CN112159409A - Asymmetric organic hole transport material with pyrrolopyrrole as mother nucleus and synthesis method and application thereof - Google Patents
Asymmetric organic hole transport material with pyrrolopyrrole as mother nucleus and synthesis method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 26
- 230000005525 hole transport Effects 0.000 title claims abstract description 25
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical compound C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000001308 synthesis method Methods 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 24
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 8
- 229940125904 compound 1 Drugs 0.000 claims description 7
- 229940125782 compound 2 Drugs 0.000 claims description 7
- 229940126214 compound 3 Drugs 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [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 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 5
- 229940079593 drug Drugs 0.000 claims 3
- 239000003814 drug Substances 0.000 claims 3
- 239000000706 filtrate Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 238000002390 rotary evaporation Methods 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical compound O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229930008407 benzylideneacetone Natural products 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229940088679 drug related substance Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses an asymmetric organic hole transport material taking pyrrolo-pyrrole as a parent nucleus, a synthesis method and application thereof, belonging to the technical field of solar cells and having the following chemical structure:
in formula (I): r' ═ OCH3Or ═ SCH3. The hole transport material is reasonable in raw material synthesis and cost, and can be efficiently applied to perovskite solar cells to obtain excellent photoelectric conversion efficiency.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly discloses preparation of an asymmetric organic hole transport material taking pyrrolo-pyrrole as a parent nucleus and application of the material in a perovskite cell.
Background
The use of fossil fuels not only causes increasingly serious pollution to the global environment, but also aggravates the exhaustion of energy. To solve this problem, solar cells that can convert light energy into electric energy have attracted our attention. Due to the good photoelectric property and carrier transmission property of Perovskite materials, researchers convert liquid electrolyte serving as a charge transmission layer into a solid hole transmission layer on the basis of dye-sensitized solar cells, and make great progress in the field of Perovskite Solar Cells (PSCs). The hole transport layer in the perovskite battery can well complete the transmission and collection work of electrons absorbed by the perovskite layer. The method has a very important role for perovskite batteries, and the novel hole transport material has been a hot spot of research of scientists for a long time.
The organic hole transport layer material is easy to synthesize, has a flexible structure, contributes to improving the photoelectric conversion efficiency of the perovskite solar cell, and also contributes to improving the stability of the cell. The problems of difficult acquisition of synthetic raw materials, high cost and low efficiency are also existed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to introduce a hole transport material which has high efficiency, easily obtained raw materials, reasonable cost and stable work in a solar cell; on the other hand, a feasible and reasonable synthesis step for providing the hole transport material is provided; finally, the method is applied to the perovskite solar cell.
The invention is realized by the following scheme:
an asymmetric organic hole transport material taking pyrrolo-pyrrole as a parent nucleus has a chemical structural formula shown as the following (I):
in formula (I): r' ═ OCH3Or ═ SCH3；
The synthesis steps are as follows:
the method comprises the following steps: 1.85g (10mmol) of compound 1, 1.31g (10mmol) of compound 2 and 2.14g (20mmol) of compound 3 are weighed out and refluxed at 90 ℃ using glacial acetic acid as solvent under catalysis of butanedione (860.9mg, 10mmol) and p-toluenesulfonic acid (950.6mg, 5mmol) to yield compound 4, compound 1: compound 2: compound 3: butanediol: adding the compound 1,2,3 and a catalyst p-toluenesulfonic acid into a two-neck flask, adding glacial acetic acid into a fume hood, condensing air, heating at 90 ℃, reacting for 30 minutes, adding 2, 3-butanedione into an injector, and reacting for 3-4 hours; after the reaction is finished, the reaction product is cooled to room temperature, filtered by a Buchner funnel, washed by methanol solution for three times, recrystallized by ethyl acetate, and dried to obtain 2.8g of crude product, wherein the yield is 51.75%.
Step two: weighing any one of the compounds 5, 6 or 7 and the compound 8, adding sodium tert-butoxide, tri-tert-butylphosphine and tris (dibenzylideneacetone) dipalladium, adding toluene under the protection of nitrogen, and reacting under the atmosphere of nitrogen. After the reaction is finished, cooling to room temperature, quenching the reaction with cold water, extracting with DCM, collecting an organic phase, drying with anhydrous sodium sulfate, stirring the sample with silica gel, evaporating the reagent by rotation, and purifying with a chromatographic column (PE: EA ═ 5:1) to obtain a compound with the equivalent weight of compound 4: compound 8: sodium tert-butoxide: tris (dibenzylideneacetone) dipalladium ═ 1: 1.2: 3: 0.005, the dosage of the tri-tert-butylphosphine is 0.5ml, condensed water needs to be introduced in the process, the reaction condition is heating, the temperature is not too high, and the reaction lasts for 8 to 12 hours;
the synthetic route is as follows:
formula 8+And (I): r' ═ OCH3Or ═ SCH3；
R ═ Br or ═ CF in formula 43Or ═ CH3The compounds are of the formulae 5, 6, 7
The invention has the beneficial effects that:
1. the asymmetric organic hole transport material taking the pyrrolopyrrole as the parent nucleus provided by the invention has the advantages of reasonable synthesis raw material, reasonable cost, higher crystallinity and higher synthesis efficiency.
2. The test result of the application of the organic hole transport material in the perovskite solar cell shows that:
the asymmetric organic hole transport material taking the pyrrolopyrrole as the parent nucleus shows better solvent cleaning resistance in device manufacturing, has the solubility of 6.45mg/ml in DMF, and has better processing performance. The photoelectric conversion efficiency reaches 16.578%.
Drawings
FIG. 1 shows YJ-PP1 of the invention1H NMR spectrum.
FIG. 2 shows that the perovskite solar cell manufactured by YJ-PP1 of the invention has an AM 1.5-100mW/cm2d test result chart.
Detailed Description
The synthetic route of the invention is as follows:
in formula (I): r' ═ OCH3Or ═ SCH3；
R ═ Br or ═ CF in formula 43Or ═ CH3The compounds are of the formulae 5, 6, 7
Examples 1 and 2 are described below by taking formula 5 as an example, and the synthetic effects of formulae 6 and 7 are the same as those of formula 5.
Example 1:
the synthesis route of the asymmetric organic hole transport material YJ-PP1 with the pyrrolopyrrole as the parent nucleus is as follows:
into a 100ml two-necked flask were charged 1.049g (2mmol) of Compound 5, 458mg (2.4mmol) of Compound 8, 384.4mg (4mmol) of sodium t-butoxide, 9.2mg (0.01 mmol) of tris (dibenzylideneacetone) dipalladium, and 40ml of anhydrous toluene and 1ml of tris (benzylideneacetone) were added under nitrogen atmosphereTert-butylphosphine. The reaction was stopped after stirring and refluxing for 12 h. Cooling to room temperature, quenching with cold water, EA extraction, and purification by chromatography (PE: EA ═ 5:1) gave 443mg (0.642mmol) of yellow solid in 32.1% yield.1H NMR(400MHz d6-DMSO) (ppm):7.67(d，J＝8Hz,2H)，7.33～7.23(m,6H)，7.18(d，J＝8Hz,4H)， 7.0(t,J1＝12Hz,J2＝4Hz,6H)，6.91(d，J＝12Hz，4H)，6.6(d，J＝12Hz,3H),6.27 (s，1H)，3.73(s，6H)，2.35(d，J＝4Hz，6H)。
Example 2:
synthetic route of compound YJ-PP 4:
the synthetic route of YJ-PP 4 was essentially the same as that of YJ-PP1, with a greenish black solid yield of 54.53%.1H NMR(400MHz d6-DMSO)(ppm):7.67(d，J＝8Hz,2H)，7.37～7.14(m,10H)，7.08(d， J＝8Hz,2H)，6.94(d,J1＝12Hz,4H)，6.81(d，J＝8Hz，4H)，6.64(d，J＝8Hz,3H),6.34 (s，1H)，2.44(s，6H)，2.35(d，J＝4Hz，6H)。
Example 3:
synthetic route of compound YJ-PP 2:
1.85g (10mmol) of compound 1, 1.31g (10mmol) of compound 2, 2.14g (20mmol) of compound 3 and p-toluenesulfonic acid as a catalyst are weighed in a two-neck flask, glacial acetic acid is used as a solvent, 2, 3-butanedione and p-toluenesulfonic acid (950.6mg, 5mmol) are added into a ventilated cabinet, 50mL of glacial acetic acid is added into the ventilated cabinet, air is condensed, heating is carried out at 90 ℃,2, 3-butanedione (860.9mg, 10mmol) is added into the mixture after reaction is carried out for 30 minutes, and the mixture is reacted for 3 to 4 hours; after the reaction is finished, the reaction product is cooled to room temperature, filtered by a Buchner funnel, washed by methanol solution for three times, recrystallized by ethyl acetate, and dried to obtain 2.8g of crude product, wherein the yield is 51.75%.1H NMR(400MHz d6-DMSO) (ppm):7.68(d，J＝8Hz,4H)，7.37～7.04(m,12H)，6.64(d，J＝4Hz,1H),6.34 (d，J＝4Hz，1H)，2.35(d，J＝12Hz，6H)，2.26(s，3H)。
Example 4:
synthetic route of compound YJ-PP 3:
the synthetic route of the compound YJ-PP 3 is the same as that of YJ-PP 2, and the yield is 62.1%.1H NMR(400MHz d6-DMSO) (ppm):7.70(d, J ═ 8Hz,4H), 7.61(d, J ═ 8Hz, 2H),7.38(m,4H), 7.29 (d, J ═ 8Hz,4H), 7.19(d, J ═ 8Hz,4H), 6.66(d, J ═ 4Hz, 1H), 6.60(d, J ═ 4Hz, 1H), 2.36(s, 6H). Of YJ-PP11The H NMR results are shown in FIG. 1.
Example 5:
synthetic route to compound 5:
1.85g (10mmol) of p-bromobenzaldehyde, 1.31g (10mmol) of p-cyanobenzaldehyde and 2.14g (20mmol) of p-toluidine were weighed out and refluxed at 90 ℃ using glacial acetic acid as solvent under the catalysis of butanedione (860.9mg, 10mmol) and p-toluenesulfonic acid (950.6mg, 5mmol) to give compound 5, using the molar equivalents of the drug substance, compound 1: compound 2: compound 3: butanediol: p-toluenesulfonic acid ═ 1:1:2:1: 0.5. Adding a compound 1,2,3 and a catalyst p-toluenesulfonic acid into a two-neck flask, adding glacial acetic acid into a fume hood, condensing air, heating at 90 ℃, reacting for 30 minutes, adding 2, 3-butanedione into an injector, and reacting for 3-4 hours; after the reaction is finished, the reaction product is cooled to room temperature, filtered by a Buchner funnel, washed by methanol solution for three times, recrystallized by ethyl acetate, and dried to obtain 2.8g of bright yellow crude product, wherein the yield is 51.75%.
Application example:
perovskite solar cell manufactured by asymmetric organic hole transport material YJ-PP1 with pyrrolopyrrole as parent nucleus. Preparing 5mg/ml solution by chlorobenzene, spin-coating at 3000r/min on ITO conductive glass, heating at 100 ℃ for 10min, naturally cooling, transferring to a glove box, blade-coating perovskite by a one-step deposition method, heating at 100 ℃, heating to finish spin-coating a conductive layer, and plating a metal electrode by a coating machine. The prepared perovskite solar cell is 1.5-100mW/cm in AM2d is measured at light intensity. The test results are shown in FIG. 2, where the open-circuit voltage (Voc) of the cell was 1.073Ve and the short-circuit current density (Jsc) was 22.213mA/cm2Fill Factor (FF)0.694, photoelectric conversion efficiency 16.578%.
Claims (8)
1. An asymmetric organic hole transport material taking pyrrolo-pyrrole as a parent nucleus is characterized by having the following chemical structure:
in formula (I): r' ═ OCH3Or ═ SCH3。
2. The asymmetric organic hole transport material with pyrrolo-pyrrole as a core according to claim 1, wherein the asymmetric organic hole transport material with pyrrolo-pyrrole as a core is shown as YJ-PP1 and YJ-PP 4 as follows:
3. the method for synthesizing the asymmetric organic hole transport material with the pyrrolopyrrole as the parent nucleus according to claim 1, which comprises the following steps:
the method comprises the following steps: using glacial acetic acid as a solvent for a compound 1, a compound 2 and a compound 3, refluxing at 90 ℃ under the catalysis of butanedione and p-toluenesulfonic acid to generate a compound 4, adding the compounds 1,2 and 3 and the catalyst p-toluenesulfonic acid into a two-neck flask, adding glacial acetic acid into a fume hood, condensing air, heating at 90 ℃, reacting for 30 minutes, adding 2, 3-butanedione into an injector, and reacting for 3-4 hours; after the reaction is finished, cooling to room temperature, carrying out suction filtration by using a Buchner funnel, washing with a methanol solution for three times, recrystallizing with ethyl acetate, and drying to obtain 2.8g of a crude product, wherein the yield is 51.75%;
step two: weighing a compound 4 and a compound 8, and dissolving the compound with toluene; adding sodium tert-butoxide, tri-tert-butylphosphine and tris (dibenzylideneacetone) dipalladium under the protection of nitrogen; reacting in nitrogen atmosphere, cooling, filtering the reaction solution after the reaction is finished, carrying out rotary evaporation on the filtrate, passing through a silica gel column to finally obtain a compound (I), introducing condensed water in the process, heating under the reaction condition, wherein the temperature is not too high, and reacting for 8-12 hours;
the synthetic route is as follows:
in formulae 8 and (I): r' ═ OCH3Or ═ SCH3；
R ═ Br or ═ CF in formula 43Or ═ CH3The compounds are of the formulae 5, 6, 7
4. The method for synthesizing an asymmetric organic hole transport material with pyrrolo-pyrrole as a core according to claim 3, wherein the molar equivalent of the drug in the first step is as follows, compound 1: compound 2: compound 3: butanediol: p-toluenesulfonic acid ═ 1:1:2:1: 0.5.
5. The method for synthesizing an asymmetric organic hole transport material using pyrrolo-pyrrole as a core according to claim 3 or 4, wherein the amounts of the drugs used in the step one are 1.85g (10mmol) of compound 1, 1.31g (10mmol) of compound 2 and 2.14g (20mmol) of compound 3, butanedione (860.9mg, 10mmol) and p-toluenesulfonic acid (950.6mg, 5 mmol).
6. The method for synthesizing an asymmetric organic hole transport material using pyrrolopyrrole as a nucleus according to claim 3, wherein the molar equivalent of the drug used in the second step is compound 4: compound 8: sodium tert-butoxide: tris (dibenzylideneacetone) dipalladium ═ 1: 1.2: 3: 0.005.
7. the method for synthesizing an asymmetric organic hole transport material with pyrrolo-pyrrole as a core according to claim 3, wherein the amount of tri-tert-butylphosphine used in the second step is 0.5 ml.
8. Use of the pyrrolopyrrole-based asymmetric organic hole transport material according to claim 1 or 2 in a perovskite solar cell.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580581A (en) * | 2009-06-12 | 2009-11-18 | 华南理工大学 | Electric field-induced red-light-emitting polymer taking pyrrolo-pyrrole-dione as lateral chain and preparation and application thereof |
| WO2014054596A1 (en) * | 2012-10-02 | 2014-04-10 | 三菱化学株式会社 | Organic electroluminescent element, organic el lighting and organic el display device |
| CN111205293A (en) * | 2020-02-12 | 2020-05-29 | 厦门天马微电子有限公司 | Heterocyclic compound, display panel and display device |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580581A (en) * | 2009-06-12 | 2009-11-18 | 华南理工大学 | Electric field-induced red-light-emitting polymer taking pyrrolo-pyrrole-dione as lateral chain and preparation and application thereof |
| WO2014054596A1 (en) * | 2012-10-02 | 2014-04-10 | 三菱化学株式会社 | Organic electroluminescent element, organic el lighting and organic el display device |
| CN111205293A (en) * | 2020-02-12 | 2020-05-29 | 厦门天马微电子有限公司 | Heterocyclic compound, display panel and display device |
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