CN110156780B - Perylene diimide non-fullerene acceptor material based on 8-hydroxyquinoline aluminum as core - Google Patents
Perylene diimide non-fullerene acceptor material based on 8-hydroxyquinoline aluminum as core Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 22
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 title claims abstract description 14
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 title claims abstract description 9
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title abstract description 12
- -1 fullerene small molecule Chemical class 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 238000013086 organic photovoltaic Methods 0.000 abstract description 4
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 abstract description 4
- 150000004325 8-hydroxyquinolines Chemical class 0.000 abstract 2
- 239000005725 8-Hydroxyquinoline Substances 0.000 abstract 1
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract 1
- 239000000539 dimer Substances 0.000 abstract 1
- 229960003540 oxyquinoline Drugs 0.000 abstract 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical group C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000007405 data analysis Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 3
- 101000609839 Dictyostelium discoideum Protein disulfide-isomerase 2 Proteins 0.000 description 3
- 101000735558 Homo sapiens Protein-arginine deiminase type-2 Proteins 0.000 description 3
- 102100035735 Protein-arginine deiminase type-2 Human genes 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004420 diamide group Chemical group 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- KZDTZHQLABJVLE-UHFFFAOYSA-N 1,8-diiodooctane Chemical compound ICCCCCCCCI KZDTZHQLABJVLE-UHFFFAOYSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed systems contains four or more hetero rings
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
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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
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
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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 discloses a wide-band-gap star-shaped perylene diimide non-fullerene small molecule acceptor material and application thereof in an organic solar cell. The invention synthesizes two 8-hydroxyquinoline derivatives by taking 8-hydroxyquinoline aluminum with electron-withdrawing property and high electron mobility as a core unit and connecting Perylene Diimide (PDI) or dimer thereof (PDI2) to the 5-position of 8-hydroxyquinoline through Suzuki reaction, and the two 8-hydroxyquinoline derivatives are mixed with Al3+The coordination forms two wide-bandgap non-fullerene acceptor materials. The micromolecule acceptor material provided by the invention and the narrow band gap donor material PPTA can form good absorption complementation and energy level matching. When the non-fullerene wide-band-gap star-shaped non-fullerene micromolecule is used in an organic solar cell, the open-circuit voltage of 0.85V and the filling factor of 71.27 percent can be obtained, so that the high-energy conversion efficiency of 9.54 percent can be obtained, and the application prospect of the wide-band-gap star-shaped non-fullerene micromolecule in the field of organic photovoltaics is fully shown.
Description
Technical Field
The invention belongs to the field of organic semiconductor materials, and relates to a perylene diimide wide band gap small molecule acceptor material taking 8-hydroxyquinoline aluminum as a core, a preparation method thereof and application thereof in an organic solar cell.
Background
Solar energy has received wide attention as an inexhaustible renewable clean energy source. Among them, the organic solar cell has advantages of light weight, flexibility, low cost, large-area production in roll-to-roll manner, etc., so that it has a wide application prospect, and is widely considered as a typical representative of the next-generation solar cell. In the last two decades, the energy conversion efficiency of the organic solar cell is greatly improved through the synthesis of materials and the optimization of a device preparation process, and the organic solar cell has an extremely good industrial prospect.
For fullerene acceptor systems, there are some drawbacks, such as: the further development of the photovoltaic devices is limited by the weak absorption of a visible light region, high synthesis and purification cost, difficult energy level regulation, poor stability of the easily-gathered inversion device and the like. In response to the shortcomings of fullerenes and their derivatives, the development of alternative, high performance, non-fullerene acceptor materials is imperative.
Polymer donor materials have been developed in a long-standing fashion, emerging as a class of high efficiency narrow bandgap materials such as PTB7-Th, PPTA, and the like. In order to form a good absorption spectrum complementary with the materials, the development of high-performance wide-band-gap acceptor materials which can replace fullerene is urgent. Perylene diimide is a typical n-type organic semiconductor material, has the characteristics of good photo-thermal stability, strong visible light region absorption, high light quantum yield and the like, and is widely applied to organic photovoltaic devices. However, the rigid structure of the perylene diimide compound can cause the self-aggregation of the molecules to be serious, and further improvement of the photovoltaic efficiency of the perylene diimide compound is severely restricted. In order to prepare the efficient non-fullerene acceptor material by utilizing the advantages of the perylene diimide, the novel perylene diimide acceptor material needs to be further developed to solve the contradiction between the molecular aggregation and the photovoltaic efficiency improvement. At present, the reported perylene diimide acceptor materials usually adopt an electron donor structure as an intermediate core unit. In order to enhance the electron transport performance of the acceptor materials, a group with high mobility and an electroabsorption property is adopted as a core unit, so that the acceptor materials have good advantages.
In the preparation of an active layer based on a perylene diimide acceptor material, 1, 8-Diiodooctane (DIO) is generally added as an additive to improve the morphology of the active layer, but this generally reduces the open circuit voltage of the device and also reduces the stability of the device. For practical needs, how to select proper additives is particularly critical for preparing efficient and stable organic photovoltaic devices.
Disclosure of Invention
The invention aims to provide a novel perylene diimide compound with a three-dimensional structure, a preparation method thereof and application of the perylene diimide compound as an acceptor material in an organic photovoltaic device. Solves the serious self-aggregation of the materials, thereby effectively improving the photoelectric conversion efficiency of the device. Meanwhile, 8-hydroxyquinoline aluminum with high electron mobility and electron absorbability is selected as a core unit, so that the electron mobility of the acceptor material can be effectively improved. When the halogen-free additive 4, 4' -bipyridyl is added, the morphology of an active layer can be effectively adjusted, the photoelectric conversion efficiency is increased, and the stability of the device is improved.
The technical scheme of the invention is as follows:
a novel perylene diimide non-fullerene acceptor material with high packing factor has the following general structure:
wherein, X is Al, Ga or In atom; ar adopts perylene diamide groups shown in formulas II, III and IV:
wherein R is1Is C1-C12Linear or branched alkyl.
In a preferred embodiment, X is an Al atom; r is C1-C12The linear alkyl group of (1); ar adopts perylene diamide groups shown in formula I and formula II:
wherein R is preferably C1-C6Linear alkyl group of (1).
The most preferred wide-bandgap non-fullerene small molecule acceptor materials based on aluminum 8-hydroxyquinoline as a core have the following molecular structural formula:
the main advantages of the invention are:
1. the wide-band-gap non-fullerene small-molecule acceptor material based on 8-hydroxyquinoline aluminum as the core has good solubility, and can be dissolved in most common organic solvents, such as: toluene, chloroform, chlorobenzene, and the like.
2. The wide-band-gap non-fullerene small-molecule acceptor material based on 8-hydroxyquinoline aluminum as the core has better absorption in a short wavelength range, and can form better optical absorption complementation with individual materials such as narrow-band-gap materials PPTA and the like.
3. The wide-band-gap star-shaped non-fullerene small-molecule acceptor material based on 8-hydroxyquinoline aluminum as the core has high electron mobility. When the halogen-free additive 4, 4' -bipyridyl is added into the active layer, the morphology of the active layer can be improved, and the efficiency and the stability of the device can be improved.
Drawings
FIG. 1 is Alq of the present invention3-uv-vis absorption spectrum of PDI small molecule receptor material;
FIG. 2 is Alq of the present invention3-PDI2 uv-visible absorption spectrum of small molecule receptor material;
FIG. 3 is a current density-voltage (J-V) graph of an organic solar cell prepared using an aluminum 8-hydroxyquinoline based wide bandgap non-fullerene small molecule acceptor according to the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A chemical structure of Alq3-PDI small molecule receptor, the synthetic route of which is as follows:
synthesis of Compound 3: compound 1(0.10 g, 0.28 mmol), compound 2(0.24 g, 0.33 mmol), 2 mol/l potassium carbonate solution (2 ml) were dissolved in 10 ml toluene, oxygen was removed, and Pd (PPh) was added under nitrogen protection3)4(1.3 mg, 2% mmol) and the reaction is refluxed for 12 hours. After the reaction is finished, the reaction product is cooled to room temperature, the solvent is removed under reduced pressure, and the product is purified by column chromatography to obtain a black solid product, wherein the yield is 52%.
Nuclear magnetic data and elemental analysis data for compound 3: nuclear magnetic hydrogen spectrum (400MHz, CDCl)3,δ/ppm):9.03(m,1H,ArH),8.66-8.73(m,4H,ArH),8.53(s,1H,ArH),7.90-7.93(m,2H,ArH),7.59-7.64(m,3H,ArH),7.43-7.49(m,3H,ArH),7.35-7.39(m,1H,ArH),7.28-7.30(m,1H,ArH),7.21(d,1H,7.3Hz,ArH),5.58(d,2H,7.2Hz,CH2),5.15(d,2H,7.2Hz,CH2),2.11-2.33(m,4H,CH2),1.76-1.96(m,4H,CH2),1.19-1.39(m,16H,CH2),0.78-0.91(m,12H,CH3). Nuclear magnetic carbon spectrum (100MHz, CDCl)3Delta/ppm) 153.08,148.66,139.03,134.48,134.36,133.39,130.70,129.17,128.94,128.81,128.70,128.59,127.92,127.25,125.22,123.62,111.09,54.78,54.61,32.09,32.01,29.71,29.37,29.12,29.08,22.64,22.59,14.06, 14.01. Elemental analysis (C)58H57N3O5) Calculating the following values: c, 79.51; h, 6.56; n, 4.80; measured value: c, 79.59; h, 6.89; and N, 4.95.
Synthesis of Compound 4: compound 3(0.20 g, 0.23 mmol) was dissolved in 50 ml of glacial acetic acid and 15 ml of hydrobromic acid were added. The reaction was allowed to react at 120 ℃ for 2 hours. After the reaction was completed, it was cooled to room temperature. Filtration and column chromatography of the resulting solid gave the product as a black solid in 56.52% yield.
Nuclear magnetic data and elemental analysis data for compound 4: nuclear magnetic hydrogen spectrum (400MHz, CDCl)3,δ/ppm):8.81-8.83(m,1H,ArH),8.65-8.75(m,3H,ArH),8.58(s,1H,ArH),7.86-7.93(m,2H,ArH),7.67-7.73(d,1H,7.2Hz,ArH),7.61-7.65(d,1H,7.2Hz,ArH),7.35-7.40(d,1H,6.8Hz,ArH),7.27-7.29(m,2H,ArH),5.04-5.25(m,2H,CH2),2.09-2.33(m,4H,CH2),1.75-1.93(m,4H,CH2),1.17-1.37(m,16H,CH2),0.77-0.91(m,12H,CH3). Nuclear magnetic carbon spectrum (100MHz, CDCl)3,δ/ppm):(100MHz,CDCl3δ/ppm) 154.97,150.15,141.36,138.06,136.44,134.97,134.31,133.94,133.02,132.34,129.16,128.95,128.81,128.66,128.13,127.90,127.31,127.27,127.23,126.39,123.60,122.84,122.60,110.82,77.35,77.23,77.03,76.71,71.04,54.76,54.59,32.08,31.99,29.11,29.09,22.64,22.60,14.07,14.05, 14.02. Elemental analysis (C)51H51N3O5) Calculating the following values: c, 77.94; h, 6.54; n, 5.35; measured value: c, 78.11; h, 6.87; n, 5.62.
Synthesis of Compound Alq 3-PDI: anhydrous AlCl3(0.017 g, 0.127 mmol) was dissolved in 10 ml of toluene, slowly added dropwise to compound 4(0.3 g, 0.382 mmol), reacted at 110 ℃ under reflux overnight, 5 ml of the solution was concentrated under reduced pressure after the reaction was completed, filtered, the resulting crude product was washed with n-hexane, recrystallized from chloroform and methanol (10:15, V/V), dried and purified by column chromatography using neutral alumina to give a black solid product with a yield of 42.52%.
Nuclear magnetic data and elemental analysis data for compound Alq 3-PDI: nuclear magnetic hydrogen spectrum (400MHz, CDCl)3,δ/ppm):8.57-8.81(m,15H,ArH),8.23(m,3H,ArH),7.49-7.52(m,18H,ArH),5.23(m,6H,CH2),2.09-2.35(m,12H,CH2),1.75-1.94(m,12H,CH2),1.15-1.39(m,48H,CH2),0.75-0.92(m,36H,CH3). Nuclear magnetic carbon spectrum (100MHz, CDCl)3Delta/ppm) 152.57,149.85,139.65,138.83,137.25,129.48,123.75,118.35,118.12,114.93,114.68,76.53,75.42,73.26,53.54,31.86,29.56,26.54,22.96,22.70,14.14,14.10, 10.93. Mass Spectrometry (MALDI-TOF, m/z): calculated value (C)153H150AlN9O15): 2380.107, respectively; measured value: 2380.106.
example 2
A chemical structure of Alq3-PDI small molecule receptor, the synthetic route of which is as follows:
synthesis of Compound 6: compound 1(0.10 g, 0.28 mmol), compound 2(0.46 g, 0.33 mmol), 2 mol/l potassium carbonate solution (2 ml) were dissolved in 10 ml toluene, oxygen was removed, and Pd (PPh) was added under nitrogen protection3)4(1.3 mg, 2% mmol) and the reaction is refluxed for 12 hours. After the reaction is finished, the reaction product is cooled to room temperature, the solvent is removed under reduced pressure, and the product is purified by column chromatography to obtain a dark red solid product, wherein the yield is 48.85%.
Nuclear magnetic data and elemental analysis data for compound 6: nuclear magnetic hydrogen spectrum (400MHz, CDCl)3,δ/ppm):10.32(m,3H,ArH),9.47(d,2H,7.2Hz,ArH),8.97-9.28(m,4H,ArH),8.31-8.51(m,2H,ArH),7.9-8.0(m,1H,ArH),7.6-7.79(m,3H,ArH),7.29-7.54(m,6H,ArH),5.67(d,2H,7.6Hz,CH2),5.19-5.42(m,4H,7.6Hz,CH2),2.16-2.47(m,8H,CH2),1.80-2.08(m,8H,CH2),1.05-1.52(m,32H,CH2),0.64-0.96(m,24H,CH3). Nuclear magnetic carbon spectrum (100MHz, CDCl)3Delta/ppm) 164.89,163.79,154.88,150.03,138.63,136.35,134.00,133.80,133.33,132.74,128.89,128.27,127.92,127.31,126.84,126.49,126.26,125.81,125.19,124.32,123.94,122.72,111.13,55.11,32.39,31.94,31.78,29.72,26.74,22.59,14.10,14.07,13.98 elemental analysis (C)102H99N5O9): calculated values: c, 79.61; h, 6.48; n, 4.55; measured value: c, 79.88; h, 6.56; and N, 4.75.
Synthesis of compound 7: compound 3(0.35 g, 0.23 mmol) was dissolved in 50 ml of glacial acetic acid and 15 ml of hydrobromic acid were added. The reaction was allowed to react at 120 ℃ for 2 hours. After the reaction was completed, it was cooled to room temperature. Filtration and column chromatography of the solid obtained gave a dark red solid product with a yield of 50.03%.
Nuclear magnetic data and elemental analysis data for compound 7: nuclear magnetic hydrogen spectrum (400MHz, CDCl)3,δ/ppm):10.33(m,3H,ArH),9.45(d,2H,7.2Hz,ArH),8.94-9.31(m,4H,ArH),8.34-8.57(m,2H,ArH),7.31-7.54(m,6H,ArH),5.66(d,2H,7.6Hz,CH2),5.19-5.44(m,4H,7.2Hz,CH2),2.16-2.49(m,8H,CH2),1.81-2.11(m,8H,CH2),1.03-1.55(m,32H,CH2),0.64-0.98(m,24H,CH3). Nuclear magnetic carbon spectrum (100MHz, CDCl)3Delta/ppm) 165.19,164.29,156.78,152.13,148.85,139.13,137.25,135.08,133.92,133.53,132.82,128.94,128.65,127.35,127.21,126.84,126.59,126.38,125.89,125.34,124.56,124.04,123.52,111.56,55.41,32.46,32.04,31.64,29.80,26.78,22.49,14.16,14.09, 13.86. Elemental analysis (C)95H93N5O9): calculated values: c, 78.76; h, 6.47; n, 4.83; measured value: c, 79.08; h, 6.58; and N, 4.95.
Synthesis of Compound Alq3-PDI 2: synthesis of Compound Alq 3-PDI: anhydrous AlCl3(0.017 g, 0.127 mmol) was dissolved in 10 ml of toluene, slowly added dropwise to compound 4(0.55 g, 0.382 mmol), reacted at 110 ℃ under reflux overnight, 5 ml of the solution was concentrated under reduced pressure after the reaction was completed, filtered, the resulting crude product was washed with n-hexane, recrystallized from chloroform and methanol (10:15, V/V), dried and purified by column chromatography using neutral alumina to give a dark red solid product with a yield of 40.85%.
Nuclear magnetic data and elemental analysis data for compound Alq3-PDI 2: nuclear magnetic hydrogen spectrum (400MHz, CDCl)3,δ/ppm)：10.35(m,9H,ArH),8.57-9.46(m,21H,ArH),7.36-7.55(m,18H,ArH),5.21-5.46(m,12H,CH2),2.15-2.51(m,24H,CH2),1.81-2.15(m,24H,CH2),1.01-1.58(m,96H,CH2),0.61-0.98(m,72H,CH3). Nuclear magnetic carbon spectrum (100MHz, CDCl)3δ/ppm): 165.11,163.71,139.87,136.75,135.65,134.98,131.26,132.67,131.66,130.56,128.98,128.12,127.98,125.26,123.45,122.76,76.35,76.24,76.02,75.69,55.45,55.06,32.68,32.36,31.98,31.78,30.76,28.68,25.48,14.98,14.28. Mass Spectrometry (MALDI-TOF, m/z): calculated value (C)285H276AlN15O27): 4367.050, respectively; measured value: 4367.050.
example 3
Alq3-PDI and Alq3UV-VIS absorption Spectroscopy testing of-PDI 2 Small molecule acceptor materials
FIG. 1 and FIG. 2 are respectively Alq3-PDI and Alq3-PDI2 uv-vis absorption spectra of small molecule receptor materials in chloroform solution and thin films.
As can be seen from FIG. 1, Alq3The film absorption maximum of the PDI is 498 nanometers, the initial absorption peak is about 636 nanometers, and the optical band gap of the PDI is 1.95 electron volts.
As can be seen from FIG. 2, Alq3PD2I has a film absorption maximum at 545 nm, an initial absorption peak at around 660 nm, and an optical band gap of 1.95 eV.
Example 4
Organic small molecule acceptor material Alq3-PDI and Alq3Photovoltaic Performance test of PDI2
The invention selects a narrow-bandgap polymer donor material PPTA (optical bandgap is near 1.60 electron volt), and the molecular structure of the material is as follows:
the preparation process and the performance test of the solar photovoltaic device are as follows: and spin-coating a ZnO precursor solution on a clean ITO glass sheet, and treating at 150 ℃ for 30 minutes to obtain a ZnO thin layer of about 30 nanometers. The receptor material of the present invention was blended with PPTEA (weight ratio 1:1.5) and 0.5% 4, 4' -bipyridine was added to the blend solution. The active layer is then prepared by spin coating. Finally, MoO with the thickness of 10 nanometers is respectively deposited by adopting a vacuum evaporation mode3And 100 nm thick Al electrodes. The photovoltaic performance of the relevant devices was measured under simulated sunlight (AM 1.5; 100 mw/cm).
Based on Alq3Photovoltaic performance of PDI, as shown in fig. 3: short-circuit current of 13.56mA cm-2The open circuit voltage was 0.87V, and the fill factor was 66.33%, so the energy conversion efficiency was 7.82%.
Based on Alq3Photovoltaic performance of PDI2, as shown in fig. 3: short-circuit current of 15.74mA cm-2The open circuit voltage was 0.85V, and the fill factor was 71.27%, so that the energy conversion efficiency was 9.54%.
Table 1 is based on Alq3-PDI and Alq3Photovoltaic performance data with PDI2 as acceptor material
Claims (4)
1. A wide-band-gap non-fullerene small-molecule acceptor material based on 8-hydroxyquinoline aluminum as a core is characterized in that the molecular structure of the acceptor material is shown as a formula I:
wherein, X is Al atom; ar adopts perylene diimide groups shown in formula II, formula III and formula IV:
wherein R is C1-C12Linear or branched alkyl.
2. The aluminum 8-hydroxyquinoline-based wide-bandgap non-fullerene small-molecule acceptor material as claimed in claim 1 wherein R is preferentially C1-C12Linear alkyl group of (1).
3. The wide-bandgap non-fullerene small-molecule acceptor material based on aluminum 8-hydroxyquinoline as core according to claim 1, wherein Ar preferentially selects the following perylene diimide structures:
4. the aluminum 8-hydroxyquinoline-based wide-bandgap non-fullerene small-molecule acceptor material as claimed in claim 3, wherein R is preferably C1-C6Linear alkyl group of (1).
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