole injection layer serves as a critical material connecting the anode to the organic functional layer. It can reduce the potential barrier for hole injection from the anode, allowing holes to be efficiently injected from the anode into the OLED device. Therefore, matching of the material energy level and the anode material needs to be considered when selecting the hole injection layer material. The injection layer has the function of well matching the work function of the anode with the HOMO of the hole transport layer material, so that holes can smoothly flow from the electrode to the transport layer, and the highest occupied orbit energy level of the luminescent material is close to the work function of the anode in a mode of actually adopting OLED structural design, so that the injection energy barrier of the holes is reduced. A hole injection layer is usually added between the anode and the hole transport layer, mainly because the energy barrier between the anode and the hole transport layer is large, which causes the driving voltage of the device to increase, and indirectly shortens the lifetime of the device, so that a layer of material with HOMO energy level between the anode and the hole transport layer is added to improve the efficiency between the hole injection and the hole transport layer. The development of suitable hole injection materials plays an important role in improving the performance of OLEDs.
Disclosure of Invention
Aiming at the defects of the existing hole injection material, the invention provides a hole injection material formed by connecting an azafluorenes alkene derivative with an electron-deficient group and application thereof.
The technical scheme of the invention is realized by the following steps: an organic hole injection material is provided, and the chemical formula is as follows:
wherein R is 1 、R 2 Each independently selected from carbonyl, ethylcyano, or propyldicyano;
x, Y is C-H, N or C-OH, identical to or different from each other;
ar is selected from benzene ring, pyridine ring, fluoro benzene ring, pyridine ring and the like;
n=0, 1,2,3 or 4.
Preferably, in one embodiment of the present invention, the hydrogen atoms or all of the atoms in the formula are deuterium atoms.
Preferably, in one embodiment of the invention, the hydrogen on the aromatic ring of the Ar group may be a partially or fully deuterated deuterium atom.
Preferably, in one embodiment of the present invention, the molecular formula thereof is selected from one of the following:
the present invention also provides an organic light emitting device comprising a cathode, an anode and respective organic layers; wherein the electron injection layer uses the organic hole injection material according to any one of the foregoing.
The efficiency of the organic/inorganic hybrid perovskite solar cell is 3.8% from 2009, and the efficiency of the organic/inorganic hybrid perovskite solar cell is developed to 25% so far, so that the organic/inorganic hybrid perovskite solar cell is the most rapid cell developed in the third generation photovoltaic technology. The device structure comprises a hole transport material and an electron transport material, which play a role of carrier transport balance.
The invention also provides a perovskite solar cell comprising a cathode, an anode and each organic layer; wherein the hole injection layer uses the organic hole injection material according to any one of the foregoing.
The beneficial effects are as follows:
the hole injection material has two units of nitrogen-containing heterofluorene derivatives and cyclic electron-deficient groups. Such materials have the following advantages over previous hole injection materials: the synthesis of the material is simpler, which is beneficial to large-scale production; the HOMO and LUMO energy level structures of the material are proper, so that the injection of carriers is facilitated; the material takes the aza fluorenes derivatives and electron-deficient groups as cores, which is beneficial to the carrier transmission in the organic layer; the material has a higher LUMO/HOMO energy level, which is advantageous for transporting holes from the anode ITO into the hole transport layer.
Drawings
Fig. 1 is a schematic structural diagram of an organic electroluminescent device according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a perovskite solar cell device according to an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention and corresponding drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention will now be described in further detail with reference to the drawings and examples.
Example 1
The synthetic route for compound 1 is shown below:
the synthesis method of the compound 1 specifically comprises the following steps:
synthesis of intermediate M1: 1H-indene-1, 3 (2H) -dione (7.31 g,50 mmol) and potassium carbonate (8.3 g,60 mmol) were taken and stirred in THF (100 mL) at room temperature for 20 hours. After 4, 5-diazafluoren-9-one (9.11 g,50 mmol) was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extraction with chloroform was performed, water washing was performed 3 times, drying over anhydrous magnesium sulfate was performed, and spin drying was performed to obtain the crude product, which was directly used as the next step without purification.
To the crude product obtained above, 200mL of a concentrated HCl/etoh=4:1 mixed solution was added and refluxed for 6 hours. Saturated potassium carbonate solution was added to adjust ph=7-8, chloroform was used for extraction, and 100mL of two were used for the aqueous phaseThe methyl chloride was extracted three times, the organic phases were combined, dried over anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography to give the compound represented by formula 1 (13.80 g, yield 89%). 1 H NMR(400MHz,Chloroform-d)δ8.81(dd,J＝3.6，1.6Hz,2H),8.05―8.02(m,2H),7.99―7.97(m,2H),7.76―7.72(m,2H),7.60―7.57(m,2H). 13 C NMR(100MHz,Chloroform-d)δ188.30,157.40,151.36,144.50,140.02,133.70,133.58,132.00,125.17,123.12,122.76.
Example 2
The synthetic route for compound 25 is shown below:
the synthesis method of the compound 25 specifically comprises the following steps:
synthesis of intermediate M25: 4,5,6,7-d 4-1H-indene-1, 3 (2H) -dione (7.51 g,50 mmol) and potassium carbonate (8.3 g,60 mmol) were taken and stirred in THF (100 mL) at room temperature for 20 hours. After 4, 5-diazafluoren-9-one (9.11 g,50 mmol) was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extraction with chloroform was performed, water washing was performed 3 times, drying over anhydrous magnesium sulfate was performed, and spin drying was performed to obtain the crude product, which was directly used as the next step without purification.
To the crude product obtained above, 200mL of a concentrated HCl/etoh=4:1 mixed solution was added and refluxed for 6 hours. Saturated potassium carbonate solution was added to adjust ph=7-8, extraction was performed with chloroform, extraction was performed three times with 100mL of dichloromethane, the organic phases were combined, dried over anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography to give the compound represented by formula 25 (15.72 g, yield 79%). 1 H NMR(400MHz,Chloroform-d)δ8.81(dd,J＝3.5，1.6Hz,2H),δ7.98(dd,J＝6.2，1.6Hz,2H),7.60―7.57(m,2H). 13 C NMR (100 MHz, chloroform-d) delta 188.32,157.40,151.36,144.50,142.15,133.70,133.41,133.98,124.47,123.12,122.18. Example 3
The synthetic route for compound 30 is shown below:
the synthesis method of the compound 30 specifically comprises the following steps:
synthesis of intermediate M30: 4,5,6, 7-tetrafluoro-1H-indene-1, 3 (2H) -dione (10.91 g,50 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at room temperature for 20 hours. After 4, 5-diazafluoren-9-one (9.11 g,50 mmol) was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extraction with chloroform was performed, water washing was performed 3 times, drying over anhydrous magnesium sulfate was performed, and spin drying was performed to obtain the crude product, which was directly used as the next step without purification.
Acetonitrile (2.26 g,55 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at r.t. for 20 hours. After the crude product obtained above was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extraction was performed with chloroform, washing was performed 3 times, drying was performed with anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography to obtain product M30 (15.87 g, yield 75%). 1 H NMR(400MHz,Chloroform-d)δ8.73―8.71(m,2H),7.72―7.70(m,2H),7.44―7.41(m,2H),5.73(s,1H),5.56(d,J＝1.3Hz,1H),4.89(d,J＝1.3Hz,1H). 13 C NMR(100MHz,Chloroform-d)δ191.40(dt),154.21,150.21,148.70(ddd),147.55(ddt),147.10(dt),146.22(ddd),144.25(ddt),137.58,129.33(ddt),128.77,122.81,122.69(ddt),117.42,101.05,60.18.
Synthesis of Compound 30: m30 (21.17 g,50 mmol) was weighed into a 500mL single-necked flask, 200mL of a concentrated HCl/etoh=4:1 mixed solution was added, and refluxed for 6 hours. Saturated potassium carbonate solution was added to adjust ph=7-8, extraction was performed with chloroform, extraction was performed three times with 100mL of dichloromethane, the organic phases were combined, dried over anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography to give the compound represented by formula 30 (16.21 g, yield 80%). 1 H NMR(400MHz,Chloroform-d)δ8.81(dd,J＝3.5，1.6Hz,2H),8.00―7.98(m,2H),7.59―7.57(m,2H),δ6.74(s,1H). 13 C NMR(100MHz,Chloroform-d)δ180.73(dt),156.76,154.21(dt),151.36,145.65(dt), 144.93 (dd), 144.86 (dd), 144.71 (dt), 143.99,143.63 (dt), 142.88 (m), 142.76 (m), 142.65 (m), 140.74 (ddd), 136.15 (t), 132.95,132.07,125.67 (ddt), 123.72 (ddt), 123.12,117.83,97.63 (d) example 4
The synthetic route for formula 39 is shown below:
the synthesis method of the compound 39 specifically comprises the following steps:
synthesis of intermediate M39: 5, 6-difluoro-1-indenone (8.40 g,50 mmol) and potassium carbonate (8.3 g,60 mmol) were taken and stirred in THF (100 mL) at room temperature for 20 hours. After 4, 5-diazafluoren-9-one (9.11 g,50 mmol) was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extraction with chloroform was performed, water washing was performed 3 times, drying over anhydrous magnesium sulfate was performed, and spin drying was performed to obtain the crude product, which was directly used as the next step without purification.
Malononitrile (3.3 g,55 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at r.t. for 20 hours. After the crude product obtained above was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extraction was performed with chloroform, washing was performed 3 times, drying was performed with anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography to obtain product M39 (15.45 g, yield 75%). 1 H NMR(400MHz,Chloroform-d)δ8.72(quant,J＝1.8Hz,2H),8.20(m,1H),7.90(m,1H),7.71(quant,J＝6.0,1.8Hz,2H),7.45―7.42(m,2H),7.36―7.33(m,4H),7.26―7.23(m,1H),5.35(s,1H),4.36(s,1H). 13 C NMR(100MHz,Chloroform-d)δ200.55(dd),154.24,153.47(dd),152.35(dd),151.54(dd),150.20,137.96,137.02,133.80,128.77,122.81,115.64(dd),113.57(dd),113.38(dd),111.67(dd),81.56,75.38,58.06.
Synthesis of Compound 39: m39 (20.60 g,50 mmol) was weighed into a 500mL single-necked flask, 200mL of a concentrated HCl/etoh=4:1 mixed solution was added, and refluxed for 6 hours. Saturated potassium carbonate solution was added to adjust ph=7-8, extraction was performed with chloroform, and 100mL of dichloro was used for the aqueous phaseThe methane extraction was performed three times, the organic phases were combined, dried over anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography to give the compound represented by formula 39 (16.75 g, yield 86%). 1 H NMR(400MHz,Chloroform-d)δ8.82(quant,J＝6.0 1.8Hz,2H),8.13(m,1H),7.98(quant,J＝6.0 1.8Hz,2H),7.60―7.58(m,1H),7.46―7.44(m,1H). 13 C NMR(100MHz,Chloroform-d)δ188.48(dd),156.85,152.12(dd),152.07(dd),151.50(dd),151.34,144.26,136.66,134.45,132.25,132.11,130.93,123.11,116.66(dd),114.24(dd),113.48(dd),110.57(dd),73.10.
Example 5
The synthetic route for compound 134 is shown below:
the synthesis method of the compound 134 specifically comprises the following steps:
synthesis of intermediate M134: 5, 6-difluoro-1-indenone (8.40 g,50 mmol) and potassium carbonate (8.3 g,60 mmol) were taken and stirred in THF (100 mL) at room temperature for 20 hours. After 4, 5-diazafluoren-9-one (9.11 g,50 mmol) was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extraction with chloroform was performed, water washing was performed 3 times, drying over anhydrous magnesium sulfate was performed, and spin drying was performed to obtain the crude product, which was directly used as the next step without purification.
Malononitrile (3.3 g,55 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at r.t. for 20 hours. After the crude product obtained above was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extracted with chloroform, washed 3 times with water, and dried over anhydrous magnesium sulfate to give a crude product without further purification. Acetonitrile (2.26 g,55 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at r.t. for 20 hours. After the crude product obtained above was added to the system, the reaction was stirred at 80℃for 20 hours. Cooling to room temperature, adding 1N hydrochloric acid solution to adjust pH to 6-7, extracting with chloroform, washing with water for 3 times, and drying with anhydrous magnesium sulfate to obtain crude productThe resultant was purified by silica gel column chromatography to give product M134 (17.85 g, yield 82%). 1 H NMR(400MHz,Chloroform-d)δ8.72(quant,J＝1.5Hz,2H),7.81(dq,J＝4.1,0.72Hz,2H),7.71(dd,J＝6.3,1.8Hz,2H),7.41(dd,J＝6.3,3.0Hz,2H),5.35(d,J＝1.4Hz,1H),5.08(s,1H),4.65(d,J＝1.3Hz,1H). 13 C NMR(100MHz,Chloroform-d)δ160.18(d),154.29,152.24(dd),150.23(dd),150.21,144.95(d),137.40,136.65(dd),135.01(dd),128.78,122.77,114.06(dd),113.57,113.38,111.54(dd),104.67,82.29,76.06,63.35.
Synthesis of Compound 134: m134 (21.77 g,50 mmol) was weighed into a 500mL single-necked flask, 200mL of concentrated HCl/etoh=4:1 mixed solution was added, and refluxed for 6 hours. Saturated potassium carbonate solution was added to adjust ph=7-8, extraction was performed with chloroform, extraction was performed three times with 100mL of dichloromethane, the organic phases were combined, dried over anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography to give the compound represented by formula 134 (16.9 g, yield 81%). 1 H NMR(400MHz,Chloroform-d)δ8.75(dd,J＝3.4,1.7Hz,2H),8.21(dd,J＝6.2,1.6Hz,2H),8.01(dd,J＝6.2,4.0Hz,1H),7.83(dd,J＝6.3,4.0Hz,1H),7.54―7.52(m,2H),6.60(s,1H). 13 C NMR(100MHz,Chloroform-d)δ163.93(d),157.30(d),155.96,151.36,150.84(dd),148.82(dd),138.93,138.29(dd),137.15,132.51(dd),131.43,130.72,123.11,117.89,117.47(dd),114.24,113.47,112.26(dd),96.28,74.18.
Example 6
The synthetic route for compound 80 is shown below:
the synthesis method of the compound 80 specifically comprises the following steps:
synthesis of intermediate M80: 4,5, 7-trifluoro-1H-indene-1, 3 (2H) -dione (10.01 g,50 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at room temperature for 20 hours. After 4, 5-diazafluoren-9-one (9.11 g,50 mmol) was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extraction with chloroform was performed, water washing was performed 3 times, drying over anhydrous magnesium sulfate was performed, and spin drying was performed to obtain the crude product, which was directly used as the next step without purification.
Malononitrile (3.3 g,55 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at r.t. for 20 hours. After the crude product obtained above was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extracted with chloroform, washed 3 times with water, and dried over anhydrous magnesium sulfate to give a crude product without further purification. Malononitrile (3.3 g,55 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at r.t. for 20 hours. After the crude product obtained above was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extraction with chloroform was performed for 3 times, and dried over anhydrous magnesium sulfate to obtain a crude product, which was purified by silica gel column chromatography to obtain product M80 (18.66 g, yield 78%). 1 H NMR(400MHz,Chloroform-d)δ8.72(dd,J＝3.1,1.6Hz,2H),7.71(dd,J＝6.3,1.6Hz,2H),7.42―7.40(m,2H),7.18―7.14(m,1H),5.09(s,1H),4.83(s,1H). 13 C NMR(100MHz,Chloroform-d)δ158.06(dd),156.04(dd),154.25,152.24,150.22(dd),150.21,148.93(dd),147.40,146.92(dd),145.55(dt),137.06,130.89(dt),128.85,123.86(dd),123.79(dd),122.77,113.58,113.39,108.09(dt),84.20,76.20(d),75.93(d),56.04(t).
Synthesis of Compound 80: m80 (23.92 g,50 mmol) was weighed into a 500mL single-necked flask, 200mL of a concentrated HCl/etoh=4:1 mixed solution was added, and refluxed for 6 hours. Saturated potassium carbonate solution was added to adjust ph=7-8, extraction was performed with chloroform, extraction was performed three times with 100mL of dichloromethane, the organic phases were combined, dried over anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography to give the compound represented by formula 80 (19.11 g, yield 83%). 1 H NMR(400MHz,Chloroform-d)δ8.75―8.74(m,2H),8.24(dd,J＝6.3,1.7Hz,2H),7.55―7.53(m,2H),7.19―7.14(m,1H). 13 C NMR(100MHz,Chloroform-d)δ162.46(dd),161.10(dt),156.07,154.20(dd),152.19(dd),151.26,150.22(dd),148.21(dd),143.12(t),140.26,139.95(dd),136.94(dd),130.75,129.75,128.08(dt),123.11,120.94(dd),120.78(dd),114.24,113.47,105.67(dt),74.93(d),74.75(d)EXAMPLE 7
The synthetic route for compound 85 is shown below:
the synthesis method of the compound 85 specifically comprises the following steps:
synthesis of intermediate M85: 5-fluoro-1H-indene-1, 3 (2H) -dione (8.2 g,50 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at room temperature for 20 hours. After 5H-indeno [1,2-b ] pyridin-5-one (9.06 g,50 mmol) was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extraction with chloroform was performed, water washing was performed 3 times, drying over anhydrous magnesium sulfate was performed, and spin drying was performed to obtain the crude product, which was directly used as the next step without purification.
To the crude product obtained above, 200mL of a concentrated HCl/etoh=4:1 mixed solution was added and refluxed for 6 hours. Saturated potassium carbonate solution was added to adjust ph=7-8, extraction was performed with chloroform, extraction was performed three times with 100mL of dichloromethane, the organic phases were combined, dried over anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography to give the compound represented by formula 85 (12.27 g, yield 75%). 1 H NMR(400MHz,Chloroform-d)δ8.85(dd,J＝3.5 1.4Hz,1H),8.40(dd,J＝6.2 1.5Hz,1H),8.28(dd,J＝6.2 1.3Hz,1H),8.15―8.10(m,2H),7.91―7.89(m,1H),7.58―7.54(m,2H),7.48―7.44(m,1H),7.41―7.37(m,1H). 13 C NMR(100MHz,Chloroform-d)δ188.58(d),187.88,167.96,165.94,160.05,150.69,148.24,139.92(d),139.16,137.08(d),135.42,135.32,131.00,130.83,128.57,126.70,126.28,124.87(d),122.75,121.46,120.11(d),110.50(d).
Example 8
The synthetic route for compound 238 is shown below:
the synthesis method of the compound 238 specifically comprises the following steps:
synthesis of intermediate M238: 4,5,6, 7-tetrafluoro-1H-indene-1, 3 (2H) -dione (10.91 g,50 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at room temperature for 20 hours. 9-hydroxy-5H-indeno [1,2-b ] pyridin-5-one (9.86 g,50 mmol) was added to the system, and the mixture was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extraction with chloroform was performed, water washing was performed 3 times, drying over anhydrous magnesium sulfate was performed, and spin drying was performed to obtain the crude product, which was directly used as the next step without purification.
Malononitrile (3.3 g,55 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at r.t. for 20 hours. After the crude product obtained above was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extracted with chloroform, washed 3 times with water, and dried over anhydrous magnesium sulfate to give a crude product without further purification. Malononitrile (3.3 g,55 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at r.t. for 20 hours. After the crude product obtained above was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extraction with chloroform was performed, water washing was performed 3 times, and then anhydrous magnesium sulfate was used for drying, and the crude product was purified by silica gel column chromatography to obtain product M238 (21.73 g, yield 85%). 1 H NMR(400MHz,Chloroform-d)δ9.31(s,1H),8.65―8.64(m,1H),7.61―7.59(m,1H)，7.36―7.34(m,1H)，7.25(t，J＝6.3Hz,1H)，7.10―7.09(m,1H)，6.91―6.89(m,1H),5.04(s,1H),4.78(s,1H). 13 C NMR(100MHz,Chloroform-d)δ154.34,152.20,151.32,148.88(dd),148.72(dd),146.91,146.86(dd),146.70(dd),145.84(dt),145.10(dt),143.09(dt),138.67,132.20,128.67,125.75,125.37(dt),125.21(dt),121.43,116.98,116.21,113.58,113.39,84.92,76.12(d),55.76(t).
Synthesis of Compound 238: m238 (25.57 g,50 mmol) was weighed into a 500mL single-necked flask, 200mL of concentrated HCl/etoh=4:1 mixed solution was added, and refluxed for 6 hours. Adding saturated potassium carbonate solution to adjust pH=7-8, extracting with chloroform, extracting water phase with 100mL of dichloromethane three times, mixing organic phases, drying with anhydrous magnesium sulfate, and purifying crude product by silica gel column chromatographyThe compound represented by formula 238 (21.22 g, yield 86%) was obtained. 1 H NMR(400MHz,Chloroform-d)δ8.73―8.72(m,1H),8.27(dd，J＝6.2,1.5Hz,1H)，7.85―7.83(m,1H)，7.55―7.48(m,2H),6.97―6.95(m,1H). 13 C NMR(100MHz,Chloroform-d)δ161.48(dt),156.74,154.08,151.71,142.95(dt),140.93(dt),139.78(dd),139.62(dd),139.56,137.77(dd),137.61(dd),132.86,131.37(t),130.31,130.03,127.23,125.46,122.56,122.45(dt),122.29(dt),117.31,115.65,114.23,113.47,74.74(d).
Example 9
The synthetic route for compound 242 is shown below:
the synthesis method of the compound 242 specifically comprises the following steps:
synthesis of intermediate M242: 2, 3-difluoro-5H-cyclopenta [ b ] pyrazine-5, 7 (6H) -dione (9.21 g,50 mmol) and potassium carbonate (8.3 g,60 mmol) were taken and stirred in THF (100 mL) at room temperature for 20 hours. After 4, 5-diazafluoren-9-one (9.11 g,50 mmol) was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extraction with chloroform was performed, water washing was performed 3 times, drying over anhydrous magnesium sulfate was performed, and spin drying was performed to obtain the crude product, which was directly used as the next step without purification.
Malononitrile (3.3 g,55 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at r.t. for 20 hours. After the crude product obtained above was added to the system, the reaction was stirred at 80℃for 20 hours. After cooling to room temperature, 1N hydrochloric acid solution was added to adjust ph=6-7, extracted with chloroform, washed 3 times with water, and dried over anhydrous magnesium sulfate to give a crude product without further purification. Malononitrile (3.3 g,55 mmol) and potassium carbonate (8.3 g,60 mmol) were taken in THF (100 mL) and stirred at r.t. for 20 hours. After the crude product obtained above was added to the system, the reaction was stirred at 80℃for 20 hours. Cooling to room temperature, adding 1N hydrochloric acid solution to adjust pH=6-7, extracting with chloroform, washing with water for 3 times, drying with anhydrous magnesium sulfate to obtain crude product, and making into silica gelPurification by column chromatography gave product M242 (18.50 g, 80% yield). 1 H NMR(400MHz,Chloroform-d)δ8.73―8.71(m,2H),7.72―7.70(m,2H)，7.42―7.40(m,2H),5.27(s,1H),5.17(s,1H). 13 C NMR(100MHz,Chloroform-d)δ155.69(d),154.29,150.20,146.40(dd),144.91(dd),137.17,128.83,122.75,113.60,113.42,83.99,71.42,55.41.
Synthesis of Compound 242: m242 (23.12 g,50 mmol) was weighed into a 500mL single-necked flask, 200mL of concentrated HCl/etoh=4:1 mixed solution was added, and refluxed for 6 hours. Saturated potassium carbonate solution was added to adjust ph=7-8, extraction was performed with chloroform, extraction was performed three times with 100mL of dichloromethane, the organic phases were combined, dried over anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography to give the compound represented by formula 242 (18.89 g, yield 85%). 1 H NMR(400MHz,Chloroform-d)δ8.75―8.74(m,2H),8.28―8.26(m,2H)，7.55―7.53(m,2H). 13 C NMR (100 MHz, chloroform-d) delta 156.13,151.77,151.35,149.12 (d), 144.48 (dd), 144.41 (dd), 141.21,130.80,129.86,123.10,114.28,113.53,73.2. Example 10
The invention provides an organic light-emitting device based on a hole injection material of two units of an azafluorenes derivative and a cyclic electron-deficient group, which is formed by sequentially stacking a metal cathode 191, an electron injection layer 180, an electron transport layer 160, a light-emitting layer 150, a hole transport layer 140, a hole injection layer 130, an anode 120 and a glass substrate 110 from top to bottom as shown in fig. 1, wherein the device preparation process is an evaporation method.
Wherein the metal cathode is aluminum, the evaporation rate is 0.1-0.3nm/s, and the thickness is 100nm;
the electron injection layer is made of commercial materials, the evaporation rate is 0.05-0.1nm/s, and the thickness is 1nm;
the electron transport layer is a compound LET003 with the following structure, the evaporation rate is 0.05-0.1nm/s, and the thickness is 40nm;
the light-emitting layer is formed by co-doping a host material and a guest material, wherein the host material is selected from the currently commercialized host material LBH001, the guest material is selected from the LBD001 with the following structure, and the mass ratio of the host material to the guest material is 90:10, the evaporation rate is 0.003-0.2nm/s, and the thickness is 40nm;
the electron blocking layer is a compound LEB001 with the following structure, the evaporation rate is 0.05-0.1nm/s, and the thickness is 10nm;
the hole transport layer is made of commercial compound NPB, the evaporation rate is 0.05-0.1nm/s, and the thickness is 100nm;
the hole injection layer is made of the material synthesized by the method, the evaporation rate is 0.05-0.1nm/s, and the thickness is 1nm;
the anode 7 is made of indium tin oxide.
TABLE 1 device Performance Table
As can be seen from Table 1, compared with the commercial material, the hole injection material provided by the invention has lower starting voltage, higher current efficiency and longer service life.
Example 11:
the perovskite solar cell structure provided in this embodiment is shown in fig. 2, and the specific preparation process is as follows:
the ITO conductive glass is washed by acetone, deionized water and isopropanol in sequence, and dried for 12 hours at the temperature of 80 ℃ in vacuum. A hole injection layer film was evaporated on the ITO, and PTAA was spin-coated as a hole transport layer. Preparing a perovskite precursor solution, dissolving in DMSO, spin-coating on a PTAA film, and annealing at 100 ℃ for 10 minutes. Preparing an electron transport layer solution, dissolving PCBM in chlorobenzene to obtain a concentration of 10mg/ml, and preparing the PCBM on a perovskite film by a spin coating method. Then, a methanol solution of BCP was spin-coated on PCBM, and finally a metallic silver electrode was vacuum evaporated.
The properties of the finally produced perovskite solar cell device are shown in table 2 below:
| hole injection layer configuration | Voc(V) | Jsc(mA/cm 2 ) | FF(％) | PCE(％) |
| Without any means for | 1.12 | 21.68 | 68.17 | 16.55 |
| Formula 1 | 1.21 | 22.28 | 73.51 | 17.95 |
| Molecular formula 25 | 1.18 | 22.37 | 77.78 | 20.15 |
| Molecular formula 30 | 1.13 | 23.01 | 75.98 | 19.88 |
| Formula 39 | 1.10 | 22.58 | 79.54 | 21.35 |
| Molecular formula 80 | 1.12 | 21.16 | 80.53 | 20.03 |
| Molecular formula 85 | 1.17 | 22.33 | 74.05 | 20.55 |
| Molecular formula 134 | 1.11 | 22.92 | 73.18 | 20.06 |
| Molecular formula 238 | 1.15 | 22.86 | 79.21 | 19.68 |
| Molecular formula 242 | 1.16 | 22.35 | 79.28 | 19.65 |
The above-listed polymer structures are only partially representative, and other organic hole injection material molecules containing the same idea are within the scope of this patent.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (6)
1. An organic hole injection material, characterized by the following chemical formula:
wherein R is 1 、R 2 Each independently selected from carbonyl, ethylcyano, or propyldicyano;
x, Y is C-H, N or C-OH, identical to or different from each other;
ar is selected from benzene ring, pyridine ring, fluoro benzene ring or pyridine ring;
n=0, 1,2,3 or 4.
2. An organic hole injecting material as claimed in claim 1, wherein hydrogen atoms in the molecular formula are partially or wholly replaced by deuterium.
3. The organic hole injecting material as claimed in claim 1, wherein hydrogen atoms in the Ar group are partially or entirely substituted with deuterium.
4. The organic hole injecting material as claimed in claim 1, wherein the molecular formula thereof is selected from one of:
5. an organic light-emitting device comprising a cathode, an anode, and organic layers; wherein the electron injection layer uses the organic hole injection material according to any one of claims 1 to 4.
6. A perovskite solar cell comprising a cathode, an anode and respective organic layers; wherein the organic hole injection material according to any one of claims 1 to 4 is used for the hole injection layer.
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| JPH07160023A (en) * | 1993-12-03 | 1995-06-23 | Konica Corp | Electrophotographic photoreceptor |
| CN101874021A (en) * | 2007-11-30 | 2010-10-27 | 出光兴产株式会社 | Azaindenofluorenedione derivative, material for organic electroluminescent element, and organic electroluminescent element |
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| CN114605435A (en) * | 2022-01-17 | 2022-06-10 | 华南理工大学 | Photoelectric and photothermal conversion material containing condensed ring electron-withdrawing end group and preparation method and application thereof |
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| JPH07160023A (en) * | 1993-12-03 | 1995-06-23 | Konica Corp | Electrophotographic photoreceptor |
| CN101874021A (en) * | 2007-11-30 | 2010-10-27 | 出光兴产株式会社 | Azaindenofluorenedione derivative, material for organic electroluminescent element, and organic electroluminescent element |
| CN113121560A (en) * | 2021-03-29 | 2021-07-16 | 北京大学深圳研究生院 | Benzothienobenzo five-membered heterocyclic material and preparation method and application thereof |
| CN114605435A (en) * | 2022-01-17 | 2022-06-10 | 华南理工大学 | Photoelectric and photothermal conversion material containing condensed ring electron-withdrawing end group and preparation method and application thereof |
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