CN111303186B - Hole transport material with aryl modified carbazole as electron donor and preparation method thereof - Google Patents
Hole transport material with aryl modified carbazole as electron donor and preparation method thereof Download PDFInfo
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- -1 aryl modified carbazole Chemical class 0.000 title claims abstract description 20
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- 238000000034 method Methods 0.000 claims description 21
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- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical group [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 18
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- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 12
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- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical group [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 8
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- 238000000926 separation method Methods 0.000 claims description 5
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical group [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
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- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims 1
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- 239000007787 solid Substances 0.000 description 7
- 239000011799 hole material Substances 0.000 description 6
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 5
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- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 2
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- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- RZEQQEXIZXEASF-UHFFFAOYSA-N lithium trifluoro(sulfinato)methane Chemical compound [Li+].C(F)(F)(F)[S-](=O)=O RZEQQEXIZXEASF-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/14—Ortho-condensed systems
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a hole transport material taking aryl modified carbazole as an electron donor, and the chemical structural formula is shown as GR-16 or GR-19; the preparation method comprises the following steps: subjecting the compound of formula (7) to a cyclization reaction to form an intermediate (8); carrying out substitution reaction on the intermediate (8) to generate an intermediate (9); carrying out coupling reaction on the intermediate (9) and the compound (4) or the compound (6) to generate a hole transport material GR-16 or GR-19; the compound (4) is prepared by the following preparation method: alkylating the compound of formula (1) to produce an intermediate (2); carrying out substitution reaction on the intermediate (2) to generate an intermediate (3); subjecting the intermediate (3) to a substitution reaction to produce a compound (4); the compound (6) is prepared by the following preparation method: carrying out substitution reaction on the intermediate (2) to generate an intermediate (5); the intermediate (5) is subjected to substitution reaction to produce a compound (6).
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, relates to a doped hole transport material, and particularly relates to a hole transport material taking aryl modified carbazole as an electron donor and a preparation method thereof.
Background
With the continuous development of the global economic society, the demand of the human society for energy is larger and larger, and the traditional fossil energy is more and more difficult to meet the development demand of the economic society. In addition, the extensive use of traditional fossil energy can cause serious damage to the natural environment and exacerbate the degree of greenhouse effect. Therefore, the search for new renewable pollution-free energy sources has become a problem to be faced by human society first. And the solar energy is inexhaustible due to the advantages of being renewable and pollution-free, and the formation period is not very long like the traditional fossil energy. Therefore, how to utilize solar energy efficiently and at low cost is receiving more and more attention.
Solar cells have a long development history and a wide variety. The perovskite solar cell has a very wide development prospect due to the simple manufacturing process, low cost and good photoelectric conversion efficiency, so that the perovskite solar cell becomes the hottest research direction in the photovoltaic field.
Hole transport materials the hole transport materials have the functions of optimizing interfaces, adjusting energy level matching and the like, and are important components forming the high-efficiency perovskite solar cell. An ideal hole transport material should have a high hole mobility; the Highest occupied Orbital (HOMO) energy level is-5.1 to-5.3 eV; the perovskite-type lithium ion battery has high thermodynamic stability, good solubility and film forming property and hydrophobicity, so that a perovskite layer is protected better and the stability of the battery is improved.
In hybrid perovskite solar cells, the hole transport layer materials currently used are limited to 2, 2', 7, 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9' -spirobifluorene (Spiro-omatad), Polytriarylamine (PTAA) and PEDOT: PSS, and the like. The hole mobility of the amorphous hole transport layer materials is generally low, wherein the Spiro-OMeTAD and the PTAA require bis (trifluoromethylsulfonyl) lithium (Li-TFSI) and 4-tert-butylpyridine (TBP) as p-type doping, and the doping molecules can bring adverse effects on the stability of a battery device; and the PEDOT: although PSS does not need to be doped, polyelectrolytes have strong hygroscopicity and easily destroy the structure of the perovskite layer, and on the other hand, PEDOT: the acidity of PSS causes corrosion to ITO glass, and at the same time, PSS is hygroscopic, resulting in a decrease in the stability of a battery device.
Therefore, selecting a suitable hole transport material to further improve the performance of the perovskite solar cell is one of the problems that the industry needs to solve urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a hole transport material taking aryl modified carbazole as an electron donor, wherein the hole transport material takes aryl modified carbazole as the electron donor, and the HOMO and LUMO energy levels of the hole transport material are obviously higher than the mixed halogen perovskite energy level (HOMO ═ 5.6eV, LUMO ═ 3.9eV), so that the high-efficiency separation and transmission of holes can be effectively ensured, and meanwhile, electrons can be effectively blocked from being transited from a perovskite layer to a hole transport layer, and the occurrence of the interface electron recombination phenomenon can be inhibited; the photoelectric conversion rate of the GR-16-based battery device can reach 17.86% at most, and meanwhile, the battery device has high-efficiency stability and potential application value; the invention also aims to provide a preparation method of the hole transport material.
The invention is realized by the following technical scheme:
a hole transport material taking aryl modified carbazole as an electron donor has a chemical structural formula shown as GR-16 or GR-19:
the invention further improves the scheme as follows:
the method for preparing the hole transport material with the aryl modified carbazole as the electron donor comprises the following steps: subjecting the compound of formula (7) to a cyclization reaction to form an intermediate (8); carrying out substitution reaction on the intermediate (8) to generate an intermediate (9); carrying out a coupling reaction on the intermediate (9) and the compound (4) or the compound (6) to generate a hole transport material GR-16 or GR-19;
further, the compound (4) is prepared by the following preparation method: alkylating the compound of formula (1) to produce intermediate (2); carrying out substitution reaction on the intermediate (2) to generate an intermediate (3); subjecting the intermediate (3) to a substitution reaction to produce a compound (4);
further, the compound (6) is prepared by the following preparation method: carrying out substitution reaction on the intermediate (2) to generate an intermediate (5); subjecting the intermediate (5) to a substitution reaction to produce a compound (6);
further, synthesis of intermediate (8): taking toluene as a solvent, and carrying out heating reflux reaction on a compound shown in a formula (7) and p-anisidine under the combined action of strong base, an organic phosphine ligand and a palladium catalyst to generate an intermediate (8) in a nitrogen atmosphere; the molar ratio of the compound of the formula (7), p-anisidine, strong base, organic phosphine ligand and palladium catalyst is 1: 1.8-2.2: 3.8-4.2: 0.02-0.06: 0.008-0.012;
synthesis of intermediate (9): taking tetrahydrofuran as a solvent, and reacting the intermediate (8) with NBS to generate an intermediate (9); the molar ratio of the intermediate (8) to NBS is 1: 2.2-2.8;
synthesis of hole transport material: 1, 4-dioxane and water are used as a mixed solvent, and under the atmosphere of nitrogen, the intermediate (9) and the compound (4) or the compound (6) are heated and refluxed to react under the combined action of alkali, an organic phosphine ligand and a palladium catalyst to generate a hole transport material GR-16 or GR-19; the molar ratio of the intermediate (9), the compound (4) or the compound (6), the strong base, the organic phosphine ligand and the palladium catalyst is 1: 2.3-2.5: 5.9-6.1: 0.24-0.26: 0.1-0.14.
Further, the preparation steps of the compound (4) are as follows:
synthesis of intermediate (2): taking dimethyl sulfoxide as a solvent, and carrying out alkylation reaction on the compound shown in the formula (1) and 1-bromohexane under the action of strong alkali to generate an intermediate (2); the molar ratio of the compound of the formula (1), 1-bromohexane and strong base is 1: 1.28-1.32: 3.8-4.2;
synthesis of intermediate (3): taking toluene as a solvent, and heating and refluxing the intermediate (2) and diphenylamine under the combined action of a catalyst, strong base and an organophosphorus ligand to generate an intermediate (3) in a nitrogen atmosphere; the molar ratio of the intermediate (2), diphenylamine, catalyst, strong base and organophosphorus ligand is 1: 0.3-0.8: 0.005-0.009: 0.6-0.9: 0.005-0.009;
synthesis of intermediate (4): heating, refluxing and reacting the intermediate (3) and the pinacol diboron under the action of alkali and a catalyst to generate an intermediate (4) by taking 1, 4-dioxane as a solvent in a nitrogen atmosphere; the molar ratio of the intermediate (3), the pinacol diboron, the base and the catalyst is 1: 1.8-2.2: 2.8-3.2: 0.02-0.04.
Further, the preparation steps of the compound (6) are as follows:
synthesis of intermediate (5): taking toluene as a solvent, and heating and refluxing the intermediate (2) and 9, 9-dimethyl-9, 10-dihydroacridine under the combined action of a catalyst, strong base and an organophosphorus ligand to generate an intermediate (5) in a nitrogen atmosphere; the molar ratio of the 9, 9-dimethyl-9, 10-dihydroacridine to the intermediate (2) to the catalyst to the strong base to the organophosphorus ligand is 1: 2.8-3.2: 0.04-0.06: 1.8-2.2: 0.08-0.12;
synthesis of intermediate (6): heating and refluxing the intermediate (5) and the pinacol diboron under the action of alkali and a catalyst by taking 1, 4-dioxane as a solvent and under the atmosphere of nitrogen to react to generate an intermediate (6); the molar ratio of the intermediate (5), the pinacol diboron, the base and the catalyst is 1: 1.8-2.2: 2.8-3.2: 0.02-0.04.
Further, during the synthesis of the intermediate (8), heating and refluxing at 110-120 ℃, wherein the reaction time is 10-14 hours; during the synthesis of the intermediate (9), NBS is added into a reaction system in batches under the ice bath condition of 0-10 ℃, and after the NBS is added, the NBS is subjected to a light-tight reaction at room temperature of 20-25 ℃ for 50-100 minutes; and during the synthesis of the hole transport material, heating and refluxing at 100-110 ℃, wherein the reaction time is 20-30 hours.
Further, in the synthesis of the intermediate (8), the strong base is sodium tert-butoxide, the organophosphorus ligand is 1,1' -bis (diphenylphosphino) ferrocene, and the palladium catalyst is tris (dibenzylideneacetone) dipalladium; during the synthesis of the hole transport material, the alkali is tripotassium phosphate, the organophosphorus ligand is 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl, and the palladium catalyst is palladium acetate.
Further, when the intermediate (2) is synthesized, the compound of the formula (1) and strong base are stirred in dimethyl sulfoxide for 0.5-1.5 hours, then 1-bromohexane is added for continuous reaction for 8-12 hours, and the reaction temperature is 20-25 ℃; during the synthesis of the intermediate (3), heating and refluxing at 110-120 ℃, wherein the reaction time is 10-14 hours; during the synthesis of the intermediate (4), heating and refluxing at 100-120 ℃, wherein the reaction time is 10-14 hours; during the synthesis of the intermediate (5), heating and refluxing at 110-120 ℃, wherein the reaction time is 10-14 hours; during the synthesis of the intermediate (6), heating and refluxing at 100-120 ℃, wherein the reaction time is 10-14 hours;
further, in the synthesis of the intermediate (2), the strong base is potassium hydroxide; during the synthesis of the intermediate (3), the strong base is sodium tert-butoxide, the catalyst is tris (dibenzylideneacetone) dipalladium, and the organophosphorus ligand is 1,1' -bis (diphenylphosphino) ferrocene (dppf); during the synthesis of the intermediate (4), the alkali is potassium acetate, and the catalyst is [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride; during the synthesis of the intermediate (5), the strong base is sodium tert-butoxide, the catalyst is tris (dibenzylideneacetone) dipalladium, and the organophosphorus ligand is 2-dicyclohexyl phosphorus-2, 4, 6-triisopropyl biphenyl (XPhos); during the synthesis of the intermediate (6), the alkali is potassium acetate, and the catalyst is [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride.
Further, each step of the method also comprises a separation and purification step.
The invention further improves the scheme as follows:
the hole transport material taking aryl modified carbazole as the electron donor is applied to perovskite solar cells.
The invention has the beneficial effects that:
according to the hole transport material, aryl modified carbazole is used as an electron donor, and the HOMO energy level and the LUMO energy level of the aryl modified carbazole are obviously higher than the halogen-mixed perovskite energy level (HOMO is-5.6 eV, LUMO is-3.9 eV), so that efficient separation and transport of holes can be effectively ensured, electrons can be effectively prevented from being transited from a perovskite layer to a hole transport layer, and the phenomenon of interface electron recombination is inhibited.
The preparation method of the hole material has the advantages of simple synthetic route and mild reaction conditions, and is a normal-pressure reaction; all reaction temperatures are completed between 0 ℃ and 120 ℃, and the industrial production is easy to realize; the required raw materials are easily obtained and are all commercial products.
The hole transport material is used in the application field of perovskite solar cells, so that the perovskite solar cells have high photoelectric conversion efficiency, and the prepared devices are subjected to photoelectric conversion efficiency test, wherein the photoelectric conversion rate of the GR-16-based cell devices can reach 17.86% at most, and meanwhile, the hole transport material has high-efficiency stability and potential application value.
Drawings
FIG. 1 shows a hole transport material GR-16 1 H NMR；
FIG. 2 shows a hole transport material GR-19 1 H NMR；
FIG. 3 is a diagram of the UV-visible absorption and fluorescence emission spectra of the hole transport materials GR-16 and GR-19 in dichloromethane solvent;
FIG. 4 is a cyclic voltammogram of the hole transport materials GR-16 and GR-19;
FIG. 5 is a water contact angle test of the hole transport materials GR-16 and GR-19;
FIG. 6 is a J-V characteristic curve of perovskite solar cell devices fabricated based on GR-16 and GR-19.
Detailed Description
Example (b): synthesis of hole transport materials
Synthesis of intermediate 2:
into a 200mL single-neck flask were added the starting material 3, 6-dibromocarbazole (10.0g,30.97mmol), potassium hydroxide (6.934g,123.88mmol) and 60mL of Dimethylsulfoxide (DMSO) solvent in that order. After stirring at room temperature for 1 hour, 1-bromohexane (6.607g,40.26mmol) was added, and then the reaction was stirred at room temperature. The reaction was stopped after 10 hours of reaction, monitored by TLC plates. The reaction solution was extracted with dichloromethane, washed with water ten times, dried with anhydrous ethanol, and the organic solvent was removed by evaporation under reduced pressure. The crude product was purified by column chromatography and isolated with petroleum ether as eluent to yield 11.64g of intermediate 2 as a white fluffy solid in 92.35% yield.
Synthesis of intermediate 3:
two-necked bottles were charged with diphenylamine (1g,5.909mmol), intermediate 2(4.81g,11.819mmol), sodium tert-butoxide (851.85mg,8.864mmol), 1,1' -bis (diphenylphosphino) ferrocene (dppf) (49.14mg,0.089 mmol) and tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 )(81.17mg,0.089mmol), followed by evacuation with nitrogen and displacement three times. 30mL of toluene was added as a solvent to the two-necked flask, and the reaction was stirred with heating and then refluxed for 12 hours. After the reaction, the reaction solution was extracted with dichloromethane, dried with anhydrous ethanol, and the organic solvent was removed by evaporation under reduced pressure. 1.7g of intermediate 3 was isolated as a yellow oily liquid with a yield of 57.98% using petroleum ether as eluent. 1 H NMR(400MHz,DMSO-d 6 ):δ8.24(s,1H),7.99(s,1H),7.56–7.42(m,4H),7.16(t,J＝7.5Hz,4H),6.92(t,J＝8.1Hz,4H),6.87(t,J＝7.3Hz,2H),4.25(t,J＝6.6Hz,2H),1.73–1.55(m,2H),1.21–1.07(m,6H),0.72(t,J＝6.4Hz,3H).
Synthesis of intermediate 4:
add intermediate 3(1.0g,2.02mmol), pinacol diboron (1.029g,4.04mmol), potassium acetate (596mg,6.06mmol) and [1,1' -bis (diphenylphosphino) ferrocene to a two-necked flask]Palladium dichloride (Pd (dppf) Cl 2 ) (44.43mg,0.061mmol), then evacuated under nitrogen and replaced three times. 30mL of 1, 4-dioxane was added as a solvent for the reaction to a two-necked flask, and the reaction was heated under reflux with stirring for 12 hours. After the reaction, the reaction solution was extracted with dichloromethane, dried with anhydrous ethanol, and the organic solvent was removed by evaporation under reduced pressure. The crude product was purified by column chromatography, with petroleum ether: dichloromethane (volume ratio 10:3) was used as eluent to isolate 971mg of white granular solid compound as intermediate 4, with 87% yield.
Synthesis of intermediate 5:
into a two-necked flask were charged 9, 9-dimethyl-9, 10-dihydroacridine (1.0g,4.782mmol), intermediate 2(5.839g,14.346mmol), sodium tert-butoxide (1.149g,11.955mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (XPh os) (227.97mg,0.478mmol) and tris (diimmoniumBenzylacetone) dipalladium (218.95mg,2.391mmol), which was then evacuated under nitrogen and replaced three times. 30mL of toluene was added as a solvent to the two-necked flask, and the reaction was heated under reflux and stirred overnight. After the reaction, the reaction solution was extracted with dichloromethane, dried with anhydrous ethanol, and the organic solvent was removed by evaporation under reduced pressure. 980mg of white granular solid compound 26 was isolated in 38.22% yield using petroleum ether as eluent. 1 H NMR(400MHz,DMSO-d 6 ):δ8.47(d,J＝11.3Hz,1H),8.29(s,1H),7.91(d,J＝8.6Hz,1H),7.67(d,J＝8.8Hz,1H),7.64–7.59(m,1H),7.50(d,J＝7.1Hz,2H),7.40(t,J＝11.8Hz,1H),6.97–6.82(m,4H),6.18(d,J＝7.8Hz,2H),4.46(dd,J＝17.6,10.6Hz,2H),1.81(dd,J＝14.1,6.9Hz,2H),1.67(s,6H),1.26(dd,J＝27.0,14.3Hz,6H),0.82(t,J＝6.8Hz,3H).
Synthesis of intermediate 6:
the synthesis procedure of intermediate 6 was the same as that of intermediate 4. Intermediate 6 was a white granular solid compound with a yield of 77%.
Synthesis of intermediate 8:
add Compound 7(1g,3.11mmol), p-anisidine (764.86mg,6.22mmol), sodium tert-butoxide (1.195g,12.44mmol), 1,1' -bis (diphenylphosphino) ferrocene (dppf) (68.91mg,0.124mmol) and tris (dibenzylideneacetone) dipalladium (Pd) to a two-necked flask 2 (dba) 3 ) (28.46mg,0.031mmol), then evacuated under nitrogen and replaced three times. To a two-necked flask was added 35mL of toluene as a solvent, and the reaction was heated under stirring and then allowed to react for 12 hours under reflux. After the reaction, the reaction solution was extracted with dichloromethane, dried with anhydrous ethanol, and the organic solvent was removed by evaporation under reduced pressure. The crude product was purified by column chromatography, with petroleum ether: dichloromethane (volume ratio of 10:1) was isolated as eluent to give 821mg of a pale yellow granular solidIntermediate 8, 92.69% yield.
Synthesis of intermediate 9:
intermediate 8(300mg,1.053mmol) was added to a single vial, and 20mL of Tetrahydrofuran (THF) was added to dissolve it completely, and then the single vial was placed in an ice bath. Weighed N-bromosuccinimide (NBS) (468.32mg,2.631mmol) is added into the reaction system in batches, and the whole reaction system is protected from light after the NBS is added. The reaction was monitored by TLC plates and quenched after 70 minutes. After the reaction, the reaction solution was extracted with dichloromethane, dried with anhydrous ethanol, and the organic solvent was removed by evaporation under reduced pressure. The crude product was purified by column chromatography, eluting with petroleum ether: methylene chloride (10: 1 by volume) was isolated as eluent to yield 440mg of intermediate 9 as a white flaky solid in 94.83% yield. Intermediate 7 cannot be stored for a long time and must be immediately put into the next reaction.
And (3) synthesizing a target product GR-16:
into a two-necked flask were charged compound 9(400mg,0.91mmol), compound 4(1.186g,2.178mmol), tripotassium phosphate (1.156g,5.44mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (SPhos) (93.13mg,0.227mmol) and palladium acetate (24.44mg,0.109mmol), followed by evacuation under nitrogen and substitution three times. 30mL of 1, 4-dioxane and 10.73mL of water were added to a two-necked flask as a mixed solvent of the reaction system, and the reaction was heated and stirred to react under reflux for 24 hours. After the reaction, the reaction solution was extracted with dichloromethane, dried with anhydrous ethanol, and the organic solvent was removed by evaporation under reduced pressure. The method comprises the following steps of: dichloromethane (5: 2 by volume) was isolated as an eluent to give 699mg of GR-16 as a yellow fluffy solid in 68.94% yield. 1 H NMR(400MHz,DMSO-d 6 ):δ8.58(s,2H),8.11(s,2H),7.73(d,J＝8.4Hz,2H),7.66(d,J＝5.5Hz,4H),7.60(dd,J＝14.9,8.8Hz,4H),7.25(t,J＝7.8Hz,10H),7.16(d,J＝8.8Hz,2H),6.99(d,J＝7.9Hz,8H),6.94(t,J＝7.3Hz,4H),4.37(s,4H),3.85(s,3H),1.77(d,J＝7.0Hz,4H),1.23(s,12H),0.81(t,J＝6.8Hz,6H)。
And (3) synthesizing a target product GR-19:
into a two-necked flask were charged compound 9(400mg,0.91mmol), compound 6(1.273g,2.178mmol), tripotassium phosphate (1.156g,5.44mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (SPhos) (93.12mg,0.227mmol) and palladium acetate (24.44mg,0.109mmol), followed by evacuation and nitrogen gas purging for three times. 30mL of 1, 4-dioxane and 10.73mL of water were added to a two-neck flask as a mixed solvent of the reaction system, and the reaction was heated with stirring and allowed to react for 24 hours under reflux. After the reaction, the reaction solution was extracted with dichloromethane, dried with anhydrous ethanol, and the organic solvent was removed by evaporation under reduced pressure. The method comprises the following steps of (1) mixing petroleum ether: dichloromethane (volume ratio 5:2) was isolated as eluent to give 707mg of the yellow-green fluffy solid compound GR-19, 65.07% yield. 1 H NMR(400MHz,DMSO-d 6 ):δ8.69(s,2H),8.31(s,2H),7.91(d,J＝7.5Hz,2H),7.82(s,2H),7.71(d,J＝8.4Hz,2H),7.65(s,4H),7.51(d,J＝7.7Hz,4H),7.41(d,J＝8.2Hz,2H),7.14(d,J＝7.7Hz,2H),7.02–6.81(m,8H),6.20(d,J＝7.5Hz,4H),4.50(s,4H),3.81(s,3H),1.88(s,4H),1.69(s,12H),1.24(s,12H),0.85(s,6H)。
Test examples: characterization of hole transport materials
1. Photophysical and electrochemical testing of hole transport materials GR-16 and GR-19
The photophysical and electrochemical properties of GR-16 and GR-19 were characterized by UV-visible absorption and fluorescence emission spectroscopy (FIG. 3) and cyclic voltammetry (FIG. 4) tests, with a summary of the relevant test results in Table 1. The test result shows that: the HOMO and LUMO energy levels of the hole transport materials GR-16 and GR-19 are significantly higher than the corresponding energy levels of the halogen-mixed perovskite (HOMO-5.6 eV and LUMO-3.9 eV), so that efficient separation and transport of holes can be ensured, transition of electrons from the perovskite layer to the hole transport layer can be effectively blocked, and recombination of interface electrons can be inhibited.
Table 1, GR-16 and GR-19 Photophysical and electrochemical Properties
2. J-V curve test and stability test of hole transport materials GR-16 and GR-19
The hole transport materials GR-16 and GR-19 prepared in the above examples were, according to the literature: wang, j.; zhang, h; wu, b.; wang, z.; sun, z.; xue, s.; wu, y.; hagfeldt, a.; liang, m.angelw.chem.2019, 58(44),15724-15725. Testing a light source: AM 1.5(solar simulator-Oriel 91160-1000,300W), data collection used Keithley 2400 digital source tables. The test results and data are shown in fig. 5 and table 2, and the photovoltaic data indicate that the highest photovoltaic conversion efficiency based on GR-16 cell devices is as high as 17.86%.
TABLE 2 photovoltaic data for GR-16 and GR-19 perovskite solar cell devices
At the same time, we also tested the steady state current of GR-16 and GR-19 cell devices as a function of time (FIG. 6), and it can be seen that GR-16 and GR-19 cell devices showed rapid current responses, indicating that GR-16 and GR-19 have efficient hole transport and collection performance. Under the bias set at the maximum output power point, the short-circuit photocurrent of the GR-16 is almost kept constant in the continuous illumination of 100s, and the stability performance is obviously higher than that of the GR-19, which shows that the GR-16 battery device has higher stability performance and wider practical application value.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A hole transport material with aryl modified carbazole as electron donor is characterized in that the chemical structural formula is shown as GR-16 or GR-19:
2. a method of preparing a hole transport material comprising an aryl-modified carbazole as an electron donor according to claim 1, comprising the steps of: subjecting the compound of formula (7) to a cyclization reaction to form an intermediate (8); carrying out substitution reaction on the intermediate (8) to generate an intermediate (9); carrying out coupling reaction on the intermediate (9) and the compound (4) or the compound (6) to generate a hole transport material GR-16 or GR-19;
3. the method for preparing a hole transport material with an aryl modified carbazole as an electron donor according to claim 2, wherein the method comprises the following steps: the compound (4) is prepared by the following preparation method: alkylating the compound of formula (1) to produce intermediate (2); carrying out substitution reaction on the intermediate (2) to generate an intermediate (3); subjecting the intermediate (3) to a substitution reaction to produce a compound (4);
the compound (6) is prepared by the following preparation method: carrying out substitution reaction on the intermediate (2) to generate an intermediate (5); subjecting the intermediate (5) to a substitution reaction to produce a compound (6);
4. the method for preparing the hole transport material with the aryl modified carbazole as the electron donor according to claim 2, comprising the following steps:
synthesis of intermediate (8): taking toluene as a solvent, and heating and refluxing the compound shown in the formula (7) and p-anisidine to react under the combined action of strong base, organic phosphine ligand and a palladium catalyst to generate an intermediate (8) in a nitrogen atmosphere; the molar ratio of the compound of the formula (7), p-anisidine, strong base, organic phosphine ligand and palladium catalyst is 1: 1.8-2.2: 3.8-4.2: 0.02-0.06: 0.008-0.012;
synthesis of intermediate (9): taking tetrahydrofuran as a solvent, and reacting the intermediate (8) with NBS to generate an intermediate (9); the molar ratio of the intermediate (8) to NBS is 1: 2.2-2.8;
synthesis of hole transport material: 1, 4-dioxane and water are used as a mixed solvent, and under the atmosphere of nitrogen, the intermediate (9) and the compound (4) or the compound (6) are heated and refluxed to react under the combined action of alkali, an organic phosphine ligand and a palladium catalyst to generate a hole transport material GR-16 or GR-19; the molar ratio of the intermediate (9), the compound (4) or the compound (6), the strong base, the organic phosphine ligand and the palladium catalyst is 1: 2.3-2.5: 5.9-6.1: 0.24-0.26: 0.1-0.14.
5. The method for preparing a hole transport material with an aryl modified carbazole as an electron donor according to claim 3, wherein the method comprises the following steps: the preparation steps of the compound (4) are as follows:
synthesis of intermediate (2): taking dimethyl sulfoxide as a solvent, and carrying out alkylation reaction on the compound shown in the formula (1) and 1-bromohexane under the action of strong alkali to generate an intermediate (2); the molar ratio of the compound of the formula (1), 1-bromohexane and strong base is 1: 1.28-1.32: 3.8-4.2;
synthesis of intermediate (3): heating and refluxing the intermediate (2) and diphenylamine under the combined action of a catalyst, strong base and an organophosphorus ligand to generate an intermediate (3) by taking toluene as a solvent and under the atmosphere of nitrogen; the molar ratio of the intermediate (2), diphenylamine, catalyst, strong base and organophosphorus ligand is 1: 0.3-0.8: 0.005-0.009: 0.6-0.9: 0.005-0.009;
synthesis of intermediate (4): heating and refluxing the intermediate (3) and the pinacol diboron under the action of alkali and a catalyst by taking 1, 4-dioxane as a solvent and under the atmosphere of nitrogen to react to generate an intermediate (4); the molar ratio of the intermediate (3), the pinacol diboron, the base and the catalyst is 1: 1.8-2.2: 2.8-3.2: 0.02-0.04.
The preparation steps of the compound (6) are as follows:
synthesis of intermediate (5): taking toluene as a solvent, and heating and refluxing the intermediate (2) and 9, 9-dimethyl-9, 10-dihydroacridine under the combined action of a catalyst, strong base and an organophosphorus ligand to generate an intermediate (5) in a nitrogen atmosphere; the molar ratio of the 9, 9-dimethyl-9, 10-dihydroacridine to the intermediate (2) to the catalyst to the strong base to the organophosphorus ligand is 1: 2.8-3.2: 0.04-0.06: 1.8-2.2: 0.08-0.12;
synthesis of intermediate (6): heating, refluxing and reacting the intermediate (5) and the pinacol diboron under the action of alkali and a catalyst to generate an intermediate (6) by taking 1, 4-dioxane as a solvent in a nitrogen atmosphere; the molar ratio of the intermediate (5), the pinacol diboron, the base and the catalyst is 1: 1.8-2.2: 2.8-3.2: 0.02-0.04.
6. The method for preparing a hole transport material with an aryl modified carbazole as an electron donor according to claim 4, wherein the method comprises the following steps: during the synthesis of the intermediate (8), heating and refluxing at 110-120 ℃, wherein the reaction time is 10-14 hours; during the synthesis of the intermediate (9), NBS is added into a reaction system in batches under the ice bath condition of 0-10 ℃, and after the addition is finished, the NBS reacts for 50-100 minutes at the room temperature of 20-25 ℃ in a dark place; and during the synthesis of the hole transport material, heating and refluxing at 100-110 ℃, wherein the reaction time is 20-30 hours.
7. The method for preparing a hole transport material with an aryl modified carbazole as an electron donor according to claim 4, wherein the method comprises the following steps: during the synthesis of the intermediate (8), the strong base is sodium tert-butoxide, the organophosphorus ligand is 1,1' -bis (diphenylphosphino) ferrocene, and the palladium catalyst is tris (dibenzylideneacetone) dipalladium; during the synthesis of the hole transport material, the alkali is tripotassium phosphate, the organophosphorus ligand is 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl, and the palladium catalyst is palladium acetate.
8. The method for preparing the hole transport material with the aryl modified carbazole as the electron donor according to claim 5, wherein the method comprises the following steps: when the intermediate (2) is synthesized, the compound shown in the formula (1) and strong base are stirred in dimethyl sulfoxide for 0.5-1.5 hours, then 1-bromohexane is added to continue to react for 8-12 hours, and the reaction temperature is 20-25 ℃; during the synthesis of the intermediate (3), heating and refluxing at 110-120 ℃, wherein the reaction time is 10-14 hours; during the synthesis of the intermediate (4), heating and refluxing at 100-120 ℃, wherein the reaction time is 10-14 hours; during the synthesis of the intermediate (5), heating and refluxing at 110-120 ℃, wherein the reaction time is 10-14 hours; and (3) heating and refluxing the intermediate (6) at 100-120 ℃ during synthesis, wherein the reaction time is 10-14 hours.
9. The method for preparing a hole transport material with an aryl modified carbazole as an electron donor according to claim 5, wherein the method comprises the following steps: in the synthesis of the intermediate (2), the strong base is potassium hydroxide; during synthesis of the intermediate (3), the strong base is sodium tert-butoxide, the catalyst is tris (dibenzylideneacetone) dipalladium, and the organophosphorus ligand is 1,1' -bis (diphenylphosphino) ferrocene (dppf); during the synthesis of the intermediate (4), the alkali is potassium acetate, and the catalyst is [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride; during the synthesis of the intermediate (5), the strong base is sodium tert-butoxide, the catalyst is tris (dibenzylideneacetone) dipalladium, and the organophosphorus ligand is 2-dicyclohexyl phosphorus-2, 4, 6-triisopropyl biphenyl (XPhos); during the synthesis of the intermediate (6), the alkali is potassium acetate, and the catalyst is [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride.
10. The method for preparing a hole transport material with an aryl modified carbazole as an electron donor according to any one of claims 2 to 9, wherein: the method also comprises a separation and purification step in each step.
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| Indeno[1,2-b]carbazole as Methoxy-Free Donor Group: Constructing Efficient and Stable Hole-Transporting Materials for Perovskite Solar Cells;Wang, Jialin;《Angewandte Chemie, International Edition》;20190916;第58卷(第44期);15721-15725 * |
| Synthesis and Hole-Transporting Properties of Highly Fluorescent N-Aryl Dithieno[3,2-b:2",3"-d]pyrrole-Based Oligomers;Ganapathy Balaji;《Journal of Physical Chemistry C》;20100219;第114卷(第10期);4628-4635页 * |
| 新型空穴传输材料在钙钛矿太阳能电池中的研究进展;宋志浩;《物理学报Acta Phys. Sin.》;20151231;第64卷(第3期);033301-1至033301-17页 * |
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Application publication date: 20200619 Assignee: Suzhou Liwei New Materials Technology Co.,Ltd. Assignor: HUAIYIN INSTITUTE OF TECHNOLOGY Contract record no.: X2023980047090 Denomination of invention: A hole transport material with aryl modified carbazole as electron donor and its preparation method Granted publication date: 20220823 License type: Common License Record date: 20231115 |