Superbase, preparation method and application thereof

Abstract

The application relates to the field of organic chemical materials, in particular to a super base, a preparation method and application in an organic perovskite solar cell. The super base is synthesized through novel molecular design, so that the super base not only plays a role of passivating defects on the perovskite surface, but also can transfer charges, and has a huge application prospect in the perovskite solar cell.

Description

Technical Field

[0001] This invention relates to the field of organic chemical materials, specifically to a super base, its preparation method, and its application in organic perovskite solar cells. Background Technology

[0002] Perovskite solar cells, as a third-generation photovoltaic technology, have developed rapidly in recent years, with efficiency increasing from 3.8% to 25.57%. Defect passivation technology on the perovskite surface has been an effective means to further improve device efficiency and stability. Conventional passivation techniques typically involve doping the perovskite precursor with small molecules of Lewis acid or base; however, these small molecules lack charge transport properties, greatly limiting the improvement of device performance. Summary of the Invention

[0003] In view of the many shortcomings of existing perovskite surface passivation technologies, this invention provides a super base, which is composed of a large conjugated planar system and pyrimidine units, which can both passivate defects on the perovskite surface and transfer charge.

[0004] The technical solution of this invention is achieved in the following way: a super base is provided, with the following general structural formula:

[0005]

[0006] This superbase is used in the fabrication of organic perovskite solar cells, where R1, R2, and R3 are independently selected from hydrogen, deuterium, or conjugated aromatic rings; the conjugated aromatic rings include benzene rings, naphthalene rings, diphenylamine, diphenylphosphine, carbazole, thiophene, furan, pyridine, pyrrole, and C. 60 .

[0007] Preferably, in one embodiment of the invention, hydrogen on the conjugated aromatic ring is partially or completely deuterated.

[0008] Preferably, in one embodiment of the present invention, the conjugated aromatic ring comprises the following groups and their derivatives:

[0009]

[0010] Preferably, in one embodiment of the present invention, the super base is selected from the following:

[0011]

[0012]

[0013]

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030] On the other hand, the present invention also provides a super base, a preparation method thereof, and its application in organic perovskite solar cells. In the process of preparing perovskite solar cells, the super base is used to passivate surface defects. This can be achieved by doping the super base after preparing the perovskite precursor solution.

[0031] The beneficial effects are as follows: Through the design and synthesis of novel super base molecules, this invention not only passivates defects on the perovskite surface but also transfers charges, showing great promise for application in perovskite solar cells. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of a perovskite solar cell device. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with specific embodiments and corresponding drawings. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0034] The present invention will now be described in further detail with reference to the accompanying drawings and embodiments.

[0035] The present invention

[0036] Example 1

[0037] The synthesis method is as follows:

[0038]

[0039] Synthesis of Formula 1: 11.75 g (50 mmol) of 2,6-dibromopyridine, 2,3,4,6,7,8-hexahydro-1H-pyrimidino[1,2-a]pyrimidine (20.85 g, 150 mmol), 1.12 g (5 mmol) of Pd(OAc)₂, 1.58 g (6 mmol), 56 g (500 mmol) of potassium tert-butoxide, and 200 mL of toluene were added to a 500 mL round-bottom flask. Argon gas was displaced, and the mixture was stirred and refluxed at 90 °C for 3.5 h. After the reaction was complete, the mixture was cooled to room temperature, and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, and the mixture was stirred thoroughly and filtered. The ether was removed by rotary evaporation to obtain the solid, which was the target product.

[0040] 1 H NMR (600MHz, CDCl3) δ1.87(quin,J=5.87Hz,3H),1.96(quin,J=6.24Hz,4H),3.15(t,J=6.46Hz,4H),3.21(t, J=6.02Hz,3H),3.41(t,J=5.58Hz,4H),3.84(t,J=6.0Hz,4H),7.12(d,J=8.22Hz,2H),7.34(t,J=8.08Hz,1H). 13 C NMR (150MHz, CDCl3) δ151.75,151.27,140.0,114.44,48.37,48.20,48.18,44.68,42.61,22.86,21.95.

[0041] Example 2

[0042] The synthesis method is as follows:

[0043]

[0044] Synthesis of Formula 4: 2,6-Dibromo-N,N-diphenylpyridin-4-amine (20.6 g, 50 mmol), 2,3,4,6,7,8-hexahydro-1H-pyrimidino[1,2-a]pyrimidine (20.85 g, 150 mmol), Pd(OAc)₂ (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. Argon gas was purged, and the mixture was stirred and refluxed at 90 °C for 3.5 h. After the reaction was complete, the mixture was cooled to room temperature, and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, and the mixture was stirred thoroughly and filtered. The ether was removed by rotary evaporation to obtain 40 g (80%) of the target product.

[0045] 1 H NMR (600MHz, CDCl3) δ4.07-4.03(m,4H),3.57-3.35(m,12H),1.96-1.88(m,8H). 13 C NMR (150MHz, CDCl3) δ159.42,153.85,151.06,146.74,129.26,124.97,124.21,107.53,48.37,48.20,48.18,44.68,42.61,22.86,21.95.

[0046] Example 3

[0047] The synthesis method is as follows:

[0048]

[0049] Synthesis of intermediate M37: 12.65 g (50 mmol) of 2,6-dibromo-4-fluoropyridine, 10.06 g (60 mmol) of carbazole, 1.12 g (5 mmol) of Cs₂CO₃, and 200 mL of DMF were added to a 500 mL round-bottom flask. Argon gas was purged, and the mixture was stirred and refluxed at 130 °C for 3.5 h. After the reaction was complete, the mixture was cooled to room temperature, and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, and the mixture was stirred thoroughly and filtered. The ether was removed by rotary evaporation to obtain the solid, which was the target product.

[0050] Synthesis of Formula 37: 2,6-Dibromo-4-carbazolyl-pyridine (20 g, 50 mmol), 2,3,4,6,7,8-hexahydro-1H-pyrimidino[1,2-a]pyrimidine (20.85 g, 150 mmol), Pd(OAc)₂ (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. Argon gas was purged, and the mixture was stirred and refluxed at 90 °C for 3.5 h. After the reaction was complete, the mixture was cooled to room temperature, and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, and the mixture was stirred thoroughly and filtered. The ether was removed by rotary evaporation to obtain 22 g (85%) of the target product.

[0051] 1 H NMR (600MHz, CDCl3) δ8.15-8.13(m,1H),7.66-7.64(m,1H),7.37-7.29(m,2 H),6.90(s,1H),4.07-4.03(m,4H),3.57-3.35(m,12H),1.96-1.88(m,8H). 13 C NMR (150MHz, CDCl3) δ158.96,151.05,146.82,140.89,126.24,124.77,120.9 3,120.26,110.78,105.92,48.37,48.20,48.18,44.68,42.61,22.86,21.95.

[0052] Example 4

[0053] The synthesis method is as follows:

[0054]

[0055] Synthesis of molecular formula 85: 15.8 g (50 mmol) of 2,6-dibromo-4,4'-bipyridine, 2,3,4,6,7,8-hexahydro-1H-pyrimidino[1,2-a]pyrimidinidine (20.85 g (150 mmol)), Pd(OAc)₂ (1.12 g (5 mmol)), triphenylphosphine (1.58 g (6 mmol)), potassium tert-butoxide (56 g (500 mmol)), and 200 mL of toluene were added to a 500 mL round-bottom flask. Argon gas was purged, and the mixture was stirred and refluxed at 90 °C for 3.5 h. After the reaction was complete, the mixture was cooled to room temperature, and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, and the mixture was stirred thoroughly and filtered. The ether was removed by rotary evaporation to obtain 18.5 g (85%) of the target product.

[0056] 1 H NMR (600MHz, CDCl3) δ8.79-8.76(m,2H),7.6-7.58(m,2H),7.17(s,2H),4.07-4.03(m,4H),3.57-3.35(m,12H),1.96-1.88(m,8H). 13 C NMR (150MHz, CDCl3) δ158.40,158.83,148.91,145.45,140.21,121.54,111.74,48.37,48.20,48.18,44.68,42.61,22.86,21.95.

[0057] Example 5

[0058] The synthesis method is as follows:

[0059]

[0060] Synthesis of intermediate M97: 13.35 g (50 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine, 14 g (50 mmol) of pyridine 2,6-dibromo-4-borate, 5.8 g (5 mmol) of Pd(PPh3)4, 69 g (500 mmol) of potassium carbonate, and 200 mL of ethanol were added to a 500 mL round-bottom flask. Argon gas was displaced, and the mixture was stirred and refluxed at 90 °C for 3.5 h. After the reaction was complete, the mixture was cooled to room temperature, and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, and the mixture was stirred thoroughly and filtered. The ether was removed by rotary evaporation to obtain a solid, which was 19.3 g (85%) of the target product.

[0061] Synthesis of molecular formula 97: Intermediate M97 (23.3 g, 50 mmol), 2,3,4,6,7,8-hexahydro-1H-pyrimidino[1,2-a]pyrimidine (20.85 g, 150 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. Argon gas was purged, and the mixture was stirred and refluxed at 90 °C for 3.5 h. After the reaction was complete, the mixture was cooled to room temperature, and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, and the mixture was stirred thoroughly and filtered. The ether was removed by rotary evaporation to obtain a solid, which was 40.5 g (81%) of the target product.

[0062] 1H NMR (600MHz, CDCl3) δ8.42-8.39(m,2H),7.69(s,1H),7.53-7.47(m,3H),4.07-4.03(m,4H),3.57-3.35(m,12H),1.96-1.88(m,8H). 13 C NMR (150MHz, CDCl3) δ171.66,165.70,159.03,151.03,137.62,136.39,13 1.91,128.90,128.70,114.35,48.20,48.18,44.68,42.61,22.86,21.95.

[0063] Example 6

[0064] The synthesis method is as follows:

[0065] Preparation of 2,6-dibromo-4-iodopyridine: 12.5 g (50 mmol) of 2,6-dibromo-4-aminopyridine was placed in a 500 mL two-necked round-bottom flask, and 100 mL of 6N sulfuric acid solution was added. NaNO2 (5.26 g, 90 mmol) and water (50 mL) were slowly added dropwise under ice bath and stirring. After the addition was complete, the reaction was continued under ice bath and stirring for 20 minutes. KI (20.0 g, 120 mmol) and water (50 mL) were slowly added dropwise under ice bath and stirring. After the addition was complete, the mixture was stirred at room temperature for 5 h. After the reaction was complete, a saturated potassium carbonate aqueous solution was added to adjust the pH to approximately 10, and then a saturated sodium thiosulfate aqueous solution was added to remove excess iodine. The product was extracted with ethyl acetate, and the volatile organic solvent was removed by vacuum distillation. Column chromatography was performed using PE:EA = 5:1 as the eluent for purification. 15 g (84%) of the target product was obtained.

[0066]

[0067] Preparation of 2-bromo-9,10-bis(naphth-2-yl)anthracene: Carbazole (8.35 g, 50 mmol) was placed in a 500 mL two-necked round-bottom flask, and the atmosphere was purged with nitrogen. 150 mL of tetrahydrofuran solution was added. 34 mL of n-butyllithium (1.6 M inTHF) was added to the reaction system while stirring at -78 °C. After the addition was complete, the reaction was maintained at -78 °C for 4 h. After the reaction was complete, 7.2 g (25 mmol) of 2-bromoanthracene-9,10(4aH,9aH)-dione was added, and the mixture was refluxed at 90 °C for 24 h with stirring. The reaction was quenched with saturated brine, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the crude product was obtained by rotary evaporation to remove volatile organic solvents.

[0068] Add ethanol / concentrated hydrochloric acid (4:1) to the crude product and heat under reflux for 12 hours. After the reaction is complete, add saturated sodium bicarbonate solution to adjust the pH to neutral. Remove volatile organic compounds by vacuum distillation, extract with water and ethyl acetate, separate the layers, remove volatile solvents by rotary evaporation under reduced pressure, and purify by column chromatography (PE / EA = 5:1) to obtain 10.9 g (75%) of the target product.

[0069] Synthesis of (9,10-bis(carbazole-2-yl)anthracene-2-yl)boronic acid: 5.86 g (10 mmol) of 2-bromo-9,10-bis(carbazole-2-yl)anthracene was placed in a 250 mL two-necked round-bottom reaction flask, purged with nitrogen, and 50 mL of dry THF was added. The intermediate obtained above was added dropwise at -78 °C under vigorous stirring. After the addition was complete, the reaction was carried out at 60 °C with stirring for 1 h to obtain the target intermediate. After the reaction was complete, the mixture was cooled to -78 °C, and tributylboronic acid ester was added. After the addition was complete, the mixture was brought to room temperature and stirred for 12 h. Pinarol and acetic acid were added, and the reaction was carried out overnight with stirring at room temperature. After the reaction was complete, volatile organic compounds were removed by vacuum distillation. The target product (5.8 g, 92%) was then obtained by recrystallization.

[0070]

[0071] Synthesis of 2,6-dibromo-4-(9,10-bis(carbazol-2-yl)anthracene-2-yl)pyridine: (9,10-bis(carbazol-2-yl)anthracene-2-yl)boronic acid (3.17 g, 5 mmol), 2,6-dibromo-4-iodopyridine (1.8 g, 5 mmol), palladium acetate (112 mg, 0.5 mmol), triphenylphosphine (158 mg, 0.6 mmol), potassium carbonate (2.07 g, 15 mmol), 40 mL toluene, and 40 mL deionized water were placed in a 250 mL reaction flask. The mixture was purged with nitrogen and refluxed at 90 °C for 24 h with stirring. After the reaction was complete, water and ethyl acetate were added, and the mixture was separated. The organic phase was dried over anhydrous sodium sulfate. Volatile organic compounds were removed by vacuum distillation, and the target product (3.19 g, 86%) was obtained by column chromatography with silica gel.

[0072]

[0073] Preparation of 1,1'-(4-(9,10-bis(2-carbazolyl)-2-anthrayl)-2,6-pyridyl)-bis(2,3,4,6,7,8-6-hydrogen)-1H-pyrimidino[1,2-a]pyrimidine) (Molecular Formula 53): 2,6-dibromo-4-(9,10-bis(carbazolyl)anthrayl-2-yl)pyridine (3.7 g, 5 mmol), 2,3,4,6,7,8- Hexahydro-1H-pyrimidino[1,2-a]pyrimidine (2.08 g, 15 mmol), Pd(OAc)₂ (112 mg, 0.5 mmol), triphenylphosphine (158 mg, 0.6 mmol), potassium tert-butoxide (5.6 g, 50 mmol), and 100 mL of toluene were added to a 250 mL round-bottom flask, purged with argon, and the mixture was stirred and refluxed at 90 °C for 24 h. After the reaction was complete, the mixture was cooled to room temperature, and volatile organic compounds were removed by vacuum distillation. Methanol was used as the eluent, and the target product was obtained by alkaline alumina column chromatography, yielding 3.1 g (72%).

[0074]

[0075] 1 H NMR (600MHz, CDCl3) δ8.43-8.42(m,1H),8.20-8.13(m,7H),7.68-7.66(m,4H),7.49-7.47(m,2 H),7.37-7.29(m,8H),7.08(s,2H),4.07-4.03(m,4H),3.57-3.35(m,12H),1.96-1.88(m,8H). 13 C NMR (150MHz, CDCl3) δ158.50,150.83,146.33,142.46,141.69,134.25,13 3.09,131.72,128.97,128.36,128.32,127.35,127.02,126.96,126.91,1 26.85,126.53,125.66,124.55,124.49,124.23,123.57,123.25,123.22, 121.09,121.04,121.0,120.52,48.20,48.18,44.68,42.61,22.86,21.95.

[0076] Example 7

[0077] The synthesis method is as follows:

[0078] Preparation of 2,6-dibromo-4-iodopyridine: 12.5 g (50 mmol) of 2,6-dibromo-4-aminopyridine was placed in a 500 mL two-necked round-bottom flask, and 100 mL of 6N sulfuric acid solution was added. NaNO2 (5.26 g, 90 mmol) and water (50 mL) were slowly added dropwise under ice bath and stirring. After the addition was complete, the reaction was continued under ice bath and stirring for 20 minutes. KI (20.0 g, 120 mmol) and water (50 mL) were slowly added dropwise under ice bath and stirring. After the addition was complete, the mixture was stirred at room temperature for 5 h. After the reaction was complete, a saturated potassium carbonate aqueous solution was added to adjust the pH to approximately 10, and then a saturated sodium thiosulfate aqueous solution was added to remove excess iodine. The product was extracted with ethyl acetate, and the volatile organic solvent was removed by vacuum distillation. Column chromatography was performed using PE:EA = 5:1 as the eluent for purification. 15 g (84%) of the target product was obtained.

[0079]

[0080] Preparation of 2-bromo-9,10-bis(2-thiophene-2-yl)anthracene: 8.1 g (50 mmol) of 2-bromothiophene was placed in a 500 mL two-necked round-bottom flask, and the atmosphere was purged with nitrogen. 150 mL of tetrahydrofuran solution was added. 34 mL (1.6 M in THF) of n-butyllithium was added to the reaction system with stirring at -78 °C. After the addition was complete, the reaction was maintained at -78 °C for 4 h. After the reaction was complete, 7.2 g (25 mmol) of 2-bromoanthracene-9,10(4aH,9aH)-dione was added, and the mixture was refluxed at 90 °C with stirring for 24 h. The reaction was quenched with saturated brine, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the volatile organic solvent was removed by rotary evaporation to obtain the crude product.

[0081] Add ethanol / concentrated hydrochloric acid (4:1) to the crude product and heat under reflux for 12 hours. After the reaction is complete, add saturated sodium bicarbonate solution to adjust the pH to neutral. Remove volatile organic compounds by vacuum distillation, extract with water and ethyl acetate, separate the layers, remove volatile solvents by rotary evaporation under reduced pressure, and purify by column chromatography (PE / EA = 5:1) to obtain 18.9 g (90%) of the target product.

[0082] Synthesis of (9,10-bis(2-thiophen-2-yl)anthracene-2-yl)boronic acid: 4.2 g (10 mmol) of 2-bromo-9,10-bis(2-thiophen-2-yl)anthracene was placed in a 250 mL two-necked round-bottom reaction flask, purged with nitrogen, and 50 mL of dry THF was added. The intermediate obtained above was added dropwise at -78 °C under vigorous stirring. After the addition was complete, the reaction was carried out at 60 °C with stirring for 1 h to obtain the target intermediate. After the reaction was complete, the mixture was cooled to -78 °C, and tributylboronic acid ester was added. After the addition was complete, the mixture was brought to room temperature and stirred for 12 h. Pinarol and acetic acid were added, and the reaction was carried out overnight with stirring at room temperature. After the reaction was complete, volatile organic compounds were removed by vacuum distillation. The target product (4.45 g, 95%) was obtained by recrystallization.

[0083]

[0084] Synthesis of 2,6-dibromo-4-(9,10-bis(2-thiophen-2-yl)anthracene-2-yl)pyridine: (9,10-bis(2-thiophen-2-yl)anthracene-2-yl)boronic acid (2.34 g, 5 mmol), 2,6-dibromo-4-iodopyridine (1.8 g, 5 mmol), palladium acetate (112 mg, 0.5 mmol), triphenylphosphine (158 mg, 0.6 mmol), potassium carbonate (2.07 g, 15 mmol), 40 mL toluene, and 40 mL deionized water were placed in a 250 mL reaction flask. The mixture was purged with nitrogen and refluxed at 90 °C for 24 h with stirring. After the reaction was complete, water and ethyl acetate were added, and the mixture was separated. The organic phase was dried over anhydrous sodium sulfate. Volatile organic compounds were removed by vacuum distillation, and the target product (2.53 g, 88%) was obtained by column chromatography with silica gel.

[0085]

[0086] Preparation of 1,1'-(4-(9,10-bis(2-thienyl)-2-anthrayl)-2,6-pyridyl)-bis(2,3,4,6,7,8-6-hydrogen)-1H-pyrimidino[1,2-a]pyrimidine (molecular formula 50): 2,6-dibromo-4-(9,10-bis(2-thienyl)anthrayl-2-yl)pyridine (2.88 g, 5 mmol), 2,3,4,6,7, 8-Hexahydro-1H-pyrimidino[1,2-a]pyrimidine (2.08 g, 15 mmol), Pd(OAc)₂ (112 mg, 0.5 mmol), triphenylphosphine (158 mg, 0.6 mmol), potassium tert-butoxide (5.6 g, 50 mmol), and 100 mL of toluene were added to a 250 mL round-bottom flask, purged with argon, and the mixture was stirred and refluxed at 90 °C for 24 h. After the reaction was complete, the mixture was cooled to room temperature, and volatile organic compounds were removed by vacuum distillation. Methanol was used as the eluent, and the target product was obtained by alkaline alumina column chromatography, yielding 2.84 g (82%).

[0087]

[0088] 1 H NMR (600MHz, CDCl3) δ8.26-8.25(m,1H),8.16-8.12(m,3H),7.93-7.91(m,1H),7.52-7.44(m,6 H),7.22-7.20(m,2H),7.10(s,2H),4.07-4.03(m,4H),3.57-3.35(m,12H),1.96-1.88(m,8H). 13 C NMR (150MHz, CDCl3) δ158.50,150.83,146.72,139.24,138.92,134.16,133.81,133.32,132.92,132.85,131.50,131.20,129.29,128.1 6,128.12,127.78,127.77,127.43,127.38,127.24,127.19,126.71,125.03,122.68,110.87,48.20,48.18,44.68,42.61,22.86,21.95.

[0089] Example 8

[0090] The synthesis method is as follows:

[0091] Preparation of 2,6-dibromo-4-iodopyridine: 12.5 g (50 mmol) of 2,6-dibromo-4-aminopyridine was placed in a 500 mL two-necked round-bottom flask, and 100 mL of 6N sulfuric acid solution was added. NaNO2 (5.26 g, 90 mmol) and water (50 mL) were slowly added dropwise under ice bath and stirring. After the addition was complete, the reaction was continued under ice bath and stirring for 20 minutes. KI (20.0 g, 120 mmol) and water (50 mL) were slowly added dropwise under ice bath and stirring. After the addition was complete, the mixture was stirred at room temperature for 5 h. After the reaction was complete, a saturated potassium carbonate aqueous solution was added to adjust the pH to approximately 10, and then a saturated sodium thiosulfate aqueous solution was added to remove excess iodine. The product was extracted with ethyl acetate, and the volatile organic solvent was removed by vacuum distillation. Column chromatography was performed using PE:EA = 5:1 as the eluent for purification. 15 g (84%) of the target product was obtained.

[0092]

[0093] Preparation of 2-naphthyl magnesium bromide: Under a nitrogen atmosphere, magnesium powder (1.3 g, 52.5 mmol) was placed in a 250 mL two-necked round-bottom flask, and 100 mL of dry tetrahydrofuran solution was added. Under vigorous stirring, 2-naphthyl bromide (10.3 g, 50 mmol) and 20 mL of tetrahydrofuran solution were added dropwise, and the mixture was stirred at room temperature for 1 h to obtain the target intermediate product.

[0094]

[0095] Preparation of 2-bromo-9,10-bis(naphthyl-2-yl)anthracene: 6.4 g (22 mmol) of 2-bromoanthracene-9,10(4aH,9aH)-dione was placed in a 500 mL two-necked round-bottom flask, and the atmosphere was purged with nitrogen. 50 mL of tetrahydrofuran solution was added. With stirring in an ice bath, the previously prepared 2-naphthyl Grignard reagent solution was added to the reaction system. After the addition was complete, the mixture was refluxed at 80 °C for 24 h. After the reaction was complete, the reaction was quenched with 1 N hydrochloric acid aqueous solution, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the volatile organic solvent was removed by rotary evaporation to obtain the crude product.

[0096]

[0097] Add ethanol / concentrated hydrochloric acid (4:1) to the crude product and heat under reflux for 12 hours. After the reaction is complete, add saturated sodium bicarbonate solution to adjust the pH to neutral. Remove volatile organic compounds by vacuum distillation, extract with water and ethyl acetate, separate the layers, remove volatile solvents by rotary evaporation under reduced pressure, and purify by column chromatography (PE / EA = 5:1) to obtain 9.6 g (86%) of the target product.

[0098] Synthesis of (9,10-bis(naphthyl-2-yl)anthracene-2-yl)boronic acid: Magnesium powder (250 mg, 10.5 mmol) was placed in a 250 mL two-necked round-bottom reaction flask, purged with nitrogen, and 30 mL of dry THF was added. Under vigorous stirring, the intermediate 2-bromo-9,10-bis(naphthyl-2-yl)anthracene (5.08 g, 10 mmol) obtained above was added dropwise with 50 mL of THF solution. After the addition was complete, the reaction was carried out at 60 °C with stirring for 1 h to obtain the target intermediate. After the reaction was complete, the mixture was cooled to -70 °C, and triisopropylboronic acid ester was added. After the addition was complete, the mixture was brought to room temperature and stirred for 12 h. Then, 3 N hydrochloric acid solution was added, and the reaction was carried out overnight with stirring at room temperature. After the reaction was complete, volatile organic compounds were removed by vacuum distillation. The target product (4.5 g, 95%) was obtained by recrystallization.

[0099]

[0100] Synthesis of 2,6-dibromo-4-(9,10-bis(naphthyl-2-yl)anthracene-2-yl)pyridine: (9,10-bis(naphthyl-2-yl)anthracene-2-yl)boronic acid (2.37 g, 5 mmol), 2,6-dibromo-4-iodopyridine (1.8 g, 5 mmol), palladium acetate (112 mg, 0.5 mmol), triphenylphosphine (158 mg, 0.6 mmol), potassium carbonate (2.07 g, 15 mmol), 40 mL toluene, and 40 mL deionized water were placed in a 250 mL reaction flask. The mixture was purged with nitrogen and refluxed at 90 °C for 24 h with stirring. After the reaction was complete, water and ethyl acetate were added, and the mixture was separated. The organic phase was dried over anhydrous sodium sulfate. Volatile organic compounds were removed by vacuum distillation, and the target product (2.7 g, 81%) was obtained by column chromatography with silica gel.

[0101]

[0102] Preparation of 1,1'-(4-(9,10-bis(2-naphthyl)-2-anthrayl)-2,6-pyridyl)-bis(2,3,4,6,7,8-6-hydrogen)-1H-pyrimidino[1,2-a]pyrimidine) (Molecular Formula 48): 2,6-dibromo-4-(9,10-bis(naphthyl)anthrayl-2-yl)pyridine (3.3 g, 5 mmol), 2,3,4,6,7,8-hexabromo-4-(9,10-bis(naphthyl)anthrayl-2-yl)pyridine (3.3 g, 5 mmol), 2,3,4,6,7,8-6-hydrogen) Hydrogen-1H-pyrimidino[1,2-a]pyrimidine (2.08 g, 15 mmol), Pd(OAc)₂ (112 mg, 0.5 mmol), triphenylphosphine (158 mg, 0.6 mmol), potassium tert-butoxide (5.6 g, 50 mmol), and 100 mL of toluene were added to a 250 mL round-bottom flask, purged with argon, and the mixture was stirred and refluxed at 90 °C for 24 h. After the reaction was complete, the mixture was cooled to room temperature, and volatile organic compounds were removed by vacuum distillation. Methanol was used as the eluent, and the target product was obtained by alkaline alumina column chromatography (3.05 g, 78%).

[0103]

[0104] 1 H NMR (600MHz, CDCl3) δ8.95-8.94(m,1H),8.30-8.27(m,2H),8.24(d,J=9. 6Hz,1H),8.21-8.19(m,2H),8.08(s,1H),8.06(s,1H),7.99-7.97(m,2H), 7.93-7.91(m,2H),7.83-7.81(m,1H),7.75-7.72(m,2H),7.55-7.49(m,6H ),7.10(s,2H),4.07-4.03(m,4H),3.57-3.35(m,12H),1.96-1.88(m,8H). 13C NMR (150MHz, CDCl3) δ158.50,150.83,146.72,137.26,136.50,134.94,134.70,134.45,134.38 ,134.27,134.03,134.00,132.34,131.89,131.70,131.48,129.02,128.99,128.97,128.85,12 8.62,128.56,128.53,128.46,128.44,128.38,128.02,127.98,127.21,127.16,126.70,126.58,126.53,126.41,126.19,125.43,123.98,110.87,48.20,48.18,44.68,42.61,22.86,21.95.

[0105] Example 9

[0106] The synthesis method is as follows:

[0107]

[0108] Synthesis of Formula 33: 2,6-Dibromo-3,4,5-triphenylpyridine (23.26 g, 50 mmol), 2,3,4,6,7,8-hexahydro-1H-pyrimidino[1,2-a]pyrimidine (20.85 g, 150 mmol), Pd(OAc)₂ (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. Argon gas was displaced, and the mixture was stirred and refluxed at 90 °C for 3.5 h. After the reaction was complete, the mixture was cooled to room temperature, and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, and the mixture was stirred thoroughly and filtered. The ether was removed by rotary evaporation to obtain a solid, which was 24.73 g (85%) of the target product.

[0109] 1 H NMR (600MHz, CDCl3) δ7.49-7.36(m,15H),4.17-4.06(m,4H),3.57-3.35(m,12H),2.00-1.85(m,8H). 13C NMR (150MHz, CDCl3) δ153.62,150.95,141.49(d),134.35,129.05,129.01,128.0 0,127.96,127.91,126.32,121.86,48.37,48.19(d),45.54,42.61,22.86,21.91.

[0110] Example 10

[0111] The synthesis method is as follows:

[0112]

[0113] Synthesis of molecular formula 225: 2,6-Dibromo-3,4-diphenylpyridine (19.45 g, 50 mmol), 2,3,4,6,7,8-hexahydro-1H-pyrimidino[1,2-a]pyrimidine (20.85 g, 150 mmol), Pd(OAc)₂ (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene were added to a 500 mL round-bottom flask. Argon gas was purged, and the mixture was stirred and refluxed at 90 °C for 3.5 h. After the reaction was complete, the mixture was cooled to room temperature, and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, and the mixture was stirred thoroughly and filtered. The ether was removed by rotary evaporation to obtain the target product, 21.49 g (85%).

[0114] 1 H NMR (600MHz, CDCl3) δ7.59-7.57(m,2H),7.48-7.36(m,8H),7.02(s,1H),4.17-4.01(m,4H),3.57-3.35(m,12H),2.00-1.85(m,8H). 13 C NMR (150MHz, CDCl3) δ155.96,154.89,150.91(d),142.96,139.20,135.40,129.02,128.41,128.19,127. 96,127.78,126.87,120.66,109.68,48.39(d),48.21(d),45.54,44.68,42.64(d),22.88(d),21.95(d).

[0115] Example 11

[0116] The synthesis method is as follows:

[0117] Synthesis of methyl 5-(4-(2,6-dibromopyridin-4-yl)phenyl)-5-oxopentanoate: 12.5 g (50 mmol) of (4-(5-methoxy-5-oxopentanoyl)phenyl)boronic acid, 18 g (50 mmol) of 2,6-dibromo-4-iodopyridine, 1.12 g (5 mmol) of palladium acetate, 1.58 g (6 mmol) of triphenylphosphine, 20.7 g (150 mmol) of potassium carbonate, 120 mL of toluene, and 120 mL of deionized water were placed in a 500 mL reaction flask. The mixture was purged with nitrogen and refluxed at 90 °C for 24 h with stirring. After the reaction was complete, water and ethyl acetate were added, and the mixture was separated. The organic phase was dried over anhydrous sodium sulfate. Volatile organic compounds were removed by vacuum distillation, and the product was separated by silica gel column chromatography to obtain 18.5 g (85%) of the target product.

[0118]

[0119] Synthesis of molecular formula 229: Methyl 5-(4-(2,6-dibromopyridin-4-yl)phenyl)-5-oxovalerate (22.06 g, 50 mmol) was added to TsNHNH2 (11.2 g, 60 mmol) and methanol solution and refluxed for 24 h. After the reaction was complete, the mixture was filtered, and volatile organic compounds were removed by vacuum distillation. The intermediate was obtained by column chromatography with silica gel. The intermediate was then reacted with 2,3,4,6,7,8-hexahydro-1H-pyrimidino[1,2-a]pyrimidine (20.85 g, 150 mmol), Pd(OAc)2 (1.12 g, 5 mmol), triphenylphosphine (1.58 g, 6 mmol), potassium tert-butoxide (56 g, 500 mmol), and 200 mL of toluene in a 500 mL round-bottom flask. Argon gas was purged, and the mixture was stirred and refluxed at 90 °C for 3.5 h. After the reaction is complete, the mixture is cooled to room temperature, and volatile organic compounds are removed by vacuum distillation. Diethyl ether is added, and the mixture is stirred thoroughly and then filtered. The ether is removed by rotary evaporation to obtain the solid, which is the intermediate.

[0120] The obtained intermediate was added to C in a 500 mL round-bottom flask. 60 Solid sodium methoxide and pyridine were stirred and refluxed at 70°C for 12 hours. After the reaction was complete, DCB was added, and the reaction was continued at 180°C for another 12 hours. After the reaction was complete, the mixture was cooled to room temperature, and volatile organic compounds were removed by vacuum distillation. Diethyl ether was added, stirred thoroughly, filtered, and the ether was removed by rotary evaporation to obtain 3.06 g (60%) of the target product.

[0121]

[0122] 11H NMR (600 MHz, CDCl3) δ 8.16 (q, J = 2.7 Hz, 2H), 8.07 - 8.06 (m, 2H), 7.62 (d, 1H), 7.54 - 7.52 (m, 2H), 7.35 (s, 2H), 7.26 - 7.24 (m, 2H), δ 4.62 (dd, J = 5.8, 1.7 Hz, 2H), 4.45 (dd, J = 5.8, 1.7 Hz, 2H), 4.04 - 4.02 (m, 2H), 3.99 - 3.96 (m, 2H), 3.64 (s, 3H), 3.58 - 3.49 (m, 9H), 3.45 - 3.37 (m, 4H), 3.30 (dd, J = 5.8, 1.7 Hz, 2H), 2.43 - 2.40 (m, 2H), 2.11 - 2.05 (m, 1H), 2.00 - 1.83 (m, 9H), 1.74 - 1.68 (m, 2H). 13 13C NMR (150 MHz, CDCl3) δ 155.70, 153.84, 146.31, 146.00, 141.41, 139.69, 139.60, 139.46, 139.34, 134.92, 133.82, 131.64, 130.84, 129.94, 128.33, 128.14, 127.86, 127.57, 127.28, 127.19, 127.04, 126.80, 126.57, 125.86, 125.84, 125.63, 125.20, 124.64, 124.56, 124.48, 124.23, 124.14, 123.17, 122.32, 121.34, 120.24, 119.85, 119.79, 119.55, 110.30, 51.37, 48.92, 47.90, 47.88, 47.85, 47.82, 43.09, 42.84, 40.99, 40.36, 40.10, 36.61, 33.86, 31.55, 23.40, 21.88, 17.54.

[0123] Example 12

[0124] Perovskite device fabrication: ITO conductive glass was sequentially ultrasonically washed with acetone, deionized water, and isopropanol, and then dried under vacuum at 80°C for 12 hours. A hole injection layer was deposited on the ITO, followed by spin-coating of PTAA as a hole transport layer. A perovskite precursor solution was prepared by adding 1% superalkali to the precursor solution and dissolving it in DMSO, then spin-coating it onto the PTAA film and annealing at 100°C for 10 minutes. An electron transport layer solution was prepared by dissolving PCBM in chlorobenzene at a concentration of 10 mg / ml and spin-coating it onto the perovskite film. Then, a methanol solution of BCP was spin-coated onto the PCBM, and finally, a metallic silver electrode was vacuum-deposited.

[0125] The performance of the finally fabricated perovskite solar cell device is shown in Table 1 below:

[0126] Perovskite layer Voc(V) <![CDATA[Jsc(mA / cm 2 )]]> FF (%) PCE (%) No super alkali 1.15 23.58 78.54 21.30 Molecular formula 1 1.19 22.78 78.41 23.67 Molecular formula 4 1.15 21.69 77.34 22.98 Molecular formula 37 1.16 22.63 78.66 22.86 Molecular formula 48 1.14 21.65 78.80 22.69 Molecular formula 50 1.17 23.69 78.20 23.52 Molecular formula 53 1.12 24.22 77.34 22.42 Molecular formula 85 1.13 25.02 78.90 23.31 Molecular formula 97 1.16 25.24 78.60 23.01 Molecular formula 33 1.15 24.25 78.50 22.10 Molecular formula 225 1.18 24.33 78.45 23.21 Molecular formula 229 1.17 24.59 77.56 21.56

[0127] The polymer structures listed above are only a partial representation; other conjugated group-substituted molecules with the same concept are all within the scope of this patent protection.

[0128] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A super base for the preparation of organic perovskite solar cells, characterized in that, The structural formula is as follows: 。 2. The application of the super base according to claim 1 in the preparation of perovskite solar cells.

3. The application according to claim 2, characterized in that, After preparing the perovskite precursor solution, the super base is doped.

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