CN112778354A - Silicon-containing thick pentacyclic hole transport material and preparation method and application thereof - Google Patents
Silicon-containing thick pentacyclic hole transport material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 25
- 230000005525 hole transport Effects 0.000 title claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 19
- 239000010703 silicon Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 89
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000011799 hole material Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000011049 filling Methods 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 244000108484 Cyperus difformis Species 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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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
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Abstract
The invention relates to the technical field of organic hole materials, and discloses a silicon-containing fused pentacyclic hole transport material, a preparation method and application thereof
The planarized molecular configuration of the hole molecules helps to promote pi-pi stacking between hole materials, enhancing hole mobility and conductivity. Meanwhile, the structural characteristics of the multi-long alkyl chain endow the hole transport material with excellent solvent film-forming property. The silicon-containing thick five-ring hole transport material is applied to perovskite solar cells, and the short-circuit light current density of the device is highThe open-circuit voltage and the fill factor are respectively 22.55mA cm‑2The open circuit voltage is 1.092V, the filling factor is 0.7685, the photoelectric conversion efficiency of 18.92 percent is obtained at most, and the method shows great commercial application value.
Description
Technical Field
The invention relates to the technical field of organic hole materials, in particular to a silicon-containing thick pentacyclic hole transport material and a preparation method and application thereof.
Background
As a new generation of photovoltaic technology, Perovskite Solar Cells (PSCs for short) have the advantages of simple preparation process, easily adjustable materials, low cost, and the like, and the latest certification efficiency has reached 25.2% (National Renewable Energy Laboratory, NREL, 2019). The hole transport layer is used as an important component of PSCs, plays a role in collecting photogenerated holes of the perovskite absorption layer and transporting the photogenerated holes to the counter electrode, effectively inhibits the recombination of device interface electrons, and plays a crucial role in influencing the efficiency and stability of the battery. Currently, the most widely used and highly efficient hole transport material in perovskite solar cells is 2,2 ', 7,7 ' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9 ' -spirobifluorene (Spiro-OMeTAD). However, the synthetic preparation cost of the Spiro-OMeTAD molecule is high, and the perovskite solar cell prepared from the Spiro-OMeTAD molecule has poor stability, so that the wide range of commercial applications of the Spiro-OMeTAD molecule is limited. Therefore, based on molecular engineering, it is important to develop a novel hole transport material that is efficient, stable, and inexpensive and can replace Spiro-OMeTAD.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a silicon-containing fused pentacyclic hole transport material, and a preparation method and application thereof. The structural characteristics of multiple long alkyl chains endow the hole transport material with excellent performanceSolvent film forming property. The hole transport material containing silicon thick five rings is applied to the perovskite solar cell, and the short-circuit photocurrent density, the open-circuit voltage and the filling factor of the device are respectively 22.55mA cm-2The open circuit voltage is 1..092V, the filling factor is 0.7685, and finally the photoelectric conversion efficiency of 18.92% is obtained, thereby showing great commercial application value.
The invention is realized by the following technical scheme:
a silicon-containing fused pentacyclic hole transport material having the chemical structure of formula (6):
the invention further improves the scheme as follows:
a process for the preparation of the compound of formula (6) above, comprising the steps of:
s1: subjecting the compound of formula (1) and the compound of formula (2) to a cyclization coupling reaction to produce a compound of formula (3);
s2: brominating a compound of formula (3) to produce a compound of formula (4);
s3: subjecting the compound of formula (4) and the compound of formula (5) to Still coupling reaction to produce the compound of formula (6);
preferably, in the S1, the compound of formula (1) reacts with the compound of formula (2) in solvent anhydrous tetrahydrofuran under the action of n-butyl lithium to generate the compound of formula (3), wherein the dosage of each substance is calculated by the amount of substance, the compound of formula (1): a compound of formula (2): n-butyl lithium ═ 1: 1-1.5: 2-4: the reaction time is 8-12 h.
Preferably, in said S2, the compound of formula (3) is subjected to bromination reaction with N-bromosuccinimide (NBS) in Tetrahydrofuran (THF) as a solvent to produce a compound of formula (4), wherein the amounts of each substance are calculated by the amount of substance, the compound of formula (3): NBS ═ 1: 2-3; the reaction time is 0.1-2 h.
Preferably, in the S3, the compound of formula (4) is subjected to a Still coupling reaction with the compound of formula (5) in a solvent of toluene under the action of a catalyst of tetrakis (triphenylphosphine) palladium to generate the compound of formula (6), wherein the amount of each substance is calculated by the amount of substance, the compound of formula (4): a compound of formula (5): tetrakis (triphenylphosphine) palladium ═ 1: 2-3: 0.02-0.1, and the reaction time is 6-12 h.
The invention further provides application of the silicon-containing thick five-ring hole transport material in a perovskite solar cell.
Compared with the prior art, the invention has the beneficial effects that:
1. the organic hole material provided by the invention takes silicon-containing thick five rings as a molecular core, and the highly conjugated and planar spatial configuration of the organic hole material is favorable for promoting the pi-pi stacking effect among molecules and enhancing the hole mobility and the conductivity of the material.
2. The central silicon atom of the molecular nucleus has high modification, can introduce substituent groups with different electronic and space characteristics, and regulates and controls the energy level matching, the dissolving and film-forming property and the interaction among molecules of the hole material. Meanwhile, the structural characteristics of polysulfide atoms can enhance the interface action of a hole transport layer and a perovskite layer, passivate the defect state of the perovskite layer and improve the separation and transmission efficiency of holes.
3. The test result of the application of the organic hole material in the perovskite solar cell shows that: open circuit voltage (V)oc) 1.092V, short-circuit photocurrent density (J)sc) Is 22.55mAcm-2The Fill Factor (FF) was 0.7685, and the photoelectric conversion efficiency was 18.92%. (see fig. 2 and 3), has practical significance for improving the efficiency of perovskite solar cells.
Drawings
FIG. 1 shows a solution of a silicon-containing thick pentacyclic hole transport material prepared in example 1 dissolved in dichloromethane (the concentration of the material is 1X 10)-5mol/L) ultraviolet-visible absorption spectrum;
FIG. 2 is a schematic structural view of a perovskite solar cell fabricated in example 4; wherein the number 1 represents a conductive glass, the number 2 represents a platinum layer, the number 3 represents a titanium dioxide film, the number 4 represents an electrolyte, and the number 5 represents a photosensitizing dye;
FIG. 3 is an I-V curve of the perovskite solar cell prepared in example 4.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
Example 1
The embodiment provides a silicon-containing thick pentacyclic hole transport material, which has a chemical formula shown in formula (6):
the preparation method of the organic hole material (the compound of formula (6)) is as follows:
the compound of formula (1) used in this example is prepared according to the literature Wang Z, Miu L, Yao H, et al, organic sensors caring 9H-thoeno [2 ', 3':4,5] thoeno [3,2-b ] thoeno [2 ', 3':4,5] thoeno [2,3-d ] phenol core for high performance force-sensitive cells, dyes Pigments 2019; 162:126-35, and preparing; the compound of formula (5) is synthesized according to the document D.F.Houston.J.Am.chem.Soc.,1949,7, 395-396; compounds of formula (5) are prepared according to the documents d.dora, j.victorien, l.philippie, b.philippie, o.yoann, c.jerome, p.ricchardo, r.jean.advanced Functional Materials,2013,23, 4854-4861; other reagents are commercially available.
S1: subjecting the compound of formula (1) and the compound of formula (2) to a cyclization coupling reaction to produce a compound of formula (3);
the method specifically comprises the following steps: under the protection of argon and at the low temperature of-78 ℃, adding 981mg of the compound of the formula (1) dissolved by 30mL of anhydrous tetrahydrofuran into a 100mL eggplant-shaped reaction bottle, reacting at the low temperature for 5 minutes, slowly adding 1.56mL (2.4mol/L) of n-butyllithium, reacting at the low temperature for 1 hour, adding 635mg of the compound of the formula (2), closing refrigeration, and slowly returning to the room temperature; and reacting for 8 hours. Water and ethyl acetate were added for extraction, the organic phase was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to give 726mg of the compound of the formula (3). It is a yellow-green viscous liquid with a yield of 64%.
The structural characterization data for the compound of formula (3) is:1HNMR(400MHz,CDCl3):δ6.91(s,2H),2.71(t,J＝7.6Hz,4H),1.53-1.47(m,4H),1.40-1.20(m,32H),1.03-0.99(m,4H),0.91-0.83(m,12H).13C NMR(100MHz,CDCl3):δ150.7,141.9,140.9,135.4,132.5,120.6,33.3,31.9,31.7,30.2,29.1,28.7,24.3,22.7,22.6,14.1,11.5.HRMS(ESI)calcd for C40H63S4Si(M+H+):699.3582,found:699.3589.
s2: brominating a compound of formula (3) to produce a compound of formula (4);
the method specifically comprises the following steps: adding 500mg of the compound of the formula (3) and 20mL of tetrahydrofuran into a 100mL single-neck round-bottom flask, then adding 268mg of N-bromosuccinimide into the system in batches, and reacting for 15min at 25 ℃ in a dark place; adding water for quenching, extracting by ethyl acetate, drying by anhydrous magnesium sulfate, and removing the solvent by reduced pressure distillation; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane 50/1-15/1) to yield 460mg of the compound of formula (4) as an off-white solid in 75% yield. The structural characterization data for the compound of formula (4) is:1HNMR(400MHz,CDCl3):δ2.71(t,J＝7.6Hz,4H),1.73-1.67(m,4H),1.54-1.21(m,36H),1.0-0.91(m,4H),0.91-0.84(m,12H).13CNMR(100MHz,CDCl3):δ149.5,140.3,139.2,134.6,134.4,108.6,33.2,31.9,31.8,31.6,29.7,29.6,29.4,29.1,29.0,28.1,24.2,22.7,22.6,22.5,14.1,11.3.HRMS(ESI)calcd for C40H61Br2S4Si(M+H+):855.1792.found:855.1851.
s3: reacting the compound of formula (4) with a compound (5) to produce a compound of formula (6);
the method specifically comprises the following steps: to a 100mL two-necked round-bottomed flask, under an argon protection, 400mg of the compound of formula (4), 427mg of the compound of formula (5), 27mg of tetrakis (triphenylphosphine) palladium, and 15mL of toluene are sequentially added; heating the reaction solution to 120 ℃, reacting for 8h, cooling to room temperature, adding water and ethyl acetate for extraction, drying an organic phase by using anhydrous magnesium sulfate, and distilling under reduced pressure to remove the solvent; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane 5/1-1/1) to yield 378mg of the compound of formula (6) as an orange solid in 62% yield.
The structural characterization data for the compound of formula (6) is:1H NMR(400MHz,THF-d8):δ7.27(d,J＝8.6Hz,4H),7.08(d,J＝8.8Hz,8H),6.91(d,J＝8.6Hz,4H),6.87(d,J＝8.8Hz,8H),3.76(s,12H),2.81(t,J＝7.8Hz,4H),1.83-1.75(m,4H),1.61-1.53(m,4H),1.41-1.22(m,32H),1.92-1.05(m,4H),0.89(t,J＝6.8Hz,6H),0.83(t,J＝6.8Hz,4H).13C NMR(400MHz,THF-d8):δ154.8,147.5,146.7,140.3,138.5,137.4,130.1,128.1,127.6,125.0,124.5,117.4,112.7,52.8,31.3,29.9,29.7,27.4,27.2,27.1,26.6,20.7,20.6,11.6,11.5,9.4,-1.48.HRMS(ESI)calcd for C80H97N2O4 S4Si(M+H+):1305.6100.found:1305.6108.
example 2
This example is substantially the same as example 1, with the main differences:
s1: synthesis of a compound of formula (3):
under the protection of argon and at the low temperature of-78 ℃, adding 981mg of the compound of the formula (1) dissolved by 30mL of anhydrous tetrahydrofuran into a 100mL eggplant-shaped reaction bottle, reacting at the low temperature for 5 minutes, slowly adding 1.56mL (2.4mol/L) of n-butyllithium, reacting at the low temperature for 1 hour, adding 582mg of the compound of the formula (2), closing refrigeration, and slowly returning to the room temperature; and reacting for 8 hours. Water and ethyl acetate were added for extraction, the organic phase was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 658mg of the compound of formula (3). It is a yellow-green viscous liquid with a yield of 58%.
S2: synthesis of a compound of formula (4):
to a 100mL single-neck round-bottom flask, 500mg of the compound of formula (3) and 20mL of tetrahydrofuran were added, followed by adding 268mg of N-bromosuccinimide to the system in portions, and reacting at 25 ℃ in the dark for 1 h; adding water for quenching, extracting by ethyl acetate, drying by anhydrous magnesium sulfate, and removing the solvent by reduced pressure distillation; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane 50/1-15/1) to give 416mg of the compound of formula (4) as an off-white solid in 68% yield.
S3: synthesis of the Compound of formula (6):
the method specifically comprises the following steps: 400mg of the compound of formula (4), 313mg of the compound of formula (5), 14mg of tetrakis (triphenylphosphine) palladium and 15mL of toluene are added to a 100mL two-necked round-bottom flask in this order under the protection of argon; heating the reaction solution to 120 ℃, reacting for 8h, cooling to room temperature, adding water and ethyl acetate for extraction, drying an organic phase by using anhydrous magnesium sulfate, and distilling under reduced pressure to remove the solvent; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane 5/1-1/1) to yield 305mg of the compound of formula (6) as an orange solid with a 50% yield.
Example 3
This example is substantially the same as example 1, with the main differences:
s1: synthesis of a compound of formula (3):
under the protection of argon, adding 981mg of the compound of the formula (1) dissolved by 30mL of anhydrous tetrahydrofuran into a 100mL eggplant-shaped reaction bottle at the low temperature of-78 ℃, slowly adding 1.56mL (2.4mol/L) of n-butyllithium after reacting for 5 minutes at the low temperature, adding 794mg of the compound of the formula (2) after reacting for 1 hour at the low temperature, closing refrigeration, and slowly returning to the room temperature; and reacting for 12 h. Water and ethyl acetate were added for extraction, and the organic phase was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to give 749mg of the compound of the formula (3). It is a yellow-green viscous liquid with a yield of 66%.
S2: synthesizing a compound of a formula (4);
adding 500mg of the compound of formula (3) and 20mL of tetrahydrofuran into a 100mL single-neck round-bottom flask, then adding 319mg of N-bromosuccinimide into the system in batches, and reacting for 15min at 25 ℃ in a dark place; adding water for quenching, extracting by ethyl acetate, drying by anhydrous magnesium sulfate, and removing the solvent by reduced pressure distillation; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane 50/1-15/1) to yield 435mg of the compound of formula (4) as an off-white solid in 76% yield.
S3: synthesis of a compound of formula (6):
to a 100mL two-necked round-bottomed flask, under an argon protection, 400mg of the compound of formula (4), 427mg of the compound of formula (5), 54mg of tetrakis (triphenylphosphine) palladium, and 15mL of toluene are sequentially added; heating the reaction solution to 120 ℃, reacting for 12h, cooling to room temperature, adding water and ethyl acetate for extraction, drying an organic phase by using anhydrous magnesium sulfate, and distilling under reduced pressure to remove the solvent; the crude product was purified by column chromatography (eluent: petroleum ether/dichloromethane 5/1-1/1) to yield 396mg of the compound of formula (6) as an orange solid in 65% yield.
Example 4
This example provides the use of a compound of formula (6), an organic hole material, prepared as in example 1, in the preparation of a perovskite solar cell. FIG. 2 is a schematic diagram of the perovskite solar cell fabricated in example 2, and the specific application method thereof is shown in the documents S.Mabrouk, M.Zhang, Z.Wang, M.Liang, B.Bahramide, Y.Wu, J.Wu, Q.Qiao, S.Yang.Dithieno [3,2-b:2 ', 3' -d ]]Pyrole-based Hole Transport Materials for Perovskite Solar Cells with Effeiciencies over 18%. J.Mater.chem.A,2018,6, 7950-. Testing a light source: AM 1.5(solar simulator-Oriel 91160-1000,300W), data collection used Keithley 2400 digital source tables. The test results are shown in FIG. 3, open circuit voltage (V)oc) 1.092V, short-circuit photocurrent density (J)sc) Is 22.55mAcm-2The Fill Factor (FF) was 0.7685, and the photoelectric conversion efficiency was 18.92%.
The above embodiments are merely illustrative of the technical concepts and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. A silicon-containing fused pentacyclic hole transport material having the chemical structure of formula (6):
2. a method for preparing the silicon-containing fused pentacyclic hole transport material of claim 1, comprising the steps of:
s1: subjecting the compound of formula (1) and the compound of formula (2) to a cyclization coupling reaction to produce a compound of formula (3);
s2: brominating a compound of formula (3) to produce a compound of formula (4);
s3: subjecting the compound of formula (4) and the compound of formula (5) to Still coupling reaction to produce the compound of formula (6);
3. the method according to claim 2, wherein the silicon-containing fused pentacyclic hole transport material comprises:
in the S1, the compound of the formula (1) reacts with the compound of the formula (2) in solvent anhydrous tetrahydrofuran under the action of n-butyl lithium to generate a compound of the formula (3), wherein the dosage of each substance is calculated by the amount of the substance, and the compound of the formula (1): a compound of formula (2): n-butyl lithium ═ 1: 1-1.5: 2-4: the reaction time is 8-12 h.
4. The method according to claim 2, wherein the silicon-containing fused pentacyclic hole transport material comprises:
in said S2, brominating the compound of formula (3) with N-bromosuccinimide in tetrahydrofuran as a solvent to produce a compound of formula (4), wherein the amount of each substance is calculated by the amount of substance, the compound of formula (3): NBS ═ 1: 2-3; the reaction time is 0.1-2 h.
5. The method according to claim 2, wherein the silicon-containing fused pentacyclic hole transport material comprises:
in the S3, the compound of the formula (4) is subjected to Still coupling reaction with the compound of the formula (5) in a solvent of toluene under the action of a catalyst of tetrakis (triphenylphosphine) palladium to generate a compound of the formula (6), wherein the dosage of each substance is calculated by the mass amount, and the compound of the formula (4): a compound of formula (5): tetrakis (triphenylphosphine) palladium ═ 1: 2-3: 0.02-0.1, and the reaction time is 6-12 h.
6. Use of a silicon-containing fused pentacyclic hole transport material of claim 1 in a perovskite solar cell.
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