CN116621848B - Perylene-based fused ring compound, preparation method and application - Google Patents

Perylene-based fused ring compound, preparation method and application Download PDF

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CN116621848B
CN116621848B CN202310892432.7A CN202310892432A CN116621848B CN 116621848 B CN116621848 B CN 116621848B CN 202310892432 A CN202310892432 A CN 202310892432A CN 116621848 B CN116621848 B CN 116621848B
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perylene
fused ring
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CN116621848A (en
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李鹏
赵文渊
李令义
周勇
雷鸣
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Valiant Co Ltd
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    • 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
    • C07D487/22—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 four or more hetero rings
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract

The invention relates to the technical field of solar cell materials, in particular to a perylene-based fused ring compound, a preparation method and application, wherein the perylene-based fused ring compound is shown as a formula I:wherein R is any one of C1-C12 alkyl or ethylene glycol monomethyl ether chain. The low-cost polycyclic aromatic perylene is used as a raw material, and is coupled with 1-chloro-2-amino naphthalene through C-N, C-C to synthesize a polypyrrole fused extended non-planar large pi-conjugated framework, and the solubility of molecules is regulated and the stacking structure of the molecules is regulated by introducing side chains, so that the charge mobility is improved. The perylene-based fused ring compounds of the present invention can be used as hole transport materials. Experimental results show that the energy conversion efficiency of the perovskite solar cell device prepared by taking the perylene-based fused ring compound prepared by the invention as the hole transport layer can reach 20.8% -23.5%.

Description

Perylene-based fused ring compound, preparation method and application
Technical Field
The invention relates to a perylene-based fused ring compound, a preparation method and application thereof, and belongs to the technical field of solar cell materials.
Background
In recent years, the photoelectric energy conversion efficiency (PCE) of organic-inorganic hybrid Perovskite Solar Cells (PSCs) is significantly improved, and the creation of a non-planar P-type small organic molecule semiconductor Hole Transport Material (HTM) plays a vital role in improving PCE. Since the interface of the charge transport layer-perovskite layer has a great influence on the performance parameters of the device (open circuit voltage (Voc), short circuit current (Jsc), fill Factor (FF)), the charge transport process of each interface in the device must be controlled in order to further raise the PCE. In PSCs, HTM avoids direct contact between perovskite layer and battery anode in hole extraction and transmission process, reduces electron hole recombination, improves perovskite layer surface morphology, and is key component of PSCs device. The HTM with excellent performance should have several properties: (1) HOMO, LUMO energy levels matched to the perovskite layer; (2) high hole mobility and conductivity; (3) The raw materials are cheap, the synthesis and the preparation are simple, and the physical and chemical properties are stable under the conditions of high temperature, high light, high humidity and the like.
The Spiro-OMeTAD is representative of Spiro type organic small molecule HTM, has good solubility, and has proper energy level, absorption spectrum and amorphous structure. Although the Spiro-OMeTAD is excellent in performance, its hole mobility (1 to 2X 10) -4 cm 2 ·V -1 ·S -1 ) And conductivity (-10) -5 S·cm -1 ) Relatively low, the hole transport property is improved by adding the doping agent when in use, and the synthesis conditions are complex, the purification is difficult and the cost is high. Numerous studies have been made on developing inexpensive, high-performance Spiro-ome tad alternative materials to obtain HTMs of different molecular space structures (e.g., triphenylamine-containing helices, stars, linear structures, and thiophene-containing structures), and to adjust energy levels, a large volume of donor (e.g., diarylamines, dicarbazolamines, etc.) needs to be introduced, which affects the effective stacking of pi-conjugated systems and is unfavorable for charge transport.
The perylene compound is a low-cost polycyclic fused large pi-conjugated system compound, and is fused with a nitrogen-containing heterocycle to be extensible to obtain a non-planar larger pi-conjugated framework, the intermolecular accumulation easily generates more intermolecular contact, and the energy level structure and the excited state charge transfer capacity of molecular states can be adjusted by utilizing the structural characteristics of different orbital interactions between hetero atoms and pi conjugated systems and different valence bond numbers of the hetero atoms; meanwhile, the non-planarity and three-dimensional intermolecular/intramolecular interaction of a pi-philic conjugated system can be increased, which is beneficial to regulating and controlling the stacking structure of molecules and improving the charge mobility; and the solubility of the molecules is improved, which is beneficial to solution processing of the device.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a perylene-based fused ring compound, a preparation method and application thereof, wherein low-cost polycyclic aromatic hydrocarbon perylene is taken as a raw material, and is coupled with 1-chloro-2-amino naphthalene through C-N, C-C to synthesize a polypyrrole fused extended non-planar large pi-conjugated skeleton, and the molecular solubility is adjusted by introducing a side chain, so that the molecular stacking structure is regulated and controlled, and the charge mobility is improved.
The technical scheme for solving the technical problems is as follows: a perylene-based fused ring compound, the perylene-based fused ring compound being represented by formula I:
；
wherein R is any one of C1-C12 alkyl or ethylene glycol monomethyl ether chain.
Further, the hydrocarbon group is any one of a linear hydrocarbon group and a branched hydrocarbon group.
Further, the perylene-based fused ring compound is selected from the following structures:
。
the invention also discloses a preparation method of the perylene-based fused ring compound, which comprises the following steps:
；
s1, preparation of an intermediate 1:
3, 9-dibromoperylene and 1-chloro-2-aminonaphthalene, pd (OAc) 2 Adding DPEPhOS and NaO (t-Bu) into a reactor, adding toluene as a solvent, heating and refluxing under the protection of nitrogen, and performing aftertreatment after the reaction is finished to obtain an intermediate 1;
s2, preparing an intermediate 2:
intermediate 1, pd (OAc) 2 、K 2 CO 3 、P(t-Bu) 3 ·HBF 4 Adding DMAc and the mixture into a reactor, heating and stirring under the protection of nitrogen to react, and after the reaction is finished, obtaining an intermediate 2 through post-treatment;
s3, preparing an intermediate 3:
dissolving the intermediate 2 in DMF and THF, slowly adding NaH under the protection of nitrogen, stirring uniformly, adding methyl iodide, stirring at room temperature for reaction, and performing aftertreatment after the reaction is finished to obtain an intermediate 3;
s3, preparing an intermediate 4:
dissolving the intermediate 3 in dichloromethane, then adding NBS, slowly heating to reflux for reaction, and after the reaction is finished, obtaining an intermediate 4 through post-treatment;
s4, preparation of an intermediate 5:
intermediate 4, 1-chloro-2-aminonaphthalene and Pd (OAc) 2 Adding DPEPhOS and NaO (t-Bu) into a reactor, adding toluene as a solvent, heating and refluxing under the protection of nitrogen, and performing aftertreatment after the reaction is finished to obtain an intermediate 5;
s5, preparing an intermediate 6:
intermediate 5, pd (OAc) 2 、K 2 CO 3 、P(t-Bu) 3 ·HBF 4 Adding DMAc and the mixture into a reactor, heating and stirring under the protection of nitrogen to react, and after the reaction is finished, obtaining an intermediate 6 through post-treatment;
s6, preparing perylene-based fused ring compounds:
dissolving the intermediate 6 in DMF and THF, slowly adding NaH under the protection of nitrogen, stirring uniformly, adding a halogenated reagent RX, stirring at room temperature for reaction, and performing aftertreatment after the reaction is finished to obtain the perylene-based fused ring compound;
x in the halogenated reagent RX is I or Br, and R in RX is any one of C1-C12 hydrocarbon group or ethylene glycol monomethyl ether chain.
Preferably, the R is selected from any one of the following structures:
。
further, the halogenating reagent RX is any one of iodohexane, 2-ethyl iododecane, 1-bromo-2- (2-methoxyethoxy) ethane and 1-bromo-2- (2- (2-methoxyethoxy) ethoxy) ethane.
The invention also discloses application of the perylene fused ring compound: the perylene-based fused ring compound is applied to perovskite solar cells.
Further, the perovskite solar cell comprises a substrate, a transparent oxide electrode, an electron transport layer, a photoactive layer, a hole transport layer and a metal electrode.
Further, the perylene-based fused ring compound is applied to a hole transport layer.
Further, the electron transport layer comprises titanium dioxide.
Further, the photoactive layer includes perovskite therein.
The beneficial effects of the invention are as follows:
the perylene-based fused ring compound takes low-cost polycyclic aromatic hydrocarbon perylene as a raw material, is coupled with 1-chloro-2-amino naphthalene through C-N, C-C to synthesize a polypyrrole fused extension non-planar large pi-conjugated framework, and adjusts the molecular solubility by introducing a side chain, thereby being beneficial to regulating and controlling the stacking structure of molecules and improving the charge mobility.
The mobility of the perylene-based fused ring compound serving as a hole transport material is high, and the PCE of the prepared PSC device is high. Experimental results show that PCE of PSC devices prepared by taking perylene-based fused ring compounds prepared by the method as hole transport layers can reach 20.8% -23.5%.
Drawings
Fig. 1 is a schematic structural diagram of a perovskite solar cell in an embodiment.
Detailed Description
The following describes the present invention in detail. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, so that the invention is not limited to the specific embodiments disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
1. Preparation example
；
S1, preparation of an intermediate 1:
3, 9-dibromoperylene and 1-chloro-2-aminonaphthalene, pd (OAc) 2 Adding DPEPhOS and NaO (t-Bu) into a reactor, adding toluene as a solvent, heating and refluxing under the protection of nitrogen, and performing aftertreatment after the reaction is finished to obtain an intermediate 1.
The specific process is as follows:
3, 9-dibromoperylene (2.05 g,410.1 g/mol,5mmol, CAS No.: 56752-35-3) and 1-chloro-2-aminonaphthalene (1.865 g,177.6 g/mol,10.5mmol, CAS No.: 16452-11-2), pd (OAc) 2 （22.5 mg，224.5g/mol，0.1 mmol，CAS NO.：3375-31-3），DPEPhOS（269.5 mg，538.6 g/mol，0.5 mmol，CASNO.：166330-10-5），NaO(tBu) (2.4 g,96.0 g/mol,25 mmol, CAS No.: 865-48-5) was added to a 500mL single neck round bottom flask, 200 mL toluene was added as solvent, heated under nitrogen at 120℃under reflux for 24h, cooled to room temperature after completion of the reaction, celite filtered to remove catalyst and base, and the filtrate concentrated and recrystallized from THF to give 2.49 g solid intermediate 1 in 82.5% yield. The structural characterization data are as follows:
1 H NMR (400 MHz, THF-d 8 ) δ 10.48-10.45 (bs, 2H), 8.22-8.20 (d, 2H), 8.12-8.09 (m, 4H), 7.83-7.81 (d, 2H), 7.66-7.59 (m, 6H), 7.48-7.47 (m, 2H), 7.32-7.30 (m,4H), 7.16-7.15 (d, 2H). 13 C NMR (101 MHz, THF-d 8 ) δ 142.9, 139.3, 130.4, 128.4, 128.2, 127.6, 127.2, 127.1, 126.9, 126.1, 124.6, 124.4, 123.0, 121.2，120.2,117.5, 116.7, 111.3, 108.8 ppm. HR-MS (ESI) m/z calcd. For (C 40 H 24 Cl 2 N 2 ): 603.5490. Found: 603.5485.
s2, preparing an intermediate 2:
intermediate 1, pd (OAc) 2 、K 2 CO 3 、P(t-Bu) 3 ·HBF 4 Adding DMAc and the mixture into a reactor, heating and stirring under the protection of nitrogen to react, and after the reaction is finished, obtaining an intermediate 2 through post-treatment;
the specific process is as follows:
intermediate 1 (1.207 g,603.6 g/mol,2 mmol), pd (OAc) 2 (90 mg,224.5 g/mol,0.4 mmol, CAS No.: 3375-31-3), potassium carbonate (K) 2 CO 3 ）（2.76 g，138.0 g/mol，20mmol，CAS NO.：584-08-7）、P(t-Bu) 3 ·HBF 4 (116.0 mg,290.0 g/mol,0.4 mmol, CAS No.: 131274-22-1) and 80 mL ultra-dry N, N-dimethylacetamide (DMAc) were added to a 250 mL single-neck round bottom flask, the reaction was stirred under heating at 130℃for 24 hours under nitrogen protection, cooled to room temperature after completion of the reaction, the reaction solution was poured into 200 mL saturated brine, extracted three times with Dichloromethane (DCM) in an amount of 100mL each time, and the organic phase was concentrated with anhydrous sodium sulfate (Na 2 SO 4 ) After drying, filtering, rotary evaporation and concentration are carried out to obtain a crude product, and a 200-mesh neutral alumina column is used for separation and purification, wherein the eluent is THF and toluene (volume ratio is 2:1) to obtain 833.0 mg solid intermediate 2, and the yield is 78.5%. The structural characterization data are as follows:
1 H NMR (400 MHz, THF-d 8 ) δ 11.71-11.68 (bs, 2H), 8.54-8.52 (d, 2H), 8.21-8.19 (d, 2H), 8.05-8.03 (s, 2H), 7.99-7.97 (d, 2H), 7.65-7.61 (m, 6H), 7.58-7.56 (d,2H), 7.53-7.52 (m, 2H), 7.48-7.46 (m, 2H). 13 C NMR (101 MHz, THF-d 8 ) δ135.5, 131.9, 130.4, 129.9, 128.4, 128.2,127.6, 127.3, 127.1, 125.3, 120.5, 120.2, 117.8, 111.1 ppm. HR-MS (ESI) m/z calcd. For (C 40 H 22 N 2 ): 530.6272. Found: 530.6269.
s3, preparing an intermediate 3:
dissolving the intermediate 2 in DMF and THF, slowly adding NaH under the protection of nitrogen, stirring uniformly, adding methyl iodide, stirring at room temperature for reaction, and performing aftertreatment after the reaction is finished to obtain an intermediate 3;
the specific process is as follows:
single at 100mLIntermediate 2 (530.6 g,530.6 g/mol,1 mmol) was dissolved in ultra-dry N, N-Dimethylformamide (DMF) and ultra-dry THF (volume ratio 1:1, total 20 mL), naH (120 mg,24 g/mol,5mmol, CAS NO.: 7646-69-7) was slowly added, stirred under nitrogen for 10 min, methyl iodide (426 mg,141.9 g/mol,3mmol, CAS NO.: 200-819-5) was added, stirred at room temperature for 2 h, after completion of the reaction was poured into 200 mL ice water, extracted three times with Dichloromethane (DCM) in 50mL portions, and the organic phase was combined with anhydrous sodium sulfate (Na) 2 SO 4 ) After drying, filtering, rotary evaporation and concentration are carried out to obtain a crude product, a silica gel column is adopted for separation, toluene and petroleum ether (volume ratio is 1:5) are eluted, and 547.5 mg solid intermediate 3 can be obtained, and the yield is 98.0%. The structural characterization data are as follows:
1 H NMR (400 MHz, THF-d 8 ) δ 8.54-8.53 (d, 2H), 8.21-8.19 (d, 2H), 8.05-8.04 (s, 2H), 8.00-7.98 (m, 2H), 7.83-7.82 (d, 2H), 7.69-7.68 (d, 2H), 7.62-7.60 (m, 4H),7.53-7.52 (m, 2H), 7.48-7.46 (m, 2H), 3.82-3.81 (s, 6H). 13 C NMR (101 MHz, THF-d 8 ) δ135.5, 131.9, 130.8, 130.6, 128.4, 128.1, 127.6, 127.3, 127.2, 127.1, 125.3, 120.5,120.2, 117.8, 111.1, 37.2 ppm. HR-MS (ESI) m/z calcd. For (C 42 H 26 N 2 ): 558.6808. Found: 558.6805.
s3, preparing an intermediate 4:
dissolving the intermediate 3 in dichloromethane, then adding NBS, slowly heating to reflux for reaction, and after the reaction is finished, obtaining an intermediate 4 through post-treatment;
the specific process is as follows:
500 A mL single neck round bottom flask was charged with intermediate 3 (558.7 mg,558.7 g/mol,1 mmol), added 130 mL Dichloromethane (DCM) to dissolve it completely, then NBS (672.8 mg,178.0 g/mol,2.1mmol, CAS No.: 128-08-5) was added, then slowly warmed to reflux and stirred for 8 h, cooled to room temperature and then sodium thiosulfate (Na) 2 S 2 O 3 ) The reaction was quenched with aqueous solution (0.1 mol/L,150 mL), extracted three times with Dichloromethane (DCM),the DCM amount was 50mL each time, and the organic phase was quenched with anhydrous sodium sulfate (Na 2 SO 4 ) After drying, filtration and spin evaporation concentration gave a crude product, which was separated by a silica gel column, and eluted with toluene and petroleum ether (volume ratio 1:6) to give 668.5 mg as solid intermediate 4 in 93.3% yield. The structural characterization data are as follows:
1 H NMR (400 MHz, THF-d 8 ) δ 8.97-8.95 (d, 2H), 8.73-8.72 (s, 2H), 8.20-8.19 (d, 2H), 8.05-8.04 (s, 2H), 7.84-7.83 (d, 2H), 7.62-7.61 (d, 2H), 7.59-7.57 (m, 2H),7.48-7.46 (m, 4H), 3.82-3.81 (s, 6H). 13 C NMR (101 MHz, THF-d 8 ) δ131.9, 130.7, 130.4, 128.4, 128.3, 128.1,127.6, 127.1, 126.3, 125.3, 121.2, 120.2, 119.7, 114.7, 112.1, 37.2 ppm. HR-MS (ESI) m/z calcd. For (C 42 H 24 Br 2 N 2 ): 716.4730. Found: 716.4735.
s4, preparation of an intermediate 5:
intermediate 4, 1-chloro-2-aminonaphthalene and Pd (OAc) 2 、DPEPhOS、NaO(tBu) is added into a reactor, toluene is added as a solvent, and under the protection of nitrogen, heating reflux reaction is carried out, and after the reaction is finished, an intermediate 5 is obtained through post treatment;
the specific process is as follows:
intermediate 4 (716.5 mg,716.48 g/mol,1 mmol) and 1-chloro-2-aminonaphthalene (373 mg,177.6 g/mol,2.1mmol, CAS No.: 16452-11-2), pd (OAc) 2 （22.5 mg，224.5g/mol，10.0% mmol，CAS NO.：3375-31-3），DPEPhOS（53.9 mg，538.6 g/mol，0.1 mmol，CASNO.：166330-10-5），NaO(tBu) (480 mg,96.0 g/mol,5mmol, CAS No.: 865-48-5) was added to a 500mL single neck round bottom flask, 200 mL toluene was added as solvent, heated under nitrogen at 120℃under reflux 24h, cooled to room temperature after completion of the reaction, catalyst and base were removed by filtration through celite layer, and the filtrate concentrated and recrystallized from Tetrahydrofuran (THF) to give 743.4g of solid intermediate 5 in 81.7% yield. The structural characterization data are as follows:
1 H NMR (400 MHz, THF-d 8 ) δ 10.48-10.45 (bs, 2H), 8.97-8.95 (d, 2H), 8.20-8.19 (d, 2H), 8.12-8.10 (m, 4H), 8.05-8.04 (s, 2H), 7.84-7.83 (d, 2H), 7.66-7.65 (d,2H), 7.62-7.59 (m, 8H), 7.50-7.47 (m, 4H), 7.32-7.30 (m, 4H), 3.82-3.81 (s, 6H). 13 C NMR (101 MHz, THF-d 8 ) δ 142.8, 133.6, 131.9, 130.9, 130.5, 128.4, 128.3, 128.1, 127.7, 127.6, 127.2, 127.1, 126.9, 126.3, 126.2, 126.0, 125.3, 124.6, 121.2,120.2, 116.7, 111.5, 111.3, 94.4, 37.2 ppm. HR-MS (ESI) m/z calcd. For (C 62 H 38 Cl 2 N 4 ): 909.9150. Found: 909.9155.
s5, preparing an intermediate 6:
intermediate 5, pd (OAc) 2 、K 2 CO 3 、P(t-Bu) 3 ·HBF 4 Adding DMAc and the mixture into a reactor, heating and stirring under the protection of nitrogen to react, and after the reaction is finished, obtaining an intermediate 6 through post-treatment;
the specific process is as follows:
intermediate 5 (909.9 mg,909.9 g/mol,1 mmol), pd (OAc) 2 (45 mg,224.5 g/mol,0.2mmol, CAS No.: 3375-31-3), potassium carbonate (K) 2 CO 3 ）（1.38 g，138.0 g/mol，10mmol）、P(t-Bu) 3 ·HBF 4 (58.0 mg,290.0 g/mol,0.2mmol, CAS No.: 131274-22-1) and 50mL ultra-dry N, N-dimethylacetamide (DMAc) were added to a 100mL single-neck round bottom flask, the reaction was stirred under nitrogen with heating at 130℃to 24h, cooled to room temperature after completion of the reaction, the reaction solution was poured into 100mL saturated saline, three times with Dichloromethane (DCM), the DCM was extracted 500mL each time, the organic phase was dried over anhydrous sodium sulfate, filtered and concentrated by rotary evaporation to give the crude product, which was purified by separation with a 200 mesh neutral alumina column with eluent THF and toluene (volume ratio 2:1) to give 640.3mg of solid intermediate 6 in 76.5% yield. The structural characterization data are as follows:
1 H NMR (400 MHz, THF-d 8 ) δ 10.48-10.45 (bs, 2H), 8.96-8.94 (d, 2H), 8.19-8.17 (d, 2H), 8.12-8.10 (m, 4H), 8.05-8.04 (s, 2H), 7.84-7.83 (d, 2H), 7.66-7.65 (d,2H), 7.62-7.59 (m, 6H), 7.50-7.47 (m, 4H), 7.32-7.30 (m, 4H), 3.82-3.81 (s, 6H). 13 C NMR (101 MHz, THF-d 8 ) δ 143.2, 134.5, 131.8, 131.2, 130.8, 128.5, 128.4, 128.2, 127.9, 127.8, 127.3, 127.1, 126.9, 126.5, 126.2, 126.0, 125.5, 124.8, 121.3,120.2, 116.7, 112.5, 111.8, 94.5, 37.2 ppm. HR-MS (ESI) m/z calcd. For (C 62 H 36 N 4 ): 836.9932. Found: 836.9929.
s6, preparing perylene-based fused ring compounds:
dissolving the intermediate 6 in DMF and THF, slowly adding NaH under the protection of nitrogen, stirring uniformly, adding a halogenated reagent RX, stirring at room temperature for reaction, and performing aftertreatment after the reaction is finished to obtain the perylene-based fused ring compound;
x in the halogenated reagent RX is I or Br, and R in RX is any one of C1-C12 hydrocarbon group or ethylene glycol monomethyl ether chain.
Specifically, the R is selected from any one of the following structures:
。
more specifically, the halogenating agent RX is any one of iodohexane, 2-ethyliododecane, 1-bromo-2- (2-methoxyethoxy) ethane and 1-bromo-2- (2- (2-methoxyethoxy) ethoxy) ethane.
Example 1
Synthesis of Compound I-1:
in a 100mL single neck round bottom flask, intermediate 6 (837 mg,837.0 g/mol,1 mmol) was dissolved in 50mL (volume ratio 1:1) of ultra dry N, N-dimethylformamide and ultra dry Tetrahydrofuran (THF), naH (72 mg,24 g/mol,3 mmol) was slowly added, stirred under nitrogen for 10 min, methyl iodide (298.0 mg,141.9 g/mol,2.1mmol, CAS NO.: 200-819-5) was added, stirred at room temperature for 2 h, after completion of the reaction was poured into 300 mL ice water, extracted three times with Dichloromethane (DCM), the DCM was used in an amount of 50mL each time, the combined organic phases were dried over anhydrous sodium sulfate, filtered, concentrated by rotary evaporation to give the crude product, which was separated with a silica gel column with toluene and petroleum ether (volume ratio 1:6) to give 821.8mg of solid compound I-1 in 95% yield. The structural characterization data are as follows:
1 H NMR (400 MHz, THF-d 8 ) δ 8.95-8.93 (d, 2H), 8.18-8.16 (d, 2H), 8.12-8.10 (m, 4H), 8.05-8.04 (s, 2H), 7.83-7.82 (d, 2H), 7.66-7.65 (d, 2H), 7.63-7.59 (m, 6H),7.51-7.47 (m, 4H), 7.33-7.30 (m, 4H), 3.82-3.81 (s, 6H), 3.79-3.78 (s, 6H). 13 C NMR (101 MHz, THF-d 8 ) δ 143.1, 134.4, 131.7, 131.2, 130.7, 128.6, 128.3, 128.2, 127.9, 127.7, 127.3,127.1, 126.8, 126.5, 126.2, 126.0, 125.6, 124.8, 121.3, 120.2, 116.7, 112.6, 111.8, 94.5, 37.2, 36.9 ppm. HR-MS (ESI) m/z calcd. For (C 64 H 40 N 4 ): 865.0468. Found: 865.0464.
example 2
Synthesis of Compound I-2:
in a 100mL single neck round bottom flask, intermediate 6 (837 mg,837.0 g/mol,1 mmol) was dissolved in 50mL (volume ratio 1:1) of ultra dry N, N-Dimethylformamide (DMF) and ultra dry Tetrahydrofuran (THF), naH (72 mg,24 g/mol,3 mmol) was slowly added, stirred under nitrogen for 10 min, iodohexane (414 mg,212.1 g/mol,2mmol, CAS NO.: 638-45-9) was added, stirred at room temperature for 2 h, after completion of the reaction solution was poured into 300 mL ice water, extracted three times with Dichloromethane (DCM), the DCM was used in an amount of 50mL each time, the combined organic phases were dried over anhydrous sodium sulfate, filtered, concentrated by spin evaporation to give the crude product, which was separated with a column of toluene and petroleum ether (volume ratio 1:8) to give 924.9mg of solid compound I-2 in 92% yield. The structural characterization data are as follows:
1 H NMR (400 MHz, THF-d 8 ) δ 8.97-8.95 (d, 2H), 8.20-8.19 (d, 2H), 8.12-8.10 (m, 4H), 8.05-8.04 (s, 2H), 7.84-7.83 (d, 2H), 7.66-7.65 (d, 2H), 7.62-7.59 (m, 6H),7.50-7.47 (m, 4H), 7.32-7.30 (m, 4H), 4.16-4.17 (t, 4H), 3.82-3.81 (s, 6H), 1.76-1.74 (m, 4H), 1.27-1.29 (m, 12H), 0.86-0.88 (t, 6H). 13 C NMR (101 MHz, THF-d 8 ) δ 142.8, 133.6, 131.9, 130.9, 130.5, 128.4, 128.3, 128.1, 127.7, 127.6, 127.2,127.1, 126.9, 126.3, 126.2, 126.0, 125.3, 124.6, 121.2, 120.2, 116.7, 111.5, 111.3, 94.4, 37.2, 31.5, 29.5, 27.1, 22.7, 14.2 ppm. HR-MS (ESI) m/z calcd. For(C 74 H 60 N 4 ): 1009.3148. Found: 1009.3145.
example 3
Synthesis of Compound I-3:
intermediate 6 (837 mg,837.0 g/mol,1 mmol) was dissolved in ultra-dry in a 100mL single neck round bottom flaskN,NDimethylformamide (DMF) and ultra-dry Tetrahydrofuran (THF) 50mL (volume ratio 1:1), naH (72 mg,24 g/mol,3 mmol) were slowly added, stirred under nitrogen for 10 min, 2-ethyliododecane (592.4 mg,296.2 g/mol,2mmol, CAS No.: 1044598-79-9) was added, stirred at room temperature for 2 h, after completion of the reaction solution was poured into 300 mL ice water, extracted three times with Dichloromethane (DCM), the DCM amount was 50mL each time, the combined organic phases were dried over anhydrous sodium sulfate, filtered, concentrated by rotary evaporation to give the crude product, which was separated using a silica gel column with eluent toluene and petroleum ether (volume ratio 1:6), to give 1073.9mg of solid compound I-3 in 91.5% yield. The structural characterization data are as follows:
1 H NMR (500 MHz, THF-d 8 ) δ 8.97-8.95 (d, 2H), 8.20-8.19 (d, 2H), 8.12-8.10 (m, 4H), 8.05-8.04 (s, 2H), 7.84-7.83 (d, 2H), 7.66-7.65 (d, 2H), 7.62-7.59 (m, 6H),7.50-7.47 (m, 4H), 7.32-7.30 (m, 4H), 3.90-3.92 (m, 2H), 3.82-3.81 (s, 6H), 3.65-3.66 (m, 2H), 1.55-1.57 (m, 4H), 1.25-1.29 (m, 26H), 1.19-1.20 (m, 4H),0.98-0.99 (t, 6H), 0.86-0.88 (t, 6H). 13 C NMR (101 MHz, THF-d 8 ) δ 142.8, 133.6, 131.9, 130.9, 130.5, 128.4,128.3, 128.1, 127.7, 127.6, 127.2, 127.1, 126.9, 126.3, 126.2, 126.0, 125.3, 124.6, 121.2, 120.2, 116.7, 111.5, 111.3, 94.4, 37.2 31.5, 29.5, 27.1, 22.7,14.2 ppm. 13 C NMR (126 MHz, THF-d 8 ) δ142.8, 133.6, 131.9, 130.9, 130.5, 128.4, 128.3, 128.1, 127.7, 127.6, 127.2, 127.1, 126.9, 126.3, 126.2, 126.0, 125.3, 124.6, 121.2,120.2, 116.7, 111.5, 111.3, 94.4, 37.2, 36.6, 32.5, 29.9, 29.6, 29.3, 27.1, 26.3, 22.7, 14.2 11.6 ppm. HR-MS (ESI) m/z calcd. For (C 86 H 84 N 4 ): 1173.6364. Found: 1173.6360.
example 4
Synthesis of Compound I-4:
intermediate 6 (837 mg,837.0 g/mol,1 mmol) was dissolved in ultra-dry in a 100mL single neck round bottom flaskN,NDimethylformamide (DMF) and ultra-dry THF 50mL (volume ratio 1:1), naH (72 mg,24 g/mol,3 mmol) were slowly added, stirred under nitrogen for 10 min, 1-bromo-2- (2-methoxyethoxy) ethane (366.2 mg,183.1 g/mol,2mmol, CAS NO.: 5414-19-7) was added, stirred at room temperature for 2 h, after completion of the reaction solution was poured into 300 mL ice water, extracted three times with Dichloromethane (DCM), the DCM extraction amount each time was 50mL, the organic phases were dried over anhydrous sodium sulfate, filtered, concentrated by rotary evaporation to give the crude product, which was separated using a silica gel column with toluene and petroleum ether (volume ratio 1:5) to give 942.3mg of solid compound I-4 in 90.5% yield. The structural characterization data are as follows:
1 H NMR (500 MHz, THF-d 8 ) δ 8.97-8.95 (d, 2H), 8.20-8.19 (d, 2H), 8.12-8.10 (m, 4H), 8.05-8.04 (s, 2H), 7.84-7.83 (d, 2H), 7.66-7.65 (d, 2H), 7.62-7.59 (m, 6H),7.50-7.47 (m, 4H), 7.32-7.30 (m, 4H), 4.46-4.44 (t, 4H), 3.86-3.88 (s, 6H), 3.65-3.64 (t, 4H), 3.55-3.52 (m, 8H), 3.41-3.40 (s, 6H). 13 C NMR (126 MHz, THF-d 8 ) δ145.9, 144.8, 136.4, 135.6, 132.1, 130.1, 129.8, 129.6, 128.8, 127.6, 127.3, 127.2,126.8, 126.6, 126.3, 125.7, 125.1, 123.2, 122.5, 120.5, 119.8, 117.9, 111.2, 71.6, 71.2, 69.8, 59.3, 57.4, 29.9 ppm. HR-MS (ESI) m/z calcd. For (C 72 H 56 N 4 O 4 ): 1041.2572. Found: 1041.2569.
example 5
Synthesis of Compound I-5:
intermediate 6 (837 mg,837.0 g/mol,1 mmol) in an ultra-dry stateN,NDimethylformamide (DMF) and ultra-dry Tetrahydrofuran (THF) 50mL (volume ratio 1:1), naH (72 mg,24 g/mol,3 mmol) were slowly added, stirred under nitrogen for 10 min, 1-bromo-2- (2- (2-methoxyethoxy) ethoxy) ethane (454.2 mg,227.1 g/mol,2mmol, CASNO.: 5414-19-7) were added, stirred at room temperature for 2 h, after completion of the reaction was poured into 300 mL ice water, extracted three times with Dichloromethane (DCM), the DCM was extracted 50mL each time, the combined organic phases were dried over anhydrous sodium sulfate, filtered, concentrated by rotary evaporation to give the crude product, which was separated using a silica gel column with toluene and petroleum ether (1:5) as eluent to give 1018.7 mg solid compound I-5 in 90.2% yield. The structural characterization data are as follows:
1 H NMR (500 MHz, THF-d 8 ) δ 8.97-8.95 (d, 2H), 8.20-8.19 (d, 2H), 8.12-8.10 (m, 4H), 8.05-8.04 (s, 2H), 7.84-7.83 (d, 2H), 7.66-7.65 (d, 2H), 7.62-7.59 (m, 6H),7.50-7.47 (m, 4H), 7.32-7.30 (m, 4H), 4.46-4.44 (t, 4H), 3.86-3.88 (s, 6H), 3.65-3.64 (t, 4H), 3.55-3.52 (m, 16H), 3.41-3.40 (s, 6H). 13 C NMR (126 MHz, THF-d 8 ) δ145.9, 144.8, 136.4, 135.6, 132.1, 130.1, 129.8, 129.6, 128.8, 127.6, 127.3, 127.2,126.8, 126.6, 126.3, 125.7, 125.1, 123.2, 122.5, 120.5, 119.8, 117.9, 111.2, 71.6, 71.2, 70.4, 70.1, 59.3, 57.4, 14.2 ppm. HR-MS (ESI) m/z calcd. For (C 76 H 64 N 4 O 6 ): 1129.3624. Found: 1129.3620.
2. perovskite solar cell application example:
as shown in fig. 1, the perovskite solar cell includes a substrate, a transparent oxide electrode, an electron transport layer, a photoactive layer, a hole transport layer, and a metal electrode. The perylene-based fused ring compound is applied to a hole transport layer. The electron transport layer includes titanium dioxide. Included in the photoactive layer is a perovskite.
The substrate and transparent oxide electrode (i.e., FTO glass) were cleaned with detergent, deionized water, acetone, and isopropyl alcohol in sequence in an ultrasonic meter for 10 minutes each. Will be 0.6 mL bis (B)Diisopropyl acylacetone titanate (CAS No.: 17927-72-9) and 0.4 mL acetylacetone (CAS No.: 123-54-6) were dissolved in 9 mL absolute ethanol to prepare a precursor solution, and the prepared precursor solution was deposited on a substrate and a transparent oxide electrode by spray pyrolysis with oxygen as a carrier gas at 450 ℃ to form a dense layer 30 nm thick. Commercially available TiO 2 The paste (30 NR-D) and absolute ethanol were diluted 1:6 by mass and then at 2000 rpm s -1 Spin-coating 10 s at a rotational speed to mesoporous TiO 2 Deposited on a substrate and a transparent oxide electrode (FTO glass) to form mesoporous TiO 100 nm thick 2 The layer was dried at 80℃for 10 min and then the TiO was dried 2 The film was thermally annealed at 450 c under dry air flow for 30 min, and then subjected to uv-ozone treatment for 30 min to obtain an electron transport layer. 1.30M PbI was dissolved in a mixed solution of DMSO/DMF (volume ratio 1:4) 2 (lead iodide CAS No.: 10101-63-0), 1.19M FAI (iodoformamidine, CASNO.: 879643-71-7), 0.14M PbBr 2 (lead bromide CAS No.: 10031-22-8) and 0.14M MABr (bromoformamidine, CAS No.: 46958-06-7) and 0.07M CsI (cesium iodide, CASNO.: 7789-17-5) (FAPbI) 3 )0.875 (MAPbBr 3 )0.075 (CsPbI 3 )0.05 (PbI 2 ) 0.03 perovskite precursor solution, and then the preparation of the photoactive layer (also referred to as perovskite layer) was carried out in a glove box with a dry air flow having a relative humidity of less than 2%, in two consecutive steps at 200 rpm s -1 Spin-coating at a rotational speed of 10 s and at 2000 rpm s -1 Is spun at 30 s, and a perovskite precursor solution is deposited on the electron transport layer. Before the end of the procedure, before 15 a s, 150 μl of chlorobenzene was dropped on the rotating photoactive layer, which was then thermally annealed at 120deg.C for 1 h to complete the photoactive layer preparation.
The preparation of the hole-transport layer was also carried out in a glove box with a dry air flow having a relative humidity of less than 2%, and the perylene-based fused ring compound synthesized in the above example was used as a hole-transport layer material, respectively, to which 0.5 equivalent of HTFSI (bis (trifluoromethylsulfonyl) amide, CAS No.: 82113-65-3) and 0.5 equivalent were dopedtBP (tert-butylpyridine, CAS No.: 3978-81-2) and compounding30 mM chlorobenzene solution is prepared and then at 4000 rpm s -1 And (3) spin-coating the film at the rotating speed of 20 and s, depositing the film on the annealed film of the photoactive layer, and finally vacuum evaporating a layer of 120 nm-thick gold as a metal electrode to finish the manufacture of the perovskite solar cell device prepared by taking the perylene-based fused ring compound as a hole transport layer, wherein the structure of the perovskite solar cell is shown in figure 1.
In this example, hole transport layers were prepared from 5 perylene-based fused ring compounds I-1, I-2, I-3, I-4 and I-5 synthesized in examples 1 to 5, respectively, to prepare 5 types of PSC devices, and the results of testing the photovoltaic properties were as follows, in comparison with PSC devices using Spiro-OMeTAD as the hole transport layer:
TABLE 1 photovoltaic performance parameters of PSC devices with different perylene-based fused ring compounds as hole transport layers
Note that: the electron transport layer is made of titanium dioxide, and the photoactive layer is perovskite (FAPbI 3 )0.875 (MAPbBr 3 )0.075 (CsPbI 3 )0.05 (PbI 2 )0.03。
Device test data show that the perylene-based fused ring compound can be used as a hole transport material of PSC devices, and PCE of the devices taking the perylene-based fused ring compound as a hole transport layer is higher than PCE of the devices taking Spiro-OMeTAD as the hole transport layer. Moreover, the PCE of the device can be enhanced by adjusting the side chain structure.
In summary, the invention provides a hole transport material based on perylene-based fused ring compounds, which has the following advantages: (1) The raw materials are cheap, the synthetic route is simple, the preparation is easy, and the commercial application value is high; (2) Because the polymer has a non-planar large pi-conjugated framework, the accumulation among molecules is easy to generate more intermolecular contact, and the combination of a proper side chain is favorable for regulating the accumulation structure of the molecules and facilitating hole transmission; (3) Good solubility and film forming property, and high PCE applied to PSC devices.
The technical features of the above-described embodiments may be arbitrarily combined, and in order to simplify the description, all possible combinations of the technical features in the above-described embodiments are not exhaustive, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims.

Claims (6)

1. The perylene-based fused ring compound is characterized in that the perylene-based fused ring compound is shown as a formula I:
；
wherein R is any one of C1-C12 alkyl or ethylene glycol monomethyl ether chain.
2. The perylene-based fused ring compound according to claim 1, wherein said hydrocarbon group is any one of a linear hydrocarbon group or a branched hydrocarbon group.
3. The perylene-based fused ring compound according to claim 1, wherein said perylene-based fused ring compound is selected from the group consisting of the following structures:
。
4. a process for the preparation of a perylene-based fused ring compound as defined in any one of claims 1 to 3, wherein said process comprises:
；
s1, preparation of an intermediate 1:
3, 9-dibromoperylene and 1-chloro-2-aminonaphthalene, pd (OAc) 2 Adding DPEPhOS and NaO (t-Bu) into a reactor, adding toluene as a solvent, heating and refluxing under the protection of nitrogen, and performing aftertreatment after the reaction is finished to obtain an intermediate 1;
s2, preparing an intermediate 2:
intermediate 1, pd (OAc) 2 、K 2 CO 3 、P(t-Bu) 3 ·HBF 4 Adding DMAc and the mixture into a reactor, heating and stirring under the protection of nitrogen to react, and after the reaction is finished, obtaining an intermediate 2 through post-treatment;
s3, preparing an intermediate 3:
dissolving the intermediate 2 in DMF and THF, slowly adding NaH under the protection of nitrogen, stirring uniformly, adding methyl iodide, stirring at room temperature for reaction, and performing aftertreatment after the reaction is finished to obtain an intermediate 3;
s3, preparing an intermediate 4:
dissolving the intermediate 3 in dichloromethane, then adding NBS, slowly heating to reflux for reaction, and after the reaction is finished, obtaining an intermediate 4 through post-treatment;
s4, preparation of an intermediate 5:
intermediate 4, 1-chloro-2-aminonaphthalene and Pd (OAc) 2 Adding DPEPhOS and NaO (t-Bu) into a reactor, adding toluene as a solvent, heating and refluxing under the protection of nitrogen, and performing aftertreatment after the reaction is finished to obtain an intermediate 5;
s5, preparing an intermediate 6:
intermediate 5, pd (OAc) 2 、K 2 CO 3 、P(t-Bu) 3 ·HBF 4 Adding DMAc and the mixture into a reactor, heating and stirring under the protection of nitrogen to react, and after the reaction is finished, obtaining an intermediate 6 through post-treatment;
s6, preparing perylene-based fused ring compounds:
dissolving the intermediate 6 in DMF and THF, slowly adding NaH under the protection of nitrogen, stirring uniformly, adding a halogenated reagent RX, stirring at room temperature for reaction, and performing aftertreatment after the reaction is finished to obtain the perylene-based fused ring compound;
x in the halogenated reagent RX is I or Br, and R in RX is any one of C1-C12 hydrocarbon group or ethylene glycol monomethyl ether chain.
5. The method for preparing a perylene-based fused ring compound as defined in claim 4, wherein said halogenated reagent RX is any one of iodohexane, 2-ethyliododecane, 1-bromo-2- (2-methoxyethoxy) ethane, and 1-bromo-2- (2- (2-methoxyethoxy) ethoxy) ethane.
6. Use of a perylene-based fused ring compound as defined in any one of claims 1 to 3, wherein said perylene-based fused ring compound is applied to a hole transport layer of a perovskite solar cell;
the perovskite solar cell consists of a substrate, a transparent oxide electrode, an electron transport layer, a photoactive layer, a hole transport layer and a metal electrode;
the electron transport layer is made of titanium dioxide, and the photoactive layer is perovskite.
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