CN115873016B - Condensed ring organic small molecule and preparation method and application thereof - Google Patents
Condensed ring organic small molecule and preparation method and application thereof Download PDFInfo
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- 150000003384 small molecules Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000004528 spin coating Methods 0.000 claims description 7
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 229940125773 compound 10 Drugs 0.000 claims description 4
- 229940125898 compound 5 Drugs 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006619 Stille reaction Methods 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 210000004556 brain Anatomy 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229940125904 compound 1 Drugs 0.000 claims description 2
- 229940125782 compound 2 Drugs 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 claims description 2
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
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- 238000003786 synthesis reaction Methods 0.000 abstract description 21
- 230000031700 light absorption Effects 0.000 abstract description 6
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000001254 matrix assisted laser desorption--ionisation time-of-flight mass spectrum Methods 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 7
- 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 description 5
- 229910003472 fullerene Inorganic materials 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 4
- MZSAMHOCTRNOIZ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylaniline Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(NC2=CC=CC=C2)C=CC=1 MZSAMHOCTRNOIZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- SAHIZENKTPRYSN-UHFFFAOYSA-N [2-[3-(phenoxymethyl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound O(C1=CC=CC=C1)CC=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 SAHIZENKTPRYSN-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- HAEQAUJYNHQVHV-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylbenzamide Chemical group NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC2=CC=CC=C2)C=CC=1 HAEQAUJYNHQVHV-UHFFFAOYSA-N 0.000 description 1
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 1
- REAYFGLASQTHKB-UHFFFAOYSA-N [2-[3-(1H-pyrazol-4-yl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound N1N=CC(=C1)C=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 REAYFGLASQTHKB-UHFFFAOYSA-N 0.000 description 1
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000007385 chemical modification Methods 0.000 description 1
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- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
-
- 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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- Photovoltaic Devices (AREA)
Abstract
The invention belongs to the technical field of organic materials, and discloses a condensed ring organic small molecule which shows excellent photoelectric conversion efficiency, wherein the condensed ring organic small molecule is synthesized by an intramolecular cyclization method under ultraviolet irradiation, has the advantages of simple and easily obtained raw materials, simple synthesis, high yield, good light absorption, simple post-treatment, such as solution processing and the like, can be used as a receptor material for an organic solar cell, and is favorable for reducing the synthesis cost of the receptor material of the organic solar cell.
Description
Technical Field
The invention belongs to the technical field of organic materials, and particularly relates to a condensed ring organic small molecule, a preparation method and application thereof.
Background
Solar cells have been a research hotspot in the field of new energy as a device for converting solar energy into electrical energy. The organic solar cell for realizing photoelectric conversion has the outstanding advantages of rich material types, solution processing, flexibility, folding, light weight and the like, and becomes a research front in the fields of new energy and organic photoelectricity. In recent years, the non-fullerene acceptor not only makes up the defect of the fullerene acceptor in light absorption, but also can be subjected to chemical modification very conveniently, so that the non-fullerene organic solar cell has high photoelectric conversion efficiency, and the further development of the solar cell is promoted.
Currently, highly efficient non-fullerene acceptor materials are generally structurally composed of fused ring structures. The conjugated main body of the condensed ring ensures the planarity and conjugation of the molecular main body, is favorable for light absorption and carrier transmission, but the condensed ring structure is generally complex to synthesize, and the most widely studied Y-series condensed ring acceptor with the current efficiency is taken as an example, and the published literature "Single-Junction Organic Solar Cell with over 15％Efficiency Using Fused-Ring Acceptorwith Electron-Deficient Core"(Joule2019,3(4),1140-1151.), uses commercial benzothiadiazole and the like as starting materials, the synthesis steps of the materials are up to 16 steps, and the total yield is lower than 5%. Moreover, the complicated reaction steps and point yield also make the subsequent regulation and control of the energy level, molecular accumulation, absorption spectrum and solution processing characteristics of the molecules of the receptor by means of substituent modification, conjugated framework expansion, alkyl modification and the like difficult.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a condensed ring organic small molecule which shows excellent photoelectric conversion efficiency, and the condensed ring organic small molecule is synthesized by an intramolecular cyclization method under ultraviolet irradiation, has the advantages of simple and easily obtained raw materials, high yield, good light absorption, simple post-treatment, such as solution processing and the like, can be used as a receptor material to be applied to an organic solar cell, is favorable for reducing the synthesis cost of the receptor material of the organic solar cell, and is expected to become a new generation of organic photovoltaic key material.
The technical scheme adopted by the invention is as follows:
A fused ring organic small molecule having the structural formula:
In the structural formula I and the structural formula II: r1 is any one of C1-C20 alkyl groups, R2 is also any one of C1-C20 alkyl groups, and the C1-C20 alkyl groups refer to straight-chain or branched-chain alkyl groups with 1-20 carbon atoms; x is hydrogen atom or halogen substituent, wherein the halogen substituent is any one of fluorine, chlorine and bromine.
The condensed ring acceptor small molecule structural formula comprises and is not limited to the following structure:
The preparation method of the compound comprises the following steps:
(1) A step of preparing a compound 3 or 8 by Stille coupling reaction of the compound 1 and the compound 2 or 7 under the catalysis of triphenylphosphine palladium,
(2) A step of preparing a compound 4 or 9 by carrying out a Wilsmeier-Hake reaction on phosphorus oxychloride and N, N-dimethylformamide and then carrying out a substitution reaction with the compound 3 or 8,
(3) A step of subjecting the compound 4 or 9 to intramolecular cyclization under the catalysis of a small amount of iodine to prepare a compound 5 or 10,
(4) A step of preparing a structural formula-1 or a structural formula-2 by carrying out a gram-brain Wen Geer condensation reaction on a compound 5 or a compound 10 and a compound 6 under the catalysis of pyridine,
Further, in the step (1), the reaction is carried out under the protection of nitrogen, and the solvent of the reaction system is dry toluene; the reaction temperature is 80-120 ℃ and the reaction time is 3-24 hours.
Further, in the step (2), the reaction is carried out under the protection of nitrogen, the temperature of the Wilsmeier-Hake reaction is 10-0 ℃, and the reaction time is 0.1-1 hour; the temperature of the substitution reaction is 40-90 ℃ and the reaction time is 2-20 hours; compound 3: phosphorus oxychloride: n, N-dimethylformamide=1:2:2 to 1:20:100.
Further, in the step (3), the solvent of the reaction system is dry toluene; the wavelength of the light source is 250-750 nm, the reaction temperature is 0-110 ℃, and the reaction time is 1-12 hours.
In the step (4), the reaction is carried out under the protection of nitrogen, the temperature of the gram brain Wen Geer condensation reaction is 65-85 ℃, and the reaction time is 8-48 hours.
The corresponding synthetic route of the condensed ring organic small molecule structural formula I is shown as follows:
the corresponding synthetic route of the condensed ring organic small molecule structural formula II is shown as follows:
The condensed ring organic small molecule has good photoelectric characteristics and can be used as an active layer acceptor material to be applied to an organic solar cell device, namely the invention also provides the application of the condensed ring organic small molecule as the active layer acceptor material to the organic solar cell device.
Preferably, the material of the active layer of the organic solar cell device is the condensed ring small organic molecule and D18, and the mass ratio of the condensed ring small organic molecule to D18 is 1.1:1.
Further preferably, the preparation process of the organic solar cell device includes: after ultrasonic treatment, degreasing and cleaning are carried out on the substrate coated with the ITO transparent motor, firstly, 30nm PEDOT: PSS is spin-coated on the ITO, and an active layer and an electron transmission layer are spin-coated in sequence under vacuum or inert gas atmosphere; the active layer is prepared by spin coating after the condensed ring small organic molecules and D18 are dissolved in chloroform solution, the thickness of the active layer is 120nm, and the mass ratio of the condensed ring small organic molecules to the D18 is 1.1:1; the electron transport layer is formed by PDIN spin coating on the active layer, and the thickness of the electron transport layer is 15nm and is used as the electron transport layer; 120nm aluminum was evaporated as cathode.
It should be noted that the chemical structures of D18 and PDIN are as follows:
Compared with the prior art, the invention has the beneficial effects that:
In a first aspect, the condensed ring organic small molecule provided by the invention is an electron withdrawing unit-electron donating unit-electron withdrawing unit (A-D-A) acceptor small molecule based on a condensed ring imide structure, and in the molecule, the condensed ring imide structure unit has good conjugation characteristic and planarity, so that effective pi-pi accumulation of a material in a film can be ensured, and further good charge mobility is possessed. The molecular structure of A-D-A can have strong push-pull electron effect in the intramolecular travel, thereby endowing the molecule with enhanced intramolecular charge transfer characteristic and enhancing the light absorption capacity of the molecule. The strong electron withdrawing characteristic of the terminal group can ensure that the molecule has low Lowest Unoccupied Molecular Orbital (LUMO) energy level, realize the electron transmission characteristic of the molecule, and further can be used as an acceptor material to be applied to an organic solar cell.
In the second aspect, the preparation method of the condensed ring small organic molecule provided by the invention has the advantages of easily available raw materials, simple synthesis, high yield, good solubility and film forming property, high yield and simple post-treatment, and can finally realize high-yield synthesis of novel condensed ring small molecule receptors.
In the third aspect, due to proper energy level, excellent light absorption property and electron transmission property, the condensed ring organic small molecule based on the invention can be applied to an organic solar cell as a non-fullerene acceptor material, and the organic solar cell prepared by blending the condensed ring organic small molecule and the donor polymer D18 based on the invention realizes 16% of photoelectric conversion efficiency, has excellent device performance and has good application prospect.
Drawings
FIG. 1 is a schematic diagram of an organic solar cell prepared by using a condensed ring organic small molecule as an electron acceptor material of an active layer;
FIG. 2 is a MALDI-TOF-MS spectrum of NFA-1 described in example 1;
FIG. 3 is a MALDI-TOF-MS spectrum of NFA-2 described in example 2;
FIG. 4 is a MALDI-TOF-MS spectrum of NFA-3 described in example 3;
FIG. 5 is a MALDI-TOF-MS spectrum of NFA-4 described in example 4;
FIG. 6 is a MALDI-TOF-MS spectrum of NFA-5 described in example 5;
FIG. 7 is a MALDI-TOF-MS spectrum of NFA-6 described in example 6.
Detailed Description
The present invention provides a method of synthesizing six fused ring small organic molecules, and in describing embodiments of the present invention, specific terminology is employed for the sake of clarity. However, the invention is not intended to be limited to the specific terminology so selected. It is to be understood that each specific element includes all technical equivalents which operate in a similar manner to accomplish a similar purpose.
The chemical structure of the condensed ring small molecule is characterized by M nuclear magnetic resonance and high-resolution mass spectrum, and the preparation method of the condensed ring small molecule comprises the following steps:
example 1: synthesis of fused Ring organic Small molecule NFA-1
The specific synthetic route for NFA-1 is shown below:
Compound 1-3 synthesis: weighing the compound 1-1 (1 equiv) and the compound 1-2 (2.5 equiv) into a reaction bottle, sequentially adding tetrahydrofuran (15 mL/mmol) and Pd (PPh 3)4 (0.05 equiv), heating and refluxing under nitrogen protection for 12 hours, cooling to room temperature, and purifying by a chromatographic column (dichloromethane: petroleum ether=1:2) to obtain the target compound 1-3 with the yield of 90%. Elemental analysis (C54H 75NO2S 4) theoretical value: C,72.19; H,8.41; N,1.56; O,3.56; actual measurement value: C,72.21; H,8.42; N, 1.57O, 3.53; HRMS (ESI) M/z: theoretical value: 897.46; actual measurement value: 898.51 (M+H).
Synthesis of Compounds 1-4: 750mg of the compound 1-3 was weighed into a reaction flask, 40mL of dichloroethane, 20mL of anhydrous N, N-formamide (20 mL) were sequentially added under ice bath, 5mL of phosphorus oxychloride, and the mixture was stirred under nitrogen protection for 2 hours. The temperature was raised to 90 ℃ and stirred overnight, cooled to room temperature, extracted with dichloromethane, the solvent was dried by spin-drying, and purified by column chromatography on silica gel (dichloromethane: petroleum ether=2:1) to give the target compound 1-4 in 85% yield. Elemental analysis: (C56H 75NO4S 4) theory: c,70.47; h,7.92; n,1.47; o,6.70; actual measurement value: c,70.51; h,7.90; n,1.49; o,6.67, HRMS (ESI) m/z: theoretical value: 953.45; actual measurement value: 954.46 (M+H).
Compound 1-5 synthesis: 500mg of compound 1-4 is weighed, added into a reaction bottle, 40mL of toluene and catalytic amount of iodine are added, stirring reaction is carried out under the condition of illumination (light source: 400nm, LED, 70W), continuous illumination reaction is carried out, TLC monitors the reaction progress, after the reaction is completed, the mixture is poured into saturated Na 2S2O3 aqueous solution, extracted by ethyl acetate, and the target compound 1-5 is obtained after separation and purification by silica gel column chromatography (dichloromethane: petroleum ether=2:1), wherein the yield is 95%. Elemental analysis: (C56H 73NO4S 4) theory: c,70.62; h,7.73; n,1.47; o,6.72; actual measurement value: c,70.58; h,7.76; n,1.49; o,6.71, HRMS (ESI) m/z: theoretical value: 951.44; actual measurement value: 951.44.
Compound NFA-1 synthesis: 190mg (0.2 mmol) of compound 1-5 and 200mg of compound 1-6 (1 mmol) were weighed, 50mL of chloroform and 2mL of pyridine were added, the mixture was heated and refluxed for 12 hours, cooled to room temperature, poured into methanol, filtered, and purified by silica gel column chromatography (dichloromethane: petroleum ether=3:1) to obtain polymer NFA-1 in 85% yield. Elemental analysis: (C80H 81N5O4S 4) theory: c,73.64; h,6.26; n,5.37; o,4.90; actual measurement value: c,73.67; h,6.27; n,5.39; o,4.87, HRMS (ESI) m/z: theoretical value: 1303.51; actual measurement value: 1304.53 (M+H). As shown in FIG. 2, the MALDI-TOF-MS spectrum of the NFA-1 is shown.
Example 2: synthesis of fused Ring organic Small molecule NFA-2
The synthesis and treatment of compound NFA-2 is the same as that of NFA-1, except that reactants 1-6 are replaced by compounds 1-7 of the following formula:
elemental analysis: (C80H 77F4N5O4S 4) theory: c,69.79; h,5.64; n,5.09; o,4.65; actual measurement value: c,69.82; h,5.61; n,5.11; o,4.62, HRMS (ESI) m/z: theoretical value: 1375.47; actual measurement value: 1376.50 (M+H). As shown in FIG. 3, the MALDI-TOF-MS spectrum of the NFA-2 is shown.
Example 3: synthesis of fused Ring organic Small molecule NFA-3
The synthesis and treatment of compound NFA-3 is the same as that of NFA-1, except that reactants 1-6 are replaced by compounds 1-8 of the following formula:
Elemental analysis: (C80H 77Cl4N5O4S 4) theory: c,66.61; h,5.38; n,4.85; o,4.44; actual measurement value: c,66.60; h,5.41; n,4.83; o,4.46, HRMS (ESI) m/z: theoretical value: 1442.36; actual measurement value: 1443.42 (M+H). As shown in FIG. 4, the MALDI-TOF-MS spectrum of the NFA-3 is shown.
Example 4: synthesis of fused Ring organic Small molecule NFA-4
The synthesis and treatment of compound NFA-4 is the same as that of NFA-1, except that reactant 1-2 is replaced with compound 2-1:
elemental analysis: (C78H 79N7O4S 4) theory: c,71.69; h,6.09; n,7.50; o,4.90; actual measurement value: c,71.72; h,6.10; n,7.47; o,4.93, HRMS (ESI) m/z: theoretical value: 1305.51; actual measurement value: 1306.57 (M+H). As shown in FIG. 5, the MALDI-TOF-MS spectrum of the NFA-4 is shown.
Example 5: synthesis of fused Ring organic Small molecule NFA-5
The synthesis and treatment of compound NFA-5 is the same as that of NFA-1, with only reactant 1-2 being replaced with compound 2-1 and reactant 1-6 being replaced with compound 1-7.
Elemental analysis: (C78H 75F4N7O4S 4) theory: c,67.95; h,5.48; n,7.11; o,4.64; actual measurement value: c,67.98; h,5.47; n,7.15; o,4.61, HRMS (ESI) m/z: theoretical value: 1377.46; actual measurement value: 1378.53 (M+H). As shown in FIG. 6, the MALDI-TOF-MS spectrum of the NFA-5 is shown.
Example 6: synthesis of fused Ring organic Small molecule NFA-6
The synthesis and treatment of compound NFA-6 is the same as that of NFA-1, with only reactant 1-2 being replaced with compound 2-1 and reactant 1-6 being replaced with compound 1-8.
Elemental analysis: (C78H 75Cl4N7O4S 4) theory: c,64.85; h,5.23; n,6.79; o,4.43; actual measurement value: c,64.88; h,5.21; n,6.82; o,4.40, HRMS (ESI) m/z: theoretical value: 1444.35; actual measurement value: 1445.37 (M+H). As shown in FIG. 7, the MALDI-TOF-MS spectrum of the NFA-6 is shown.
The condensed ring organic small molecules prepared in the above embodiments 1-6 are respectively used as an active layer electron acceptor material to prepare an organic solar cell, and the organic solar cell adopts a bulk heterojunction structure, as shown in fig. 1, and the specific structure is as follows: ITO/hole transport layer (PEDOT: PSS)/active layer (D18:NFA)/electron transport material (PDIN)/cathode (Al);
battery device 1:
Ultrasonic treatment of the ITO-coated transparent motor substrate in a commercial cleaning agent, rinsing in deionized water, and washing in acetone: ultrasonic degreasing in an ethanol mixed solvent (volume ratio of 1:1), baking in a clean environment until water is completely removed, then cleaning with ultraviolet light and ozone, and performing device preparation after substrate cleaning operation is completed, wherein the specific operation comprises the following steps: spin-coating 30nm PEDOT: PSS (annealing at 100 ℃ for 10 minutes) on ITO, and sequentially spin-coating 120nm active layers in a glove box, wherein the active layers are chloroform solutions of the compounds NFA-1 and D18, the concentration of chloroform is 15mg/mL, and the mass ratio of NFA-1 to D18 is=1.1:1; spin-coating PDIN (15 nm) on the active layer as an electron transport layer; 120nm aluminum was evaporated as cathode.
The chemical structures of D18 and PDIN are shown below:
battery device 2
The present battery device is different from the battery device 1 in that: the acceptor material NFA-1 of the organic solar cell device is replaced with NFA-2.
Battery device 3
The present battery device is different from the battery device 1 in that: the acceptor material NFA-1 of the organic solar cell device is replaced with NFA-3.
Battery device 4
The present battery device is different from the battery device 1 in that: the acceptor material NFA-1 of the organic solar cell device is replaced with NFA-4.
Battery device 5
The present battery device is different from the battery device 1 in that: the acceptor material NFA-1 of the organic solar cell device is replaced with NFA-5.
Battery device 6
The present battery device is different from the battery device 1 in that: the acceptor material NFA-1 of the organic solar cell device is replaced with NFA-6.
Carrying out photovoltaic performance test on the battery devices 1 and 6, wherein the effective area of each device is 0.4cm 2; test conditions: spectral distribution AM1.5G, illumination intensity 100mW/cm 2, AAA solar simulator (Beijing Zhuo Lihan light company), J-V curve was measured with Keithly 2400 digital source meter, all devices were simply packaged with UV glue, and the test was performed normally in an atmospheric environment. The test results are shown in Table 1
Table 1: device embodiment correspondence performance
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Claims (6)
1. A condensed ring organic small molecule is characterized in that: the condensed ring organic small molecule has a structural formula shown as follows:
In the structural formula I and the structural formula II: r1 is any one of C1-C20 alkyl groups, R2 is also any one of C1-C20 alkyl groups, and the C1-C20 alkyl groups refer to straight-chain or branched-chain alkyl groups with 1-20 carbon atoms; x is hydrogen atom or halogen substituent, wherein the halogen substituent is any one of fluorine, chlorine and bromine.
2. The fused ring organic small molecule of claim 1, wherein: the condensed ring organic small molecule has the structural formula as follows:
3. The method for preparing the condensed ring organic small molecule according to claim 1, which comprises the following steps:
(1) A step of preparing a compound 3 or 8 by Stille coupling reaction of the compound 1 and the compound 2 or 7 under the catalysis of triphenylphosphine palladium;
(2) Carrying out Wilsmeier-Hake reaction on phosphorus oxychloride and N, N-dimethylformamide, and carrying out substitution reaction on the phosphorus oxychloride and the N, N-dimethylformamide and the compound 3 or 8 to prepare a compound 4 or 9;
(3) A step of subjecting the compound 4 or 9 to intramolecular cyclization under the catalysis of iodine to prepare a compound 5 or 10;
(4) A step of preparing a structural formula-1 or a structural formula-2 by performing a gram-brain Wen Geer condensation reaction on a compound 5 or a compound 10 and a compound 6 under the catalysis of pyridine;
in the step (1), the reaction is carried out under the protection of nitrogen, and the solvent of the reaction system is dry toluene; the reaction temperature is 80-120 ℃ and the reaction time is 3-24 hours;
In the step (2), the reaction is carried out under the protection of nitrogen, the temperature of the Wilsmeier-Hake reaction is 10-0 ℃, and the reaction time is 0.1-1 hour; the temperature of the substitution reaction is 40-90 ℃ and the reaction time is 2-20 hours; compound 3: phosphorus oxychloride: n, N-dimethylformamide=1:2:2 to 1:20:100;
In the step (3), the solvent of the reaction system is dry toluene; the wavelength of the light source is 250-750 nm, the reaction temperature is 0-110 ℃, and the reaction time is 1-12 hours;
in the step (4), the reaction is carried out under the protection of nitrogen, the temperature of the gram brain Wen Geer condensation reaction is 65-85 ℃, and the reaction time is 8-48 hours.
4. Use of a fused ring organic small molecule according to any one of claims 1 or 2 as an active layer acceptor material in an organic solar cell device.
5. The use of the fused ring organic small molecule of claim 4 as an active layer acceptor material in an organic solar cell device, wherein the fused ring organic small molecule has the structural formula: The active layer of the organic solar cell device is made of condensed ring small organic molecules NFA-1 and D18, and the mass ratio of the NFA-1 to the D18 is 1.1:1.
6. The use of the fused ring organic small molecule of claim 5 as an active layer acceptor material in an organic solar cell device, wherein the process for preparing the organic solar cell device comprises: after ultrasonic treatment, degreasing and cleaning are carried out on the substrate coated with the ITO transparent motor, firstly, 30nm PEDOT: PSS is spin-coated on the ITO, and an active layer and an electron transmission layer are spin-coated in sequence under vacuum or inert gas atmosphere; the active layer is prepared by dissolving the condensed ring small organic molecules NFA-1 and D18 in chloroform solution and then spin-coating, the thickness of the active layer is 120nm, and the mass ratio of the condensed ring small organic molecules NFA-1 to D18 is 1.1:1; the electron transport layer is formed by PDIN spin coating on the active layer, and the thickness of the electron transport layer is 15nm and is used as the electron transport layer; 120nm aluminum was evaporated as cathode.
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| CN110606856A (en) * | 2019-07-24 | 2019-12-24 | 南京理工大学 | 3-alkyl thiophene-based hepta-fused heterocyclic conjugated small molecule and preparation method and application thereof |
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