CN106589325B - Conjugated polymer containing benzo [ c ] cinnoline and synthesis method and application thereof - Google Patents

Conjugated polymer containing benzo [ c ] cinnoline and synthesis method and application thereof Download PDF

Info

Publication number
CN106589325B
CN106589325B CN201611102108.7A CN201611102108A CN106589325B CN 106589325 B CN106589325 B CN 106589325B CN 201611102108 A CN201611102108 A CN 201611102108A CN 106589325 B CN106589325 B CN 106589325B
Authority
CN
China
Prior art keywords
drying
polymer
monomer
cinnoline
intermediate compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201611102108.7A
Other languages
Chinese (zh)
Other versions
CN106589325A (en
Inventor
赵斌
曾昭魁
黄美华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiangtan University
Original Assignee
Xiangtan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiangtan University filed Critical Xiangtan University
Priority to CN201611102108.7A priority Critical patent/CN106589325B/en
Publication of CN106589325A publication Critical patent/CN106589325A/en
Application granted granted Critical
Publication of CN106589325B publication Critical patent/CN106589325B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three 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
    • C07F5/02—Boron compounds
    • 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
    • C07F7/22—Tin compounds
    • C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/411—Suzuki reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/414—Stille reactions
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The invention discloses a compound containing benzo [ c]Cinnoline conjugated polymer and its synthesis process and application. Based on benzo [ c ] s as mentioned in the present invention]Conjugated polymer structural formula of cinnoline. Based on benzo [ c ] s of the invention]Most common organic solar cell (OPVs) devices prepared by using cinnoline conjugated Polymer as photosensitive material (device structure: ITO/PEDOT: PSS/Polymer: PC)71BM/LiF/Al), which has high open-circuit voltage, wide and strong spectral response range, ideal filling factor, large short-circuit current density and energy conversion efficiency as high as 7.92 percent, and fully shows the potential and good application prospect of the polymer in OPVs.

Description

Conjugated polymer containing benzo [ c ] cinnoline and synthesis method and application thereof
Technical Field
The invention relates to the field of organic photovoltaic cell (OPVs) materials and structures, in particular to a conjugated polymer and a preparation method and application thereof.
Background
With the development of society, energy problems have become an increasingly important topic, and especially clean energy represented by solar energy, wind energy, water energy and the like is the focus of exploration and research of people. Organic photovoltaic cells (OPVs) are devices that convert solar energy into electrical energy using organic/polymeric semiconductor materials as photoactive layers. Compared with other types of solar cells, OPVs have the advantages of low cost, light weight, simple manufacturing process, large-scale printing, flexibility, and the like, and have shown great commercial application prospects. The PCE of the organic solar cell is over 10% at present, but the photoelectric conversion efficiency of the organic solar cell is still a certain gap from the requirement of realizing commercial application. In order to further improve the performance of organic solar cells, new structural units must be continuously explored, and new high-performance photovoltaic materials must be designed and synthesized.
Benzo [ c ] cinnoline (ZL) is a nitrogen-containing heterocyclic compound and has good coplanarity, and ZL-based polymers are used in the fields of organic field-effect transistors and organic light emission. Jyh-Chien Chen et al performed a Horner-Wattsworth-Eimens reaction of a dialdehyde derivative of benzo [ C ] cinnoline and diphosphine ester of benzene to successfully obtain a polymer with n-type carrier transport characteristics and prepare an organic field effect transistor (Synthesis and Properties of air-stable n-channel semiconductor based on MEH-PPV derivative connecting tubes [ C ] cinnoline moieties, Journal of Materials Chemistry C,2014,2, 4835-4846); subsequently, they copolymerized benzo [ c ] cinnoline with fluorene, and the obtained polymer achieved ultraviolet radiation-enhanced photoluminescence (UV-irradiation-enhanced photoluminescence emission of polyfluorenes compatible heterocyclic ketones [ c ] cinnoline moieties, Macromolecules,2015,48(13), 4373-containing 4381). However, to date, the use of benzo [ c ] cinnoline in OPVs has not been found. The invention introduces benzo [ c ] cinnoline into OPVs for the first time, and simultaneously introduces two fluorine atoms into the benzo [ c ] cinnoline to enhance the intermolecular force of the polymer, improve the carrier mobility, reduce the HOMO and LUMO energy levels of the polymer and obtain a2, 9-difluorobenzo [ c ] cinnoline conjugated unit (DFZL).
Disclosure of Invention
In view of the above problems, the present invention provides a benzo [ c ] cinnoline-based conjugated polymer, a preparation method thereof, and use thereof in OPVs.
The technical scheme of the invention is as follows:
a conjugated polymer containing benzo [ c ] cinnoline having the following general formula (I):
Figure BDA0001170657150000021
in the formula (I), X is hydrogen or fluorine; ar is a conjugated aromatic ring derivative containing an alkyl side chain; n is a natural number of 5 to 1000.
In the formula (I), Ar is a conjugated aromatic ring derivative containing an alkyl side chain, and the structural formula of the derivative is shown as a formula (II) or a formula (III):
Figure BDA0001170657150000022
in the formulas (II) and (III), R is straight-chain alkane or branched alkane with 4-30 carbon atoms; d is an electron-rich conjugated structural unit; a is an electron-deficient conjugated structural unit.
D in formula (II) is an electron-rich conjugated structural unit, and the structure of D is as follows, but not limited to the following formula:
Figure BDA0001170657150000023
in the structural formula of each unit, R is straight-chain alkane or branched-chain alkane with 4-30 carbon atoms.
A in formula (III) is an electron-deficient conjugated structural unit, and the structure is listed as follows, but not limited to the following formula:
Figure BDA0001170657150000031
in the structural formula of each unit, R is straight-chain alkane or branched-chain alkane with 4-30 carbon atoms.
A conjugated polymer PZL-D based on a benzo [ c ] cinnoline derivative and an electron-rich conjugated structural unit (D) in formula (I) and a synthesis method thereof: the dibromide monomer of benzo [ c ] cinnoline derivative flanked by alkylthiophene (M1) and the bilateral tin reagent monomer of electron-rich conjugated structural unit D (M2) were subjected to Stille coupling polymer reaction, as shown below:
Figure BDA0001170657150000032
in the structural formula, X is hydrogen or fluorine; r is straight-chain alkane or branched-chain alkane with 4-30 carbon atoms.
A conjugated polymer PZL-A based on benzo [ c ] cinnoline derivatives and electron-deficient conjugated structural units in formula (I) is synthesized by the following method: obtained by carrying out Suzuki coupled polymerization reaction on a dibromo compound monomer M1 of benzo [ c ] cinnoline derivative flanked by alkylthiophene and a bilateral pinacol borate monomer M3 of an electron-deficient conjugated structural unit A as follows:
Figure BDA0001170657150000033
in the structural formula, X is hydrogen or fluorine; r is straight-chain alkane or branched-chain alkane with 4-30 carbon atoms.
The above-mentioned bisbromine compound monomer (M1) of a benzo [ c ] cinnoline derivative of a dialkylthiophene is prepared as shown in the following formulae (IV), (V), (VI):
Figure BDA0001170657150000041
wherein, the intermediate compound 1 is synthesized by the following steps: 1-10mmol of 1, 4-dibromobenzene (1, 4-dibromo-2-fluorobenzene), a magnetic stirrer, 50-150mL of weak polar solvent, 5-10mL of trifluoroacetic acid and 10-20mL of trifluoroacetic anhydride are sequentially added into a dry single-neck round-bottom flask, and the mixture is stirred for 10-60min under ice bath. Adding 2-20mmol of NH in batches4NO3Solid powder, when the solution became orange, the solution was removed from the ice bath and reacted for 6-48 hours. Pouring the reaction mixed solution into 50-400mL of distilled water, extracting with a weak polar solvent, combining organic phases, washing with water, drying the organic phases with anhydrous magnesium sulfate, filtering, carrying out spin-drying on the solvent in the filtrate by using a rotary evaporator to obtain a crude product, and passing the crude product through a silica gel column (using petroleum ether/dichloromethane as an eluent) to obtain white solid powder, namely the intermediate compound 1.
The weak polar solvent is dichloromethane, chloroform, diethyl ether, acetone, benzene, toluene, tetrahydrofuran, etc.
The synthesis steps of the intermediate compound 2 are as follows: adding 1-10mmol of intermediate compound 1 into a reaction bottle, adding 10-30mmol of copper powder, adding 20-100mL of strong polar solvent, heating to 60-180 ℃ under the protection of nitrogen, reacting for 1-12 hours, cooling the reaction to room temperature, adding 10-100mL of toluene, filtering out the residual copper powder, and washing with saturated brine. Finally, the organic layer is dried and spin-dried by anhydrous magnesium sulfate, and finally recrystallized by ethanol to obtain yellow crystals as the intermediate compound 2.
The strong polar solvent is N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, methanol and the like.
Preferably, the synthesis steps of the intermediate compound 3 are as follows: adding 1-10mmol of intermediate compound 2, 1-10mmol of 4-alkyl-2-tributyltin-thiophene, 0.01-1mmol of palladium catalyst and 10-200mL of weak polar solvent in sequence into a clean and dried three-necked bottle, and adding the mixture into the bottle in the presence of N2Heating to 60-150 ℃ under protection and reacting for 6-48h in a dark place. And (3) cooling the reaction mixture to room temperature, extracting with a weak polar solvent, washing the organic phase with water, drying with anhydrous magnesium sulfate, filtering, drying the solvent in the filtrate by spinning to obtain a crude product, and performing column chromatography on the crude product by using petroleum ether/dichloromethane as an eluent to obtain a yellow solid as an intermediate compound 3.
The weak polar solvent is dichloromethane, chloroform, diethyl ether, acetone, benzene, toluene, tetrahydrofuran, etc. The palladium catalyst is tetratriphenylphosphine palladium, tris (dibenzylideneacetone) dipalladium (0), or the like. The synthesis steps of the intermediate compound 4 are as follows: and (2) sequentially adding 1-10mmol of lithium aluminum hydride and 10-100mL of a weak polar solvent into a clean and dried three-necked bottle, and slowly dropwise adding a mixed solution of 1-10mmol of the intermediate compound 3 and the weak polar solvent under the condition of refluxing under the protection of inert gas (such as nitrogen and argon). And after the addition is finished, refluxing for 1-10 hours, cooling to room temperature, extracting the reaction mixed solution by using a weak-polarity solvent, washing an organic phase by using water, drying by using anhydrous magnesium sulfate, filtering, and carrying out column chromatography on the filtrate by using petroleum ether/dichloromethane as an eluent to obtain a yellow solid, namely the intermediate compound 4.
The weak polar solvent is dichloromethane, chloroform, diethyl ether, acetone, benzene, toluene, tetrahydrofuran, etc.
The synthesis steps of the polymerized monomer M1 are as follows: and (2) sequentially adding 1-10mmol of the intermediate compound 4 and 20-200mL of a weak polar solvent into a clean and dried three-necked bottle to fully dissolve the intermediate compound, and then transferring the three-necked bottle to an ice bath condition to stir for 10-60 min. Slowly adding 1-20mmol NBS, reacting at room temperature for 6-24 hours after the addition, extracting the reaction mixture by using a weak polar solvent, washing an organic phase by using water, drying by using anhydrous magnesium sulfate, filtering, carrying out column chromatography purification on the filtrate by using petroleum ether as an eluent to obtain a yellow solid, namely the monomer M1.
The weak polar solvent is dichloromethane, chloroform, diethyl ether, acetone, benzene, toluene, tetrahydrofuran, etc.
The monomer M2 can be synthesized by the following method: dissolving 1-10mmol of a compound with a structure of a D conjugated unit in a solvent weak polar solvent, dropwise adding n-butyl lithium at the temperature of-78-25 ℃ (the feeding ratio of D to n-butyl lithium is 1: 0.5-4), reacting the reaction mixed solution at the temperature of-78-25 ℃ for 0.5-12 hours, then adding trimethyl tin chloride (the feeding ratio of D to trimethyl tin chloride is 1: 0.5-4), and reacting for 0.5-12 hours; adding water, extracting with nonpolar solvent, washing with water, drying, filtering, and spin drying. Recrystallization from a nonpolar solvent/methanol afforded monomer M2 based on D6.
The weak polar solvent is dichloromethane, chloroform, diethyl ether, acetone, benzene, toluene, tetrahydrofuran, etc. The nonpolar solvent is petroleum ether or n-hexane.
The synthesis process of the monomer M3 can adopt the following method: the dibromide compound of the electron-deficient conjugated structural unit A and bis-pinacol borate are synthesized under the condition of taking 1, 1-bis (diphenylphosphino) ferrocene palladium dichloride as a catalyst, and the preparation method is shown in a formula (VII) and comprises the following steps:
Figure BDA0001170657150000051
the conjugated polymer PZL-D is synthesized by a Stille coupling polymerization method, and the synthesis method comprises the following steps: dissolving 0.5mmol of monomer M1 and 0.5mmol of monomer M2 in 2-20mL of toluene, adding 0.005-0.05mmol of tetrakis (triphenylphosphine) palladium (or other palladium catalysts) under the protection of nitrogen, heating to 60-140 ℃, reacting for 6-48h, cooling to room temperature, adding CH3OH is settled, the solid obtained by filtration is wrapped by filter paper and is placed in a Soxhlet extractor to be sequentially coated by CH3OH, acetone, petroleum ether and CHCl3Extracting to obtain CHCl3The solution was spin dried and vacuum dried to give orange, redAnd (3) a colored or purple black solid (different colors according to the structural difference of the electron-rich conjugated structural units) is the polymer PZL-D.
The conjugated polymer PZL-A is synthesized by a Suzuki coupling polymerization method, and the synthesis method comprises the following steps: dissolving 0.5mmol of monomer M1 and 0.5mmol of monomer M3 in 2-20mL of toluene under the protection of nitrogen, adding 0.005-0.05mmol of tetrakis (triphenylphosphine) palladium (or other palladium catalysts) and 1-10mL of 2mol/L potassium carbonate aqueous solution, heating to 60-140 ℃ for reaction for 6-48h, cooling to room temperature after the reaction is finished, and reacting with CH3OH is settled, the solid obtained by filtration is wrapped by filter paper and is placed in a Soxhlet extractor to be sequentially coated by CH3OH, acetone, petroleum ether and CHCl3Extracting to obtain CHCl3And (3) spin-drying the solution, and performing vacuum drying to obtain a purple black, blue or green solid (different colors according to the structural difference of the electron-deficient conjugated structural units), namely the polymer PZL-A.
The benzo [ c ] cinnoline-based conjugated polymer of the present invention is specifically a polymer represented by the following formula P1-P6.
Figure BDA0001170657150000061
The polymer of formula (I) is applied to the preparation of forward OPVs and reverse OPVs as shown in FIGS. 6 and 7. The forward OPVs device and the reverse OPVs device are shown in the following figures, wherein the anode modification layer is PEDOT: PSS or MoO3, the photoactive layer is polymer (PZL-D or PZL-A)/PCBM or polymer (PZL-D or PZL-A)/non-fullerene electron acceptor material; the cathode modification layer is LiF, PFN, calcium and the like; the metal is aluminum or silver.
The preparation process of the positive OPVs device comprises the following steps: spin-coating PEDOT/PSS solution (2000rpm, time is 30s) on cleaned ITO (indium tin oxide) conductive glass, then placing the ITO/PSS solution in an oven to bake for 10-30 minutes at the temperature of 150 ℃ (or evaporating a layer of MoO3 with the thickness of 10-30 nm), then spin-coating the solution of polymer (PZL-D or PZL-A)/fullerene derivative or polymer (PZL-D or PZL-A)/non-fullerene electron acceptor material on the ITO/PSS solution as an optical active layer (the spin-coating speed of the mixed solution is 600-4000rpm), then spin-coating a layer of PFN with the thickness of 2-15nm on the optical active layer, or evaporating LiF with the thickness of 0.2-0.8nm, or calcium with the thickness of 5-30nm, and then evaporating metallic aluminum or silver with the thickness of 50-150 nm. Thus, a positive OPVs device is fabricated.
The preparation process of the reverse OPVs device comprises the following steps: spin-coating a layer of PFN with the thickness of 2-15nm on cleaned ITO (indium tin oxide) conductive glass, then spin-coating a solution of polymer (PZL-D or PZL-A)/fullerene derivative or polymer (PZL-D or PZL-A)/non-fullerene electron acceptor material on the PFN to form a photoactive layer (the spin-coating speed of the mixed solution is 600 plus 4000rpm), then vapor-coating a layer of MoO3 with the thickness of 5-20nm on the photoactive layer, and finally vapor-coating metallic aluminum or silver with the thickness of 50-150 nm. Thereby fabricating an inverted OPVs device.
The invention introduces benzo [ c ] cinnoline into OPVs for the first time, and simultaneously introduces two fluorine atoms into the benzo [ c ] cinnoline to enhance the intermolecular force of the polymer, improve the carrier mobility, reduce the HOMO and LUMO energy levels of the polymer and obtain a2, 9-difluorobenzo [ c ] cinnoline conjugated unit (DFZL).
Based on benzo [ c ] s of the invention]Most common organic solar cell (OPVs) devices prepared by using cinnoline conjugated Polymer as photosensitive material (device structure: ITO/PEDOT: PSS/Polymer: PC)71BM/LiF/Al), which has high open circuit voltage, wide and strong spectral response range, ideal filling factor, large short circuit current density, high energy conversion efficiency up to 7.92%, low process cost and environmental friendliness, and fully shows potential and good application prospect in OPVs.
Drawings
FIG. 1 is a thermogravimetric analysis curve of the P1P2P3P5P6 conjugated polymer obtained in the example preparation.
FIG. 2 shows the UV absorption spectrum of P1P2P3P5P6 conjugated polymer in chloroform solution prepared in example.
FIG. 3 is a cyclic voltammogram of the P1P2P3P5P6 conjugated polymer prepared in the example.
FIG. 4 shows P1P2P3P5P6 conjugated polymer and P prepared by the example71Current density of photoelectric device prepared by blending CBMDegree (J) -voltage (V) curve.
FIG. 5 shows the UV absorption spectra of P3 and ITIC prepared in the example in chloroform solution.
Fig. 6 is a block diagram of a forward OPVs device.
Fig. 7 is a block diagram of an inverted OPVs device.
Figure 8 polymer photovoltaic device performance.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited to the structures described in the following examples.
Example 1
Synthesis of benzo [ c ] cinnoline-based conjugated Polymer (P1)
Figure BDA0001170657150000081
The preparation method of the intermediate 1(1, 4-dibromo-2-fluoro-5-nitrobenzene) is carried out according to the above equation, and the specific operation is as follows: to a 100mL dry single neck round bottom flask was added (5.0g, 19.70mmol)1, 4-dibromo-2-fluorobenzene, magnetic stirrer, 30mL Dichloromethane (DCM), 8mL trifluoroacetic acid (TFA), 16mL trifluoroacetic anhydride (TFAA) in that order, and stirred in ice bath for 30 min. Ammonium nitrate (2.0g, 25.0mmol) as a solid powder was added portionwise. After the addition was complete, the reaction was continued at room temperature for 24 h. Pouring the solution into 100mL of distilled water, extracting with dichloromethane, combining organic phases, drying the organic phases with anhydrous magnesium sulfate, filtering, evaporating the filtrate in a rotating manner to obtain a crude product, and performing column chromatography on the crude product by using a silica gel column (petroleum ether is used as an eluent) to obtain white solid powder, namely the intermediate 1, wherein the yield is 85%.1H NMR(400MHz,CDCl3,δ/ppm):8.19-8.18(d,J＝5.43Hz,1H),7.54-7.53(d,J＝6.85Hz,1H).
The preparation method of the intermediate 2 is carried out according to the above equation, and the specific operation is as follows: adding the intermediate 1(5.0g, 16.73mmol) into a reaction bottle, adding copper powder (1.4g, 22.02mmol), adding 60mL of N, N-Dimethylformamide (DMF), introducing nitrogen for protection, placing the system into a 120-DEG bath kettle for reaction for three hours, and cooling to room temperatureAt room temperature, adding 30mL of toluene, filtering out the residual copper powder, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, carrying out spin-drying on the solvent in the filtrate to obtain a crude product, recrystallizing the crude product with ethanol, and finally obtaining a yellow crystal, namely the intermediate 2, wherein the yield is 46%.1H NMR(400MHz,CDCl3,δ/ppm):8.56-8.54(d,J＝6.07Hz,2H),7.08-7.06(d,J＝7.53Hz,2H).
Intermediate 3-C6C8The preparation method is carried out according to the equation, and the specific operation is as follows: the intermediate compounds 2(2g, 4.57mmol), 2- (tributyltin) -4- (2-hexyldecanoyl) thiophene (6g,10.5mmol) and Pd (PPh) were added in this order to a clean and dried three-necked flask3)4(0.20g,0.18mmol) and 100mL of freshly distilled toluene, then N2Raising the temperature to 110 ℃ under protection and reacting for 30 h. The reaction was cooled to room temperature and then quenched with CH2Cl2Extracting, washing organic phase with water, drying with anhydrous magnesium sulfate, filtering, spin-drying the filtrate with solvent to obtain crude product, performing column chromatography with petroleum ether/dichloromethane as eluent to obtain yellow solid as intermediate 3-C6C8The yield was 80.1%.1H NMR(400MHz,CDCl3,δ/ppm):8.55-8.53(d,J＝6.89Hz,2H),7.43(s,2H),7.11(s,2H),7.08(s,2H),7.07(s,2H)2.60-2.58(d,J＝6.68Hz,4H),1.64-1.59(t,1H),1.37-1.26(m,48H),0.93-0.85(m,12H).
Intermediate 4-C6C8The preparation method is carried out according to the equation, and the specific operation is as follows: adding lithium aluminum hydride (0.61g,16.00mmol) and 70mL of newly distilled ether in sequence into a clean and dried three-necked bottle, and introducing N for 30min2Flow then at N2Slowly dropping the intermediate 3-C under the condition of reflux under protection6C8(1.79g,2.00mmol) and benzene. After the addition, the reaction is carried out for 2 hours under the condition of reflux, and CH is used after the reaction system is cooled to room temperature2Cl2Extracting, washing organic phase with water, drying with anhydrous magnesium sulfate, filtering, spin-drying the filtrate with solvent to obtain crude product, performing column chromatography with petroleum ether/dichloromethane as eluent to obtain yellow solid as intermediate 4-C6C8The yield was 79%.1H NMR(400MHz,CDCl3,δ/ppm):9.01-8.99(d,J＝7.43Hz,2H),8.10-8.07(d,J＝11.37Hz,2H),7.56(s,2H),7.09(s,2H),2.64-2.62(d,J＝6.64Hz,2H),1.68(s,2H),1.31-1.27(m,48H),0.88-0.85(m,12H)
Monomer M1-C6C8The preparation method is carried out according to the equation, and the specific operation is as follows: adding the intermediate compound 4-C into a clean and dried 250mL three-necked bottle in sequence6C8(0.83g,1.00mmol) and chloroform were dissolved sufficiently, and the mixture was transferred to an ice bath and stirred for 30 min. N-bromosuccinimide (0.38g, 2.1mmol) was slowly added thereto, followed by reaction at room temperature overnight, and after completion of the reaction, CH was added thereto2Cl2Extracting, washing the organic phase with water, drying with anhydrous magnesium sulfate, filtering, spin-drying the filtrate to obtain crude product, purifying by column chromatography with petroleum ether as eluent to obtain yellow solid monomer M1-C6C8The yield was 80%.1H NMR(400MHz,CDCl3,δ/ppm):8.90-8.89(d,J＝6.13Hz,2H),8.06-8.03(d,J＝11.02Hz,2H),7.40(s,2H),7.09(s,2H),2.58-2.56(d,J＝6.03Hz,2H),1.73(s,2H),1.31-1.27(m,48H),0.88-0.85(m,12H)。
The preparation method of the conjugated polymer P1 is carried out according to the above equation, and the specific operation is as follows: adding M1-C into a 50mL three-necked bottle6C8(0.20g, 0.2mmol), M3-A1(0.16g,0.2mmol) and 10mL of toluene were introduced with nitrogen for 15 minutes, tetrakis (triphenylphosphine) palladium (4.6mg,0.004mmol) and 4mL of a 2M aqueous solution of potassium carbonate were added, the mixture was heated to 110 ℃ and stirred for reaction for 48 hours, after the reaction was completed, the mixture was cooled to room temperature, the reacted solution was dropped into 200mL of methanol, and then suction filtration was carried out to collect a black solid. Then, a Soxhlet extractor is adopted to extract the polymer by methanol (12h), acetone (12h), normal hexane (12h) and chloroform (12h) in sequence, and the chloroform extract of the polymer is dried by spinning to obtain a purple black polymer solid, namely the polymer P1.
Example 2
Synthesis of benzo [ c ] cinnoline-based conjugated Polymer (P2)
Figure BDA0001170657150000101
Intermediate 3-C8C10The preparation method is carried out according to the equation, and the specific operation is as follows: the intermediate compound 2(2g, 4.57mmol), 2- (tributyltin) -4- (2-octyldecyl) thiophene (6.86g,10.5mmol), Pd (PPh) were added in this order to a clean and dried three-necked flask3)4(0.21g,0.18mmol) and 100mL of freshly distilled toluene, then N2Raising the temperature to 110 ℃ under protection and reacting for 30 h. The reaction was cooled to room temperature and then quenched with CH2Cl2Extracting, washing organic phase with water, drying with anhydrous magnesium sulfate, filtering, spin-drying the filtrate with solvent to obtain crude product, performing column chromatography with petroleum ether/dichloromethane as eluent to obtain yellow solid as intermediate 3-C8C10The yield was 80.1%.1H NMR(400MHz,CDCl3,δ/ppm):8.55-8.53(d,J＝6.89Hz,2H),7.43(s,2H),7.11(s,2H),7.08(s,2H),7.07(s,2H)2.60-2.58(d,J＝6.68Hz,4H),1.64-1.59(m,1H),1.37-1.26(m,64H),0.93-0.85(m,12H).
Intermediate 4-C6C8The preparation method is carried out according to the equation, and the specific operation is as follows: adding lithium aluminum hydride (0.68g,18.00mmol) and 70mL of newly distilled ether in sequence into a clean and dried three-necked bottle, and introducing N for 30min2Flow then at N2Slowly dropping the intermediate 3-C under the condition of reflux under protection8C10(1.90g,2.00mmol) and benzene. After the addition, the reaction is carried out for 2 hours under the condition of reflux, and CH is used after the reaction system is cooled to room temperature2Cl2Extracting, washing organic phase with water, drying with anhydrous magnesium sulfate, filtering, spin-drying the filtrate with solvent to obtain crude product, performing column chromatography with petroleum ether/dichloromethane as eluent to obtain yellow solid as intermediate 4-C8C10The yield was 79%.1H NMR(400MHz,CDCl3,δ/ppm):9.01-8.99(d,J＝7.43Hz,2H),8.10-8.07(d,J＝11.37Hz,2H),7.56(s,2H),7.09(s,2H),2.64-2.62(d,J＝6.64Hz,2H),1.68(m,2H),1.31-1.27(m,64H),0.88-0.85(m,12H).
Monomer M1-C8C10The preparation method is carried out according to the equation, and the specific operation is as follows: adding the intermediate compound 4-C into a clean and dried 250mL three-necked bottle in sequence8C10(0.94g,1.00mmol) and chloroform were dissolved sufficiently, and then the mixture was transferred to an ice bath and stirred for 30 min. N-bromosuccinimide (0.37g, 2.1mmol) was slowly added thereto, followed by reaction at room temperature overnight, and after completion of the reaction, CH was added thereto2Cl2Extracting, washing the organic phase with water, drying with anhydrous magnesium sulfate, filtering, spin-drying the filtrate to obtain crude product, purifying by column chromatography with petroleum ether as eluent to obtain yellow solid monomer M1-C8C10The yield was 80%.1H NMR(400MHz,CDCl3,δ/ppm):8.90-8.89(d,J＝6.13Hz,2H),8.06-8.03(d,J＝11.02Hz,2H),7.40(s,2H),2.58-2.56(d,J＝6.03Hz,2H),1.73(m,2H),1.31-1.27(m,64H),0.88-0.85(m,12H)。
The preparation method of the conjugated polymer P2 is carried out according to the above equation, and the specific operation is as follows: adding M1-C into a 50mL three-necked bottle8C10And 0.2mmol of each of M2-D1, dissolving the mixture in a solvent of toluene (6mL), adding tetrakis (triphenylphosphine) palladium (4.62mg0.004mmol) under the protection of nitrogen, heating to 110 ℃, stirring for reaction for 48 hours, cooling to room temperature after the reaction is finished, dropwise adding the reacted solution into 50mL of methanol, and then carrying out suction filtration to collect black solids. Then, a Soxhlet extractor is adopted to extract the polymer by methanol (12h), acetone (12h), normal hexane (12h) and chloroform (12h) in sequence, and the chloroform extract of the polymer is dried by spinning to obtain a purple black polymer solid, namely the polymer P2. Yield 57%, GPC: mn＝21.8kDa，Mw/Mn＝2.4，1HNMR(400MHz,CDCl3,δ/ppm):8.90-8.89(br,J＝6.13Hz,2H),8.06-8.03(br,J＝11.02Hz,2H),7.56(br,2H),7.09(s,2H),2.58-2.93(br,J＝6.03Hz,2H),1.11-1.97(m,64H),0.88-0.85(m,12H)。
Example 3
Synthesis of benzo [ c ] cinnoline-based conjugated Polymer (P3)
Figure BDA0001170657150000111
The preparation method of the conjugated polymer P3 is carried out according to the above equation, and the specific operation is as follows: taking a monomer M1-C8C10And M2-D3 were dissolved in toluene (6mL) at 0.2mmol, tetrakis (triphenylphosphine) palladium (4.62mg0.004mmol) was added under nitrogen protection, and polymerization was stopped after 24h at toluene reflux temperature. The polymer solution was cooled to room temperature, slowly precipitated into methanol (50mL), and the precipitated solid polymer was sequentially extracted with methanol, n-hexane, acetone, dichloromethane, and chloroform in a soxhlet extractor. Finally, the chloroform extract was added dropwise to methanol, filtered, and the solid obtained was dried in vacuo for one day to give a reddish brown solid powder, i.e., polymer P3, yield 69%, GPC: mn＝24.8kDa，Mw/Mn＝2.1，1H NMR(400MHz,CDCl3,δ/ppm):8.90-8.89(br,J＝6.13Hz,2H),8.06-8.03(br,J＝11.02Hz,2H),7.56(br,2H),6.09(br,4H),2.58-2.93(br,J＝6.03Hz,2H),1.11-1.97(m,64H),0.88-0.85(m,12H)。
Example 4
Synthesis of benzo [ c ] cinnoline-based conjugated Polymer (P4)
Figure BDA0001170657150000121
Taking the monomer M1-C according to the reaction equation8C10And M2-D4 were dissolved in toluene (6mL) in an amount of 0.2mmol each, and then tetrakis (triphenylphosphine) palladium (4.62mg0.004mmol) was added under nitrogen, followed by polymerization at toluene reflux temperature for 24 hours and then stopped. The polymer solution was cooled to room temperature, slowly precipitated into methanol (50mL), and the precipitated solid polymer was extracted in a soxhlet extractor with methanol, n-hexane, acetone, dichloromethane, and chloroform in this order. And finally, dripping the chloroform extract into methanol, and drying the filtered filter residue in vacuum for one day to obtain a reddish brown solid powder, namely the polymer shown as the formula P5, wherein the polymer is too poor in solubility and has no relevant test.
Example 5
Synthesis of benzo [ c ] cinnoline-based conjugated Polymer (P5)
Figure BDA0001170657150000122
Taking the monomer M1-C according to the reaction equation6C8And M2-D8 were dissolved in toluene (6mL) in an amount of 0.2mmol each, and then tetrakis (triphenylphosphine) palladium (4.62mg0.004mmol) was added under nitrogen, followed by polymerization at toluene reflux temperature for 24 hours and then stopped. The polymer solution was cooled to room temperature, slowly precipitated into methanol (50mL), and the precipitated solid polymer was extracted in a soxhlet extractor with methanol, n-hexane, acetone, dichloromethane, and chloroform in this order. Finally, the chloroform extract was added dropwise to methanol, and the filtered residue was dried in vacuo for one day to obtain a reddish brown solid powder, i.e., a polymer represented by formula P5, in a yield of 76%, GPC: mn＝26.8kDa，Mw/Mn＝2.8，1H NMR(400MHz,CDCl3,δ/ppm):8.90-8.89(br,J＝6.13Hz,2H),8.06-8.03(br,J＝11.02Hz,2H),8.03(s,2H),7.54(s,4H),7.02(s,4H),8.21-6.67(br,6H)，2.58-2.93(br,J＝6.03Hz,2H),1.11-1.97(m,64H),0.88-0.85(m,12H)。
Example 6
Synthesis of benzo [ c ] cinnoline-based conjugated Polymer (P6)
Figure BDA0001170657150000131
Taking the monomer M1-C according to the reaction equation6C8And M2-D9 (0.2 mmol each), which were dissolved in toluene (6mL), tetrakis (triphenylphosphine) palladium (4.62mg0.004mmol) was added under nitrogen, and the reaction was allowed to polymerize at the toluene reflux temperature for 24h, and then stopped. The polymer solution was cooled to room temperature, slowly dropped into methanol (50mL), and the precipitated solid polymer was extracted in a soxhlet extractor with methanol, n-hexane, acetone, dichloromethane, and chloroform in this order. Finally, the chloroform extract is dripped into methanol, and the filtered filter residue is vacuumizedAfter drying for one day, a reddish-brown solid powder was obtained, representing the polymer of formula P6, in 88% yield, GPC: mn＝39.6kDa，Mw/Mn＝2.0，1H NMR(400MHz,CDCl3,δ/ppm):8.90-8.89(br,J＝6.13Hz,2H),8.06-8.03(br,J＝11.02Hz,2H),8.03(s,2H),7.54(s,4H),7.02(s,4H),8.21-6.67(br,6H)，2.58-2.93(br,J＝6.03Hz,2H),1.11-1.97(m,64H),0.88-0.85(m,12H)。
Example 7
Solubility and film formation testing of the polymers of the invention
The polymers P1, P2, P3, P5 and P6 prepared in the examples 1,2, 3, 5 and 6 are placed in common solvents, such as chlorobenzene, 1, 2-dichlorobenzene, chloroform, toluene, trichlorobenzene, methanol, n-hexane, petroleum ether, acetone and the like, and the polymers P1, P2, P3, P5 and P6 have better solubility in chlorobenzene, 1, 2-dichlorobenzene, chloroform, toluene and trichlorobenzene, but are not dissolved in methanol, n-hexane, petroleum ether and acetone. The polymer P4 prepared in example 4 was not soluble in solvents such as chlorobenzene, 1, 2-dichlorobenzene, chloroform, toluene, trichlorobenzene, tetrahydrofuran, etc., probably due to an excessively large molecular weight. Thus, polymer P4 did not characterize other properties.
Example 8
Thermal stability of polymers by thermogravimetric analysis
The polymers P1, P2, P3, P5 and P6 are placed in a Q50 thermogravimetric analyzer of the American TA company, and the thermal decomposition temperature of the polymers is tested under the test conditions that the temperature rising and falling speed is 20 ℃/min and the test temperature range is 50-700 ℃. The test curve is shown in FIG. 1.
Example 9
Testing light absorption capability of polymer by ultraviolet-visible spectrometer
The polymers P1, P2, P3, P5 and P6 were dissolved in chloroform and the absorbance of the solution was measured by a PE Lamda25 type UV-Vis spectrometer. The absorption spectrum is shown in FIG. 2.
Example 10
Electrochemical energy level and energy gap of polymer tested by electrochemical workstation
Mixing polymers P1, P2. Dissolving P3, P5 and P6 in chloroform, dripping onto ITO conductive glass, volatilizing the solvent to obtain working electrode, using metal platinum wire as counter electrode, Ag/AgNO3The electrode is used as a reference electrode, 0.1mol/L acetonitrile solution of tetrabutylammonium hexafluorophosphate is used as an electrolyte solution, and a cyclic voltammetry spectrum (the scanning speed is 100mV/s) of the polymer film is measured on a ZAHNER ZENNIUM electrochemical workstation, and the cyclic voltammetry spectrum is shown in figure 3.
Example 11
The polymer shown in the formula P1 is used as a polymer photovoltaic material to prepare forward organic solar cell (OPVs) devices (also called polymer solar cell PSCs), the device structure of which is shown in FIG. 6, and the specific process is shown as follows.
The ITO glass was subjected to ultrasonic cleaning (30 minutes each) sequentially with an ITO cleaning agent having a concentration of about 5%, deionized water, acetone, ethanol, and isopropyl alcohol. And (3) after the ITO glass is dried, treating the ITO glass with ultraviolet ozone for 5 minutes, then spin-coating PEDOT (PEDOT: PSS) on the ITO glass at the rotating speed of 4000rpm, and then placing the ITO glass in a high-temperature oven at the temperature of 150 ℃ for baking for 15 minutes, so that residual solvents and water on the surfaces of the PEDOT (PEDPSS) can be fully removed (the film thickness is 30-40 nm). The polymer P1 prepared by the invention and PC71BM was dissolved in dichlorobenzene (concentration: 15mg/mL) in a weight ratio of 1:1, and 2 vol% of 1, 8-diiodooctane was added. The blended active layer solution is spin-coated on ITO glass coated with a PEDOT PSS thin layer (the thickness of the active layer is about 100nm), and then the ITO glass is transferred into a vacuum coating chamber until the pressure in the vacuum coating chamber is reduced to 4 multiplied by 10-4Pa, evaporating lithium fluoride with the thickness of 0.5nm, and evaporating metal aluminum with the thickness of about 100nm to prepare a forward solar cell device based on the P1 conjugated Polymer (the structure of the device is ITO/PEDOT: PSS/Polymer: P)71CBM/LiF/Al). AM1.5G sunlight (100 mW/cm) is simulated and obtained by using AAA level sunlight simulator2) The prepared solar cell device was exposed to AM1.5G simulated sunlight, and a current density (J) -voltage (V) curve of the OPVs device was recorded using a digital source meter, thereby obtaining an open circuit voltage (V) of the OPVs deviceoc) Short circuit current density (J)sc) Fill Factor (FF) and energy conversion efficiency(PCE), etc. The photovoltaic parameters are shown in Table 1, and the J-V curves are shown in FIG. 4.
Example 12
The polymers shown in formulas P2, P3, P5 and P6 are used as polymer photovoltaic materials, and the positive-direction OPVs device is prepared by referring to the OPV device structure based on P1 and a preparation method. The photovoltaic parameters are shown in Table 1, and the J-V curves are shown in FIG. 4.
Example 13
An OPVs device of a polymer/non-fullerene system is prepared by taking the polymer shown in the formula P3 as a polymer photovoltaic material and referring to an OPV device structure (figure 6) based on P1 and a preparation method. The prepared polymer P3 of the invention was dissolved in dichlorobenzene in a 1:1 weight ratio with non-fullerene acceptor ITIC (uv-vis spectrum of P3 and ITIC in solution is shown in fig. 5). The blended active layer solution is spin-coated on ITO glass coated with a PEDOT PSS thin layer (the thickness of the active layer is about 100nm), and then the ITO glass is transferred into a vacuum coating chamber until the pressure in the vacuum coating chamber is reduced to 4 multiplied by 10-4Pa, evaporating lithium fluoride with the thickness of 0.5nm, and evaporating metal aluminum with the thickness of about 100nm to prepare the P3 conjugated polymer-based forward solar cell device (the device structure is ITO/PEDOT: PSS/P3: ITIC/LiF/Al). Simulation of obtaining AM1.5G sunlight (100 mW/cm) by using AAA level sunlight simulator2) The prepared solar cell device is exposed to AM1.5G simulated sunlight, and the current density (J) -voltage (V) curve of the OPVs device is recorded by a digital source meter, so that the V of the OPVs device is obtainedoc、JscAnd photovoltaic parameters such as FF and PCE. The photovoltaic parameters are shown in FIG. 8.

Claims (4)

1. A conjugated polymer containing benzo [ c ] cinnoline, which has the structure of formula (I):
Figure FDA0002373718980000011
wherein X is fluorine; ar is a conjugated aromatic ring derivative containing an alkyl side chain, and is characterized in that the structural formula of Ar is shown as a formula (II):
Figure FDA0002373718980000012
wherein, A is an electron-deficient conjugated structural unit, and the structure is as follows:
Figure FDA0002373718980000013
wherein R is straight-chain alkane or branched-chain alkane, and n is a natural number of 5-1000.
2. The method of claim 1, wherein said benzo [ c ] is flanked by alkylthiophenes]Carrying out Suzuki coupled polymerization reaction on a dibromide monomer M1 of cinnoline derivative and a bilateral pinacol borate monomer M3 of an electron-deficient conjugated structural unit A to obtain the cinnoline derivative, dissolving 0.5mmol of a monomer M1 and 0.5mmol of a monomer M3 in 2-20mL of methylbenzene, adding 0.005-0.05mmol of tetrakis (triphenylphosphine) palladium or other palladium catalysts under the protection of nitrogen, heating to 60-140 ℃ for reaction for 6-48h by using 1-10mL of 2mol/L potassium carbonate aqueous solution, cooling to room temperature after the reaction is finished, and reacting with CH3OH is settled, the solid obtained by filtration is wrapped by filter paper and is placed in a Soxhlet extractor to be sequentially coated by CH3OH, acetone, petroleum ether and CHCl3Extracting to obtain CHCl3Spin-drying the solution, and vacuum-drying to obtain purple black, blue or green solid, namely the polymer PZL-A; wherein X in the monomer M1 and the conjugated polymer PZL-A is fluorine, wherein A, R is as defined in claim 1
Figure FDA0002373718980000014
3. The method for synthesizing a conjugated polymer according to claim 2, wherein the method for preparing the monomer M1 comprises the following steps:
(1) sequentially adding 1-10mmol of 1, 4-dibromo-2-fluorobenzene, a magnetic stirrer, 50-150mL of dichloromethane, 5-10mL of trifluoroacetic acid and 10-20mL of trifluoroacetic anhydride into a dry single-mouth round-bottom flask, stirring for 10-60min under ice bath,adding 2-20mmol of NH in batches4NO3Solid powder, when the solution turns orange, removing ice bath from the solution, reacting for 6-48 hours, pouring the reaction mixed solution into 50-400mL of distilled water, extracting with dichloromethane, combining organic phases, washing with water, drying the organic phases with anhydrous magnesium sulfate, filtering, and then spin-drying the solvent in the filtrate by using a rotary evaporator to obtain a crude product, and passing the crude product through a silica gel column by using petroleum ether/dichloromethane as an eluent to obtain white solid powder, namely an intermediate compound Y1;
Figure FDA0002373718980000021
(2) adding 1-10mmol of intermediate compound Y1 into a reaction bottle, adding 10-30mmol of copper powder, finally adding 20-100mL of N, N-dimethylformamide, heating to 60-180 ℃ under the protection of nitrogen, reacting for 1-12 hours, cooling the reaction to room temperature, adding 10-100mL of toluene, filtering out residual copper powder, washing with saturated saline solution, drying and spin-drying an organic layer with anhydrous magnesium sulfate, and finally recrystallizing with ethanol to obtain a yellow crystal which is intermediate compound Y2;
Figure FDA0002373718980000022
(3) adding 1-10mmol intermediate compound Y2, 1-10mmol 4-alkyl-2-tributyltin-thiophene, and 0.01-1mmol Pd (PPh) into a clean and dried three-necked bottle3)4And 10-200mL of toluene, heating to 60-150 ℃ under the protection of N2, reacting for 6-48h in a dark place, cooling the reaction mixture to room temperature, extracting with dichloromethane, washing the organic phase with water, drying with anhydrous magnesium sulfate, filtering, spin-drying the filtrate with a solvent to obtain a crude product, and performing column chromatography on the crude product with petroleum ether/dichloromethane as an eluent to obtain a yellow solid as an intermediate compound Y3, wherein R is defined as in claim 2;
Figure FDA0002373718980000031
(4) sequentially adding 1-10mmol of lithium aluminum hydride and 10-100mL of freshly distilled toluene into a cleaned and dried three-necked bottle, slowly dropwise adding a mixed solution of 1-10mmol of an intermediate compound Y3 and benzene under the condition of reflux under the protection of inert gas, refluxing for 1-10 hours after adding, cooling to room temperature, extracting the reaction mixed solution by using dichloromethane, washing an organic phase by using water, drying by using anhydrous magnesium sulfate, filtering, spin-drying the filtrate by using a solvent to obtain a crude product, and performing column chromatography on the crude product by using petroleum ether/dichloromethane as an eluent to obtain a yellow solid as an intermediate compound Y4, wherein R is defined in claim 2;
Figure FDA0002373718980000032
(5) the intermediate compound Y4 is brominated by N-bromosuccinimide (NBS) to obtain a polymerized monomer M1, which comprises the following steps: sequentially adding 1-10mmol of intermediate compound Y4 and 20-200mL of trichloromethane into a clean and dried three-necked bottle to fully dissolve the intermediate compound Y4 and the trichloromethane, then moving the three-necked bottle to an ice bath condition to stir for 10-60min, then slowly adding 1-20mmol of NBS, reacting at room temperature for 6-24 h after the addition is finished, extracting a reaction mixture by using dichloromethane, washing an organic phase by using water, drying by using anhydrous magnesium sulfate, filtering, drying a filtrate by using a solvent to obtain a crude product, and purifying the crude product by using petroleum ether as an eluent to obtain a yellow solid as a monomer M1, wherein R is defined as claim 2, wherein the yellow solid is a yellow solid, and the yellow solid is a monomer
Figure FDA0002373718980000033
4. The use of a conjugated polymer containing benzo [ c ] cinnoline according to claim 1, wherein the conjugated polymer represented by formula (I) is used for the production of forward OPVs devices and reverse OPVs devices.
CN201611102108.7A 2016-12-05 2016-12-05 Conjugated polymer containing benzo [ c ] cinnoline and synthesis method and application thereof Active CN106589325B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611102108.7A CN106589325B (en) 2016-12-05 2016-12-05 Conjugated polymer containing benzo [ c ] cinnoline and synthesis method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611102108.7A CN106589325B (en) 2016-12-05 2016-12-05 Conjugated polymer containing benzo [ c ] cinnoline and synthesis method and application thereof

Publications (2)

Publication Number Publication Date
CN106589325A CN106589325A (en) 2017-04-26
CN106589325B true CN106589325B (en) 2020-05-05

Family

ID=58594835

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611102108.7A Active CN106589325B (en) 2016-12-05 2016-12-05 Conjugated polymer containing benzo [ c ] cinnoline and synthesis method and application thereof

Country Status (1)

Country Link
CN (1) CN106589325B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019090229A1 (en) * 2017-11-06 2019-05-09 The Regents Of The University Of Michigan Organic photovoltaic cells and non-fullerene acceptors thereof
CN108084408A (en) * 2017-12-13 2018-05-29 湘潭大学 A kind of polymer active layer material containing alkylthio group thiophene-fluoro diazosulfide and preparation method thereof
KR102329624B1 (en) * 2020-04-24 2021-11-22 부경대학교 산학협력단 Polymer solar cell having cathode buffer layer including acid derivative modified conjugate polymer electrolyte

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4956862B2 (en) * 2001-03-23 2012-06-20 Ｔｄｋ株式会社 Polymer compounds and methods for producing and using the same

Also Published As

Publication number Publication date
CN106589325A (en) 2017-04-26

Similar Documents

Publication Publication Date Title
CN101407574B (en) Donor-receptor type conjugated polymer containing dithiophen b pyrrole, preparation method and application thereof
CN108948327B (en) Quinoxaline conjugated polymer, preparation method thereof and application thereof in polymer solar cell
CN107778319B (en) A-D-A type micromolecule compound containing hepta-fused ring structure indacene and preparation method thereof
CN106749428B (en) Polymeric metal complex containing N-thienyl phenylenediamine derivative Co (II) and preparation method and application thereof
CN109641914B (en) Design and synthesis of porphyrin materials for organic photovoltaics
CN110922569B (en) Donor-receptor type ultralow band gap conjugated polymer based on imide pyrazine heterocycle and preparation method and application thereof
CN103857724B (en) The method comprising the polymer of benzo miscellaneous [1,3] diazole unit for preparation
Miao et al. Photochemical synthesis of π-extended ullazine derivatives as new electron donors for efficient conjugated D–A polymers
Lee et al. The effect of acceptor end groups on the physical and photovoltaic properties of A–π–D–π–A type oligomers with same S, N-heteropentacene central electron donor unit for solution processed organic solar cells
CN106589325B (en) Conjugated polymer containing benzo [ c ] cinnoline and synthesis method and application thereof
Morvillo et al. Low band gap polymers for application in solar cells: synthesis and characterization of thienothiophene–thiophene copolymers
CN107698744B (en) Preparation method and application of polymer receptor material
CN104031245A (en) Polymer photovoltaic material, preparation method and use thereof
Chen et al. A Novel Thiophene Derivative‐based Conjugated Polymer for Polymer Solar Cells with High Open‐circuit Voltage
CN110483555B (en) Pyrazine indole terminal receptor-based D (Pi-A)2Small molecular donor material, preparation method and application
CN114716460A (en) Conjugated organic small molecule and preparation method and application thereof
KR101828012B1 (en) Conjugated polymer for organic solar cell and manufacturing method thereof
Lee et al. Benzodithiophene-based wide-bandgap small-molecule donors for organic photovoltaics with large open-circuit voltages
Zhou et al. Novel carbazole-based main chain polymeric metal complexes containing complexes of phenanthroline with Zn (II) or Cd (II): Synthesis, characterization and photovoltaic application in DSSCs
CN116375732A (en) Non-fullerene acceptor material and preparation method and application thereof
CN110577548A (en) Asymmetric fused heterocycle micromolecule electron acceptor material based on dithienopyrrole and application thereof
US11114619B2 (en) Conjugated polymer for a photoactive layer, a coating composition including the conjugated polymer, and an organic solar cell including the photoactive layer
Cui et al. Fluorine functionalized asymmetric indo [2, 3-b] quinoxaline framework based DA copolymer for fullerene polymer solar cells
CN110982047B (en) Indacarbazine difuranyl organic solar cell donor material, and preparation method and application thereof
CN109337046B (en) Polymer donor material containing dibenzothiophene sulfoxide unit and preparation thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20170426

Assignee: HUNAN CHANGLI RAIL TRANSPORTATION EQUIPMENT Co.,Ltd.

Assignor: XIANGTAN University

Contract record no.: X2023980033020

Denomination of invention: A conjugated polymer containing benzo [c] miso line and its synthesis method and application

Granted publication date: 20200505

License type: Common License

Record date: 20230301