WO2017107573A1 - Heptacyclic unit-based conjugated macromolecule, method of preparing same, and application thereof in solar cell - Google Patents

Heptacyclic unit-based conjugated macromolecule, method of preparing same, and application thereof in solar cell Download PDF

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WO2017107573A1
WO2017107573A1 PCT/CN2016/098397 CN2016098397W WO2017107573A1 WO 2017107573 A1 WO2017107573 A1 WO 2017107573A1 CN 2016098397 W CN2016098397 W CN 2016098397W WO 2017107573 A1 WO2017107573 A1 WO 2017107573A1
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formula
group
independently selected
hexyl
compound represented
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Chinese (zh)
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占肖卫
林禹泽
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北京大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to the field of solar cells, in particular to a conjugated macromolecule based on a hepta-fused ring unit, a preparation method thereof and application in a solar cell.
  • Organic solar cells have received a lot of attention in academia because of their low cost, light weight, flexibility, solution processing, and large-area preparation.
  • polymers and small-molecule solar cells have developed rapidly and achieved remarkable results. So far, the photoelectric conversion efficiency of solar cells prepared by blending polymer donors or small molecule donors with fullerene receptors has exceeded 10% through optimization of molecular structure, device structure and processing technology. This shows a huge application prospect of organic solar cells.
  • the polymer material has a relatively high photoelectric conversion efficiency due to its relatively wide range of absorption of sunlight. Through the optimization of material structure and device structure, the highest photoelectric conversion efficiency reported in the literature has reached 10.8%.
  • polymers also have their own shortcomings, such as polydispersity of molecular weight distribution, poor repeatability between batches, and difficulty in purification.
  • organic small molecules and macromolecular semiconductor materials exhibit certain advantages, such as: defined molecular structure and molecular weight, high purity and batch stability. Therefore, recent research on organic small molecules and macromolecular solar cells has become hotter.
  • Receptor materials develop slowly compared to the rapid development of donor materials.
  • fullerene derivatives represented by PC 61 BM and PC 71 BM are firmly in the dominant position. This is because PCBM has many advantages, such as large electron affinity, excellent isotropic electron transport performance, and the ability to mix with donor materials to form nano-sized phase separations.
  • fullerene derivatives represented by PCBM also have many disadvantages, such as weak absorption in the visible region, difficulty in energy level regulation, and difficulty in purification.
  • PCE photoelectric conversion rate
  • the present invention provides a conjugated macromolecule based on a hepta-fused ring unit which is a compound represented by the following formula (1):
  • R 2 are each independently selected from a group shown; two R 1 are each independently selected from a group shown; wherein each Z is independently selected from C or Si; each X and each Y are each independently selected from O, S or Se; m is an integer from 1 to 6; n is an integer from 0 to 6
  • Each R 3 , each R 4 , R 5 , each R 6 and each R 7 are each independently selected from the group consisting of H, a C1-C30 alkyl group, a C1-C30 alkoxy group, and a C6-C12 aryl group; 8 are each independently selected from the group consisting of H, alkyl, halogen, alkoxy, and alkylthio.
  • the present invention also provides a method for producing the above conjugated macromolecule based on a hepta-fused ring unit, wherein the method comprises: compounding a compound represented by the following formula (2) in the presence of a basic compound and in an organic solvent The compound represented by the formula (B) is subjected to a dehydration condensation reaction to obtain a compound represented by the formula (1);
  • Formula (B) is selected from one or more of the following compounds:
  • the present invention also provides a method for producing the above conjugated macromolecule based on a hepta-fused ring unit, wherein the method comprises: compounding a compound represented by the following formula (3) in the presence of a palladium-containing catalyst and in an organic solvent The compound represented by the formula (C) is subjected to a coupling reaction to obtain a compound represented by the formula (1);
  • Formula (C) is selected from one or more of the following compounds:
  • the present invention also provides a photovoltaic material comprising the above conjugated macromolecule based on a hepta-fused ring unit.
  • the present invention also provides a solar cell comprising a light-trapping active layer, wherein the electron-trapping material and/or electron acceptor material in the light-trapping active layer contains the above-described hepta-fused ring unit Conjugated macromolecules.
  • the present invention also provides a method of preparing a solar cell, wherein the method comprises using an electron donor material and/or an electron acceptor material containing the above-mentioned conjugated macromolecule based on a hepta-fused ring unit for forming light trapping. Active layer.
  • the conjugated macromolecule based on hepta-fused ring unit provided by the invention has strong light absorption and high electric charge
  • the transmission performance and a suitable electronic energy level are suitable for use as an electron donor or electron acceptor material for the preparation of a solar cell, and in particular, a solar cell having a photoelectric conversion efficiency of 10% or more can be obtained.
  • Example 1 is an ultraviolet-visible absorption spectrum of a conjugated macromolecule based on a hepta-fused ring unit represented by the formula (1-2) obtained in Example 1 of the present invention, wherein the solution is obtained by using chloroform as a solvent.
  • Solution (10 -6 mol/L) film refers to a film (100 nm thickness) spin-coated with a chloroform solution.
  • Example 2 is a cyclic voltammetry curve of a conjugated macromolecule based on a hepta-fused ring unit represented by the formula (1-2) obtained in Example 1 of the present invention.
  • Fig. 3 is a graph showing the thermogravimetric curve of a conjugated macromolecule based on a hepta-fused ring unit represented by the formula (1-2) obtained in Example 1 of the present invention.
  • Example 4 is a graph showing the space charge-limited current of a conjugated macromolecule based on a hepta-fused ring unit represented by the formula (1-2) obtained in Example 1 of the present invention.
  • Fig. 5 is an I-V curve (current-voltage curve) of the solar cell obtained in Example 3.
  • Fig. 6 is an I-V curve of the solar cell obtained in Example 4.
  • Fig. 7 is an I-V curve of the solar cell obtained in Example 5.
  • Fig. 8 is an I-V curve of the solar cell obtained in Example 6.
  • the dotted line in the structure with a dotted connection key indicates the connection site, indicating the connection key;
  • a solid line in a structure with a solid-line bond that is not connected to any group or atom also indicates a connection site, indicating a linkage.
  • the present invention provides a conjugated macromolecule based on a hepta-fused ring unit which is a compound represented by the following formula (1):
  • R 2 are each independently selected from A group represented by; two R 1 are each independently selected from the formulas a group shown; wherein each Z is independently selected from C or Si (two Zs of formula (1) may be the same or different, independently selected); each X and each Y are each independently selected from O , S or Se (representing when the formula (1) has a plurality of X and Y, the plurality of Xs may be the same or different, and are independently selected; the plurality of Ys may also be the same or different and independently selected); m is an integer from 1 to 6; n is an integer from 0 to 6; each R 3 , each R 4 , R 5 , each R 6 and each R 7 are each independently selected from H, C1-C30 alkyl, C1- An alkoxy group of C30 and an aryl group of C6-C12 (representing that when each group appears simultaneously in multiple places in the compound of formula (1), they are independently selected, may be the same, or may be different For example, despite There are two R 6
  • each of the four R 2 is independently selected from the formula a group shown and two R 1 are each independently selected from
  • the compound of the formula (1) can be represented by the following formula (1'):
  • m is preferably an integer of 1-4
  • n is An integer from 0-4.
  • n 0, and R 1 is considered to be absent, and the group A is directly bonded to the hepta-fused ring unit main body of the compound represented by the formula (1) to form a conjugated structure.
  • each of R 8 is selected from H, and the resulting group A is represented by the following formula:
  • each R 8 is independently selected from the group consisting of alkyl, halogen, alkoxy and alkylthio, preferably selected from C1-C6 alkyl, halogen, C1-
  • the alkoxy group of C6 and the alkylthio group of C1-C6 are preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, F, Cl, Br, methoxy, ethoxy, and C.
  • each R 3 , each R 4 , each R 6 and each R 7 are each independently selected from the group consisting of H, a C1-C30 alkyl group and a C1-C30 alkoxy group, and R 5 is a C6-C12 aryl group. .
  • each R 3 , each R 4 , each R 6 and each R 7 are each independently selected from the group consisting of H, C1-C12 alkyl and C1-C12 alkoxy, and R 5 is selected from phenyl or benzyl. base.
  • m is 1, 2 or 3
  • n is 0, 1, 2 or 3
  • Z is C
  • X is O or S
  • Y is S
  • each R 3 , each R 4 , each R 6 and each R 7 are each independently selected from the group consisting of H and C1-C8 alkyl
  • R 5 is selected from phenyl (Ph) or benzyl (Bn)
  • each R 8 is independently selected from H, A.
  • Base ethyl, n-propyl, isopropyl, n-butyl, F, Cl, Br, methoxy, ethoxy, propoxy, butoxy, methylthio (CH 3 -S-), Ethylthio (CH 3 CH 2 -S-), propylthio (CH 3 CH 2 CH 2 -S-) and butylthio (CH 3 CH 2 CH 2 CH 2 -S-).
  • alkyl group of C1-C8 may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a n-pentyl group, a n-hexyl group or the like.
  • Specific examples of the alkyl group of C1-C6 may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a n-pentyl group, a n-hexyl group or the like.
  • the alkoxy group of C1-C6 may be an alkoxy group formed by the above C1-C6 alkyl group
  • the C1-C6 alkylthio group may be an alkylthio group formed by the above C1-C6 alkyl group.
  • specific examples of the alkoxy group of C1-C12 may be, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group or the like.
  • the above group A is preferably selected from the following structures:
  • the group A in the conjugated macromolecule based on the hepta-fused ring unit of the present invention has a strong tensile electron effect, and the group A is located at both ends of the hepta-fused ring unit to enable the obtained conjugated macromolecule to have strong visible light absorption.
  • Capacities, high charge transport properties, and suitable electronic energy levels are suitable for use as electron donor or electron acceptor materials for the preparation of organic solar cells.
  • conjugated macromolecule of the present invention may be, for example, one of the compounds represented by the following formula:
  • Formula (1-1) A is R 1 does not exist; R 2 is a formula A group represented by and R 3 is n-hexyl group; Z is C.
  • Formula (1-5) A is R 1 does not exist; R 2 is a formula a group shown, and R 3 is n-hexyl; Z is C.
  • Formula (1-9) A is R 1 does not exist; R 2 is a formula a group shown, and R 3 is n-hexyl; Z is C.
  • Formula (1-10) A is R 1 does not exist; R 2 is a formula a group shown, and R 3 is n-hexyl; Z is C.
  • the present invention also provides a method for producing the above conjugated macromolecule based on a hepta-fused ring unit, wherein the method comprises: compounding a compound represented by the following formula (2) in the presence of a basic compound and in an organic solvent The compound represented by the formula (B) is subjected to a dehydration condensation reaction to obtain a compound represented by the formula (1);
  • Formula (B) is selected from one or more of the following compounds:
  • R 2 are each independently selected from the formulas a group shown; two R 1 are each independently selected from a group shown; wherein each Z is independently selected from C or Si; each X and each Y are each independently selected from O, S or Se; m is an integer from 1 to 6; n is an integer from 0 to 6
  • Each R 3 , each R 4 , R 5 , each R 6 and each R 7 are each independently selected from the group consisting of H, a C1-C30 alkyl group, a C1-C30 alkoxy group, and a C6-C12 aryl group; 8 are each independently selected from the group consisting of H, alkyl, halogen, alkoxy, and alkylthio.
  • each Z, each X and each Y , n, m, and each R 8 are as defined in the foregoing, and are not described herein again.
  • the compound represented by the formula (2) may be a commercially available product, or may be produced by a conventional method in the art, for example, by an aldehyde group on a butyllithium reaction.
  • the compound represented by the formula (B) may be a commercially available product, or may be produced by a conventional method in the art, and will not be further described herein.
  • the aldehyde group attached to both ends of the compound represented by the formula (2) can be dehydrated and condensed with the compound represented by the formula (B) to form a compound represented by the formula (1), wherein
  • the amount of the compound represented by the formula (2) and the compound represented by the formula (B) is not particularly limited as long as the compound represented by the formula (1) can be obtained, and preferably, the formula (2) is shown.
  • the molar ratio of the compound to the compound represented by the formula (B) is from 1:2 to 100, more preferably from 1:4 to 10.
  • the reaction is carried out in the presence of a basic compound to provide an alkaline environment for the reaction system
  • the basic compound may be, for example, one or more of piperidine, pyridine and triethylamine.
  • the amount of the basic compound to be used is not particularly limited as long as it can provide an alkaline environment and contribute to the progress of the dehydration condensation reaction, for example, with respect to 1 mmol of the compound represented by the formula (2), the basic compound
  • the amount used is from 0.1 to 1000 mmol, more preferably from 50 to 100 mmol.
  • the organic solvent is, for example, chloroform and/or dichloromethane.
  • the organic solvent may be used in an amount of, for example, 20 to 200 mL (preferably 40 to 200 mL) based on 1 mmol of the compound represented by the formula (2).
  • the conditions of the dehydration condensation reaction include a temperature of 20 to 100 ° C (for example, 50 to 100 ° C) for a time of 10 min to 48 h (for example, 10 to 20 h). More preferably, the conditions of the dehydration condensation reaction include a temperature of 60-80 ° C and a time of 10-15 h.
  • the method further comprises maintaining the reaction system under an inert atmosphere before the reaction, for example, after the raw materials are added, the reaction system is introduced with an inert gas for 20-40 minutes to remove air.
  • the inert gas may be, for example, argon gas, helium gas, nitrogen gas or the like.
  • the method further comprises a post-treatment step such as dehydration condensation reaction product with methanol (relative to the total volume of the reaction liquid of 100 mL, for example, the amount of methanol, for example It can be mixed with 200-500mL), then subjected to solid-liquid separation.
  • methanol relative to the total volume of the reaction liquid of 100 mL, for example, the amount of methanol, for example It can be mixed with 200-500mL
  • the obtained solid phase is a silica gel column (200-300 mesh silica gel can be used, and the eluent can be petroleum ether and dichloride in a volume ratio of 1:2-3).
  • the methane mixture was subjected to chromatographic separation.
  • the present invention also provides a method for preparing the above conjugated macromolecule based on a hepta-fused ring unit, wherein the method comprises: in the presence of a palladium-containing catalyst and in an organic solvent, the formula (3) The compound is subjected to a coupling reaction with a compound represented by the formula (C) to obtain a compound represented by the formula (1);
  • Formula (C) is selected from one or more of the following compounds:
  • R 2 are each independently selected from the formula a group shown; two R 1 are each independently selected from a group; wherein each Z is independently selected from C or Si; each X and each Y are each independently selected from O, S or Se; each M is independently selected from halogen; each R' is independently An alkyl group selected from C1-C4; m is an integer from 1 to 6; n is an integer from 0 to 6; each R 3 , each R 4 , each R 6 and each R 7 are each independently selected from H, C1-C30 An alkyl group, a C1-C30 alkoxy group and a C6-C12 aryl group; each R 8 is independently selected from the group consisting of H, alkyl, halogen, alkoxy and alkylthio.
  • the compound represented by the formula (3) and the compound represented by the formula (C) can be selected according to the compound represented by the formula (1) to be produced, and therefore, the above substituent, each Z, each X and each Y are selected. , n and m are as defined in the foregoing, and are not described here.
  • the halogen as M may be, for example, selected from the group consisting of Br, I, and Cl.
  • the C1-C4 alkyl group as R' may be, for example, selected from the group consisting of methyl (Me), ethyl, propyl, and butyl.
  • Formula (3-1) R' is a methyl group; R 1 is absent; R 2 is a formula a group shown, and R 3 is n-hexyl; Z is C.
  • R ' is methyl; R 1 absent; R 2 is a formula a group shown, and R 3 is methyl; Z is C.
  • Formula (3-3) R' is a methyl group; R 1 is absent; R 2 is a formula a group shown, and R 3 is ethyl; Z is C.
  • R ' is methyl; R 1 absent; R 2 is a formula a group shown, and R 3 is n-butyl; Z is C.
  • the compound represented by the formula (3) may be a commercially available product, or may be produced by a conventional method in the art, for example, by a method in which a butyllithium reaction is carried out on a trialkyltin.
  • the compound represented by the formula (C) may be a commercially available product, or may be produced by a conventional method in the art, for example, by a method of bromination of NBS.
  • the SnR' 3 attached at both ends of the compound represented by the formula (3) can be coupled with the halogen M in the compound represented by the formula (C) to remove a portion of Sn(M)R. ' 3 , the compound represented by the formula (1) is formed, and the amount of the compound represented by the formula (3) and the compound represented by the formula (C) is not particularly limited as long as the formula can be obtained ( 1)
  • the compound shown may be used.
  • the molar ratio of the compound represented by the formula (3) to the compound represented by the formula (C) is from 1:2 to 10, more preferably from 1:2 to 5.
  • the reaction is carried out in the presence of a palladium-containing catalyst which catalyzes the progress of the coupling reaction, which may for example be tetrakis(triphenylphosphine)palladium and/or bis(triphenylphosphine) ) Palladium dichloride.
  • a palladium-containing catalyst which catalyzes the progress of the coupling reaction
  • the amount of the palladium-containing catalyst to be used is not particularly limited as long as it can catalyze the progress of the coupling reaction.
  • the palladium-containing catalyst is used in an amount of 0.01 to 0.1 with respect to 1 mmol of the compound represented by the formula (3). M, more preferably 0.03-0.08 mmol.
  • the organic solvent is, for example, toluene and/or tetrahydrofuran.
  • the organic solvent may be used in an amount of, for example, 40 to 200 mL based on 1 mmol of the compound represented by the formula (3).
  • the conditions of the coupling reaction include a temperature of 70 to 150 ° C (for example, 90 to 150 ° C) and a time of 6 to 50 h (for example, 20 to 50 h). More preferably, the conditions of the coupling reaction include a temperature of 100 to 120 ° C and a time of 20 to 40 h (for example, 30 to 40 h).
  • the method further comprises maintaining the reaction system under an inert atmosphere before the reaction, for example, after the raw materials are added, the reaction system is introduced with an inert gas for 20-40 minutes to remove air.
  • the inert gas may be, for example, argon gas, helium gas, nitrogen gas or the like.
  • the method further comprises a post-treatment step, for example, coupling the reaction product with methanol (relative to the total volume of the reaction liquid of 100 mL, for example, the amount of methanol, for example It can be mixed with 200-500mL), then subjected to solid-liquid separation.
  • methanol relative to the total volume of the reaction liquid of 100 mL, for example, the amount of methanol, for example It can be mixed with 200-500mL
  • the obtained solid phase is a silica gel column (200-300 mesh silica gel can be used, and the eluent can be petroleum ether and dichloride in a volume ratio of 1:2-3).
  • the methane mixture was subjected to chromatographic separation.
  • the present invention provides a photovoltaic material comprising the above conjugated macromolecule based on a hepta-fused ring unit.
  • the photovoltaic material is not particularly limited as long as it contains the above-mentioned conjugated macromolecule based on a hepta-fused ring unit of the present invention, and the photovoltaic material preferably refers to a light-trapping active layer in a solar cell.
  • the electron donor material polymer material PDBT-T1 and/or the polymer material PTB7-Th may be combined with the conjugated macromolecule based on the hepta-fused ring unit provided by the present invention in a weight ratio of 0.5-4:1.
  • the photovoltaic material in particular, a photovoltaic material as a light-trapping active layer of a solar cell, wherein the conjugated macromolecule based on the hepta-fused ring unit provided by the present invention serves as an electron acceptor material.
  • the structural units of the polymer material PDBT-T1 and the polymer material PTB7-Th are as follows:
  • -C 8 H 17 represents n-octyl group and -C 4 H 9 represents n-butyl group.
  • the present invention also provides a solar cell comprising a light-trapping active layer, wherein the electron-trapping material and/or electron acceptor material in the light-trapping active layer contains the above-described hepta-fused ring unit Conjugated macromolecules.
  • the configuration of the solar cell of the present invention is not particularly limited as long as the electron donor material and/or the electron acceptor material in the light-trapping active layer contains the above-mentioned conjugated macromolecule based on a hepta-fused ring unit. Yes, this can effectively improve the photoelectric conversion efficiency of the solar cell.
  • the conjugated macromolecules based on hepta-fused ring units of the present invention are suitable for use in organic solar cells, particularly as an electron acceptor material in combination with other electron donor materials to form a light-trapping active layer of a solar cell.
  • an electron donor material for example, may be a polymer material PDBT-T1 and/or a polymer material PTB7-Th, as defined above.
  • the polymer material PDBT-T1 and/or the polymer material PTB7-Th can be combined with the conjugated macromolecule based on the hepta-fused ring unit provided by the present invention in a weight ratio of 0.5-4:1 to form light-trapping. Active layer.
  • the present invention also provides a method of preparing a solar cell, wherein the method comprises using an electron donor material and/or an electron acceptor material containing the above-mentioned conjugated macromolecule based on a hepta-fused ring unit for forming light trapping. Active layer.
  • the preparation process of the solar cell is not particularly limited and may be carried out by a method conventional in the art.
  • the preparation process may include:
  • a ZnO layer is coated on the conductive glass (for example, indium tin oxide glass, ITO) as a cathode as a cathode modification layer (thickness may be, for example, 20 to 50 nm), and after drying, a polymer material PDBT- is coated on the ZnO layer.
  • a living layer a mixture of T1 and/or polymer material PTB7-Th and a conjugated macromolecule based on a hepta-fused ring unit provided by the present invention is dried, and then vacuum-deposited with molybdenum oxide (the thickness may be, for example, 5-10 nm).
  • Ag may be, for example, 50-100 nm as an anode.
  • the conjugated macromolecule based on hepta-fused ring unit provided by the invention has strong visible light absorption peak, for example, has a strong absorption peak in a wavelength range of 500-800 nm; the conjugated macromolecule has good thermal stability and can withstand The temperature around 300 °C does not decompose; cyclic voltammetry test results show that its HOMO level and LUMO level can be Most common electron donor materials have energy level matching, and they have good ability to accept electrons or holes, which is very beneficial as a photovoltaic material for solar cells, especially electron acceptors and/or electron donor materials, especially as Electron acceptor material.
  • the solar cell provided by the invention has a high short-circuit current, for example, can reach 14 mA ⁇ cm -2 or more, preferably can reach 17 mA ⁇ cm -2 or more; a high open circuit voltage can reach, for example, 0.8 V or more, preferably achievable Higher than 0.85V; higher filling factor, for example, can reach more than 65%, preferably can reach more than 68%; higher photoelectric conversion rate (PCE), for example, can reach 8.5% or more, preferably can reach more than 10%.
  • a high short-circuit current for example, can reach 14 mA ⁇ cm -2 or more, preferably can reach 17 mA ⁇ cm -2 or more
  • a high open circuit voltage can reach, for example, 0.8 V or more, preferably achievable Higher than 0.85V
  • higher filling factor for example, can reach more than 65%, preferably can reach more than 68%
  • higher photoelectric conversion rate (PCE) for example, can reach 8.5% or more, preferably can reach more than 10%.
  • 1 H NMR and 13 C NMR were measured using a nuclear magnetic resonance apparatus of the Bruker AVANCE 400 model.
  • MS MALDI
  • MS was measured using a mass spectrometer of the Bruker Daltonics Biflex III MALDI-TOF Analyzer model. Elemental analysis was performed using an elemental analyzer of the Flash EA1112elemental analyzer model.
  • the UV-Vis absorption spectrum was measured using an ultraviolet-visible spectrophotometer of the Jasco V-570 Spectrophotometer model.
  • the cyclic voltammetry curve was measured using a cyclic voltammetry tester of the CHI660C electrochemical workstation model.
  • thermogravimetric curve was measured using a thermogravimetric analyzer model Shimadzu thermogravimetric analyzer (Model DTG-60).
  • the space charge limited current curve was measured using the B2912A Precision Source/Measure Unit (Agilent Technologies) model.
  • the IV curve is measured by the B2912A Precision Source/Measure Unit (Agilent Technologies). Short-circuit current, open circuit voltage, fill factor, and photoelectric conversion efficiency can be obtained from the IV curve.
  • This example is intended to illustrate the conjugated macromolecule based on the hepta-fused ring unit of the present invention and a process for the preparation thereof.
  • the compound represented by the formula (2-1) (220 mg, 0.2 mmol; purchased from Polyene Organic Optoelectronics (Beijing) Co., Ltd.) and the compound represented by the formula (B-2) (200 mg, as shown in the above reaction formula) 1 mmol; purchased from TCI), chloroform (50 mL) and pyridine (10 mL, 12 mmol) were added to the reaction vessel, and argon gas was passed for 30 min to remove air, followed by reflux at 65 ° C for 12 h.
  • the ultraviolet-visible absorption spectrum of the conjugated macromolecule based on the hepta-fused ring unit represented by the formula (1-2) is shown in Fig. 1, wherein a strong absorption peak and a maximum molar ratio are in the wavelength range of 500 to 800 nm.
  • the extinction coefficient is 1.5 ⁇ 10 5 M –1 ⁇ cm –1 , and the absorption is strongest at around 700 nm;
  • the cyclic voltammetry curve is shown in Figure 2.
  • the HOMO level is -5.66 eV and the LUMO level is -3.93 eV, indicating that the compound of formula (1-2) has good electron acceptability and can be used with most General purpose electron donor material level matching;
  • thermogravimetric curve is shown in Fig. 3, indicating that the compound represented by the formula (1-2) has good thermal stability and can be decomposed to 300 °C.
  • the space charge limited current curve is shown in Fig. 4, indicating that the compound represented by the formula (1-2) has a high electron mobility, that is, 6.1 ⁇ 10 -4 cm 2 ⁇ V -1 ⁇ s -1 .
  • This example is intended to illustrate the conjugated macromolecule based on the hepta-fused ring unit of the present invention and a process for the preparation thereof.
  • the compound represented by the formula (3-1) (275 mg, 0.2 mmol; purchased from Polyene Organic Optoelectronics (Beijing) Co., Ltd.) and the compound represented by the formula (C-1-1) are shown in the above reaction formula ( 116 mg, 0.4 mmol; purchased from Suzhou Nakai Technology Co., Ltd.), toluene (50 mL) and tetrakis(triphenylphosphine)palladium (10 mg, 0.009 mmol) were added to the reaction vessel, and argon gas was passed for 30 min to remove air, and then It was refluxed at 110 ° C for 36 h.
  • the solid obtained by spin-drying was chromatographed on a silica gel column (with 200-300 mesh silica gel, eluent eluted with petroleum ether/dichloromethane of 1:2) to give a dark blue solid (280 mg, yield It is 95%), which is a conjugated macromolecule based on a hepta-fused ring unit represented by formula (1-8).
  • the ultraviolet-visible absorption spectrum of the conjugated macromolecule based on the hepta-fused ring unit represented by the formula (1-8) shows a strong absorption peak in a wavelength range of 500 to 800 nm;
  • the cyclic voltammetry curve indicates that the compound represented by the formula (1-8) has a HOMO level of -3.8 eV and a LUMO level of -5.6 eV, indicating that the compound represented by the formula (1-8) has good electron acceptability. , can match the energy level of most common electronic donor materials;
  • thermogravimetric curve shows that the compound represented by the formula (1-8) has good thermal stability and can be decomposed to 300 °C.
  • the space charge limited current curve indicates that the compound represented by the formula (1-8) has a high electron mobility, that is, 5 ⁇ 10 -4 cm 2 ⁇ V -1 ⁇ s -1 .
  • This embodiment is for explaining the solar cell of the present invention.
  • ITO Indium tin oxide
  • cathode purchased from Shenzhen CSG Float Glass Co., Ltd.
  • ITO Indium tin oxide
  • the solar light source was simulated with an AM1.5 filter (XES-70S1 model of SAN-EI ELECTRIC Co., Ltd.), and the device was tested for photovoltaic performance at a light intensity of 100 mW/cm 2 , and the light intensity passed through a standard single crystal. Silicon solar cells (purchased from VLSI Standards Inc) are calibrated. The resulting IV curve was measured using a B2912A Precision Source/Measure Unit (Agilent Technologies) and controlled by a computer using Labview software.
  • the resulting IV curve is shown in Figure 5.
  • the short-circuit current J sc of the solar cell was 17 mA ⁇ cm -2 , the open circuit voltage V oc was 0.88 V, the fill factor FF was 70%, and the photoelectric conversion efficiency PCE was 10.5%.
  • Example 3 1.5 mg of the conjugated macromolecule based on the hepta-fused ring unit represented by the above formula (1-2) and 1 mg of the polymer donor material PTB7-Th (purchased from hydrazine) Lun Organic Photoelectric Technology (Beijing) Co., Ltd. mixed in 0.1 mL of o-dichlorobenzene to obtain a mixed solution, which was then spin-coated on the above ZnO layer, and dried to obtain a light-trapping active layer.
  • PTB7-Th purchased from hydrazine
  • the resulting IV curve is shown in Figure 6.
  • the short-circuit current J sc of the solar cell was 19 mA ⁇ cm -2 , the open circuit voltage V oc was 0.80 V, the fill factor FF was 68%, and the photoelectric conversion efficiency PCE was 10.4%.
  • the resulting IV curve is shown in Figure 7.
  • the solar cell can be obtained by the IV curve shown in FIG. 7 of the short circuit current J sc 14.5mA ⁇ cm -2, the open circuit voltage V oc was 0.90 V, 69% fill factor FF, the photoelectric conversion efficiency of 9.0% PCE.
  • the resulting IV curve is shown in Figure 8.
  • the short-circuit current J sc of the solar cell was 15.6 mA ⁇ cm -2
  • the open circuit voltage V oc was 0.85 V
  • the fill factor FF was 67%
  • the photoelectric conversion efficiency PCE was 8.9%.

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Abstract

Provided are a heptacyclic unit-based conjugated macromolecule and a method of preparing same. The conjugated macromolecule is a compound expressed by Formula (I). Further provided are a photovoltaic material that contains the heptacyclic unit-based conjugated macromolecule, a solar cell, and a method of preparing the same. The heptacyclic unit-based conjugated macromolecule has relatively strong light absorption, relatively high charge transport performance, and a suitable electron energy level, and is suitable for serving as an electron donor material or an electron acceptor material for use in a solar cell.

Description

基于七并稠环单元的共轭大分子及其制备方法和在太阳能电池中的应用Conjugated macromolecule based on hepta-fused ring unit, preparation method thereof and application in solar battery 技术领域Technical field
本发明涉及太阳能电池领域，具体地，涉及一种基于七并稠环单元的共轭大分子及其制备方法和在太阳能电池中的应用。The invention relates to the field of solar cells, in particular to a conjugated macromolecule based on a hepta-fused ring unit, a preparation method thereof and application in a solar cell.
背景技术Background technique
有机太阳能电池拥有成本低、重量轻、可弯曲、可溶液加工并且可以大面积制备等优点，因此在学术界受到广泛的关注。近年来，聚合物和小分子太阳能电池发展迅速，并取得了显著的成果。到目前为止，经过对分子结构、器件结构和加工工艺的优化，基于聚合物给体或小分子给体与富勒烯受体共混制备的太阳能电池的光电转换效率已突破10％。这显示出有机太阳能电池的巨大应用前景。其中聚合物材料由于其吸收太阳光的范围相对较宽，其光伏器件的光电转换效率较高。通过对材料结构及器件结构的优化，文献报道的最高光电转换效率已经达到10.8％。但聚合物也有自身缺点，如：分子量分布的多分散性，批次间重复性较差，纯化难等问题。相对于此，有机小分子和大分子半导体材料则表现出特定优点，如：确定的分子结构及分子量，高纯度及批次稳定等。因而，近来有机小分子和大分子太阳能电池研究渐趋于热。Organic solar cells have received a lot of attention in academia because of their low cost, light weight, flexibility, solution processing, and large-area preparation. In recent years, polymers and small-molecule solar cells have developed rapidly and achieved remarkable results. So far, the photoelectric conversion efficiency of solar cells prepared by blending polymer donors or small molecule donors with fullerene receptors has exceeded 10% through optimization of molecular structure, device structure and processing technology. This shows a huge application prospect of organic solar cells. Among them, the polymer material has a relatively high photoelectric conversion efficiency due to its relatively wide range of absorption of sunlight. Through the optimization of material structure and device structure, the highest photoelectric conversion efficiency reported in the literature has reached 10.8%. However, polymers also have their own shortcomings, such as polydispersity of molecular weight distribution, poor repeatability between batches, and difficulty in purification. In contrast, organic small molecules and macromolecular semiconductor materials exhibit certain advantages, such as: defined molecular structure and molecular weight, high purity and batch stability. Therefore, recent research on organic small molecules and macromolecular solar cells has become hotter.
相比于给体材料的迅速发展，受体材料则发展缓慢。在受体材料方面，以PC61BM和PC71BM为代表的富勒烯衍生物牢牢地占据着主导地位。这是因为PCBM拥有诸多优点，如大的电子亲和力、优秀的各向同性的电子传输性能、并且能够与给体材料混合形成纳米尺寸的相分离等。然而以PCBM为代表的富勒烯衍生物也存在着诸多缺点，如在可见光区吸收弱、能级调控难、提纯困难等。而对于已报道的非富勒烯受体材料来说，却难以获得较高的光电转换率(PCE)的太阳能电池，例如PCE<8.5％。因此合成新型的受体材料依然非常有必要。Receptor materials develop slowly compared to the rapid development of donor materials. In terms of acceptor materials, fullerene derivatives represented by PC 61 BM and PC 71 BM are firmly in the dominant position. This is because PCBM has many advantages, such as large electron affinity, excellent isotropic electron transport performance, and the ability to mix with donor materials to form nano-sized phase separations. However, fullerene derivatives represented by PCBM also have many disadvantages, such as weak absorption in the visible region, difficulty in energy level regulation, and difficulty in purification. For the reported non-fullerene acceptor materials, it is difficult to obtain a solar cell with a high photoelectric conversion rate (PCE), such as PCE <8.5%. Therefore, the synthesis of new receptor materials is still very necessary.
发明内容Summary of the invention
本发明的目的在于提供一种新型的能够用于太阳能电池作为电子给体或电子受体材料的具有较强的光吸收、较高的电荷传输性能以及合适的电子能级的基于七并稠环单元的共轭大分子及其制备方法以及光伏材料和太阳能电池及其制备方法。SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel heavier-based fused ring capable of being used as a electron donor or electron acceptor material for solar cells with strong light absorption, high charge transport properties, and suitable electron energy levels. Conjugated macromolecule of unit and preparation method thereof, and photovoltaic material and solar cell and preparation method thereof.
为了实现上述目的，本发明提供一种基于七并稠环单元的共轭大分子，该共轭大分子为下式(1)所示的化合物： In order to achieve the above object, the present invention provides a conjugated macromolecule based on a hepta-fused ring unit which is a compound represented by the following formula (1):
Figure PCTCN2016098397-appb-000001
Figure PCTCN2016098397-appb-000001
其中，两个基团A独立地选自以下结构：Wherein two groups A are independently selected from the following structures:
Figure PCTCN2016098397-appb-000002
Figure PCTCN2016098397-appb-000002
四个R2各自独立地选自式
Figure PCTCN2016098397-appb-000003
所示的基团；两个R1各自独立地选自式
Figure PCTCN2016098397-appb-000004
所示的基团；其中，各个Z各自独立地选自C或Si；各个X和各个Y各自独立地选自O、S或Se；m为1-6的整数；n为0-6的整数；各个R3、各个R4、R5、各个R6和各个R7各自独立地选自H、C1-C30的烷基、C1-C30的烷氧基和C6-C12的芳基；各个R8各自独立地选自H、烷基、卤素、烷氧基和烷硫基。Four R 2 are each independently selected from
Figure PCTCN2016098397-appb-000003
a group shown; two R 1 are each independently selected from
Figure PCTCN2016098397-appb-000004
a group shown; wherein each Z is independently selected from C or Si; each X and each Y are each independently selected from O, S or Se; m is an integer from 1 to 6; n is an integer from 0 to 6 Each R 3 , each R 4 , R 5 , each R 6 and each R 7 are each independently selected from the group consisting of H, a C1-C30 alkyl group, a C1-C30 alkoxy group, and a C6-C12 aryl group; 8 are each independently selected from the group consisting of H, alkyl, halogen, alkoxy, and alkylthio.
本发明还提供了上述基于七并稠环单元的共轭大分子的制备方法，其中，该方法包括：在碱性化合物存在下且在有机溶剂中，将下式(2)所示的化合物与式(B)所示的化合物进行脱水缩合反应，得到式(1)所示的化合物；其中，The present invention also provides a method for producing the above conjugated macromolecule based on a hepta-fused ring unit, wherein the method comprises: compounding a compound represented by the following formula (2) in the presence of a basic compound and in an organic solvent The compound represented by the formula (B) is subjected to a dehydration condensation reaction to obtain a compound represented by the formula (1);
Figure PCTCN2016098397-appb-000005
Figure PCTCN2016098397-appb-000005
式(B)选自以下化合物中的一种或多种： Formula (B) is selected from one or more of the following compounds:
Figure PCTCN2016098397-appb-000006
Figure PCTCN2016098397-appb-000006
本发明还提供了上述基于七并稠环单元的共轭大分子的制备方法，其中，该方法包括：在含钯催化剂存在下且在有机溶剂中，将下式(3)所示的化合物与式(C)所示的化合物进行偶联反应，得到式(1)所示的化合物；其中，The present invention also provides a method for producing the above conjugated macromolecule based on a hepta-fused ring unit, wherein the method comprises: compounding a compound represented by the following formula (3) in the presence of a palladium-containing catalyst and in an organic solvent The compound represented by the formula (C) is subjected to a coupling reaction to obtain a compound represented by the formula (1);
Figure PCTCN2016098397-appb-000007
Figure PCTCN2016098397-appb-000007
式(C)选自以下化合物中的一种或多种：Formula (C) is selected from one or more of the following compounds:
Figure PCTCN2016098397-appb-000008
Figure PCTCN2016098397-appb-000008
本发明还提供了一种含有上述基于七并稠环单元的共轭大分子的光伏材料。The present invention also provides a photovoltaic material comprising the above conjugated macromolecule based on a hepta-fused ring unit.
本发明还提供了一种太阳能电池，该太阳能电池包括光捕获的活性层，其中，所述光捕获的活性层中电子给体材料和/或电子受体材料含有上述基于七并稠环单元的共轭大分子。The present invention also provides a solar cell comprising a light-trapping active layer, wherein the electron-trapping material and/or electron acceptor material in the light-trapping active layer contains the above-described hepta-fused ring unit Conjugated macromolecules.
本发明还提供了一种太阳能电池的制备方法，其中，该方法包括将含有上述基于七并稠环单元的共轭大分子的电子给体材料和/或电子受体材料用于形成光捕获的活性层。The present invention also provides a method of preparing a solar cell, wherein the method comprises using an electron donor material and/or an electron acceptor material containing the above-mentioned conjugated macromolecule based on a hepta-fused ring unit for forming light trapping. Active layer.
本发明提供的基于七并稠环单元的共轭大分子，具有较强的光吸收、较高的电荷 传输性能以及合适的电子能级，适合于作为电子给体或电子受体材料应用于制备太阳能电池，特别是能够获得光电转换效率为10％以上的太阳能电池。The conjugated macromolecule based on hepta-fused ring unit provided by the invention has strong light absorption and high electric charge The transmission performance and a suitable electronic energy level are suitable for use as an electron donor or electron acceptor material for the preparation of a solar cell, and in particular, a solar cell having a photoelectric conversion efficiency of 10% or more can be obtained.
本发明的其它特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the invention will be described in detail in the detailed description which follows.
附图说明DRAWINGS
附图是用来提供对本发明的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本发明，但并不构成对本发明的限制。在附图中：The drawings are intended to provide a further understanding of the invention, and are intended to be a In the drawing:
图1为本发明的实施例1所得的式(1-2)所示的基于七并稠环单元的共轭大分子的紫外－可见吸收光谱，其中，溶液是指以氯仿为溶剂制得的溶液(10-6mol/L)，薄膜是指氯仿溶液旋涂成的薄膜(100纳米厚度)。1 is an ultraviolet-visible absorption spectrum of a conjugated macromolecule based on a hepta-fused ring unit represented by the formula (1-2) obtained in Example 1 of the present invention, wherein the solution is obtained by using chloroform as a solvent. Solution (10 -6 mol/L), film refers to a film (100 nm thickness) spin-coated with a chloroform solution.
图2为本发明的实施例1所得的式(1-2)所示的基于七并稠环单元的共轭大分子的循环伏安曲线。2 is a cyclic voltammetry curve of a conjugated macromolecule based on a hepta-fused ring unit represented by the formula (1-2) obtained in Example 1 of the present invention.
图3为本发明的实施例1所得的式(1-2)所示的基于七并稠环单元的共轭大分子的热失重曲线。Fig. 3 is a graph showing the thermogravimetric curve of a conjugated macromolecule based on a hepta-fused ring unit represented by the formula (1-2) obtained in Example 1 of the present invention.
图4为本发明的实施例1所得的式(1-2)所示的基于七并稠环单元的共轭大分子的空间电荷限制电流曲线。4 is a graph showing the space charge-limited current of a conjugated macromolecule based on a hepta-fused ring unit represented by the formula (1-2) obtained in Example 1 of the present invention.
图5为实施例3所得的太阳能电池的I-V曲线(电流-电压曲线)。Fig. 5 is an I-V curve (current-voltage curve) of the solar cell obtained in Example 3.
图6为实施例4所得的太阳能电池的I-V曲线。Fig. 6 is an I-V curve of the solar cell obtained in Example 4.
图7为实施例5所得的太阳能电池的I-V曲线。Fig. 7 is an I-V curve of the solar cell obtained in Example 5.
图8为实施例6所得的太阳能电池的I-V曲线。Fig. 8 is an I-V curve of the solar cell obtained in Example 6.
具体实施方式detailed description
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It is to be understood that the specific embodiments described herein are merely illustrative and not restrictive.
本发明中，
Figure PCTCN2016098397-appb-000009
等带有虚线连接键的结构中的虚线指明了连接位点，表示连接键；
Figure PCTCN2016098397-appb-000010
等带有实线连接键的结构中的未连接任何基团或原子的实线也指明了连接位点，表示连接键。In the present invention,
Figure PCTCN2016098397-appb-000009
The dotted line in the structure with a dotted connection key indicates the connection site, indicating the connection key;
Figure PCTCN2016098397-appb-000010
A solid line in a structure with a solid-line bond that is not connected to any group or atom also indicates a connection site, indicating a linkage.
本发明提供一种基于七并稠环单元的共轭大分子，该共轭大分子为下式(1)所示的化合物： The present invention provides a conjugated macromolecule based on a hepta-fused ring unit which is a compound represented by the following formula (1):
Figure PCTCN2016098397-appb-000011
Figure PCTCN2016098397-appb-000011
其中，两个基团A独立地选自以下结构：Wherein two groups A are independently selected from the following structures:
Figure PCTCN2016098397-appb-000012
Figure PCTCN2016098397-appb-000012
四个R2各自独立地选自式
Figure PCTCN2016098397-appb-000013
所示的基团；两个R1各自独立地选自式
Figure PCTCN2016098397-appb-000014
所示的基团；其中，各个Z各自独立地选自C或Si(表示式(1)的两个Z可以相同或不同，独立地进行选择)；各个X和各个Y各自独立地选自O、S或Se(表示当式(1)的具有多个X和Y时，该多个X可以相同或不同，独立地进行选择；该多个Y也可以相同或不同，独立地进行选择)；m为1-6的整数；n为0-6的整数；各个R3、各个R4、R5、各个R6和各个R7各自独立地选自H、C1-C30的烷基、C1-C30的烷氧基和C6-C12的芳基(表示当各个基团同时且在式(1)中的化合物中多处出现时，它们都是独立地选择，可以是相同的，也可以是不同的，例如，尽管
Figure PCTCN2016098397-appb-000015
所示的基团中具有两个R6，但是这两个R6是可以独立地进行选择的，可以相同也可以不同)；各个R8各自独立地选自H、烷基、卤素、烷氧基和烷硫基。Four R 2 are each independently selected from
Figure PCTCN2016098397-appb-000013
A group represented by; two R 1 are each independently selected from the formulas
Figure PCTCN2016098397-appb-000014
a group shown; wherein each Z is independently selected from C or Si (two Zs of formula (1) may be the same or different, independently selected); each X and each Y are each independently selected from O , S or Se (representing when the formula (1) has a plurality of X and Y, the plurality of Xs may be the same or different, and are independently selected; the plurality of Ys may also be the same or different and independently selected); m is an integer from 1 to 6; n is an integer from 0 to 6; each R 3 , each R 4 , R 5 , each R 6 and each R 7 are each independently selected from H, C1-C30 alkyl, C1- An alkoxy group of C30 and an aryl group of C6-C12 (representing that when each group appears simultaneously in multiple places in the compound of formula (1), they are independently selected, may be the same, or may be different For example, despite
Figure PCTCN2016098397-appb-000015
There are two R 6 in the group shown, but the two R 6 may be independently selected and may be the same or different); each R 8 is independently selected from H, alkyl, halogen, alkoxy Base and alkylthio group.
根据本发明，在满足四个R2各自独立地选自式
Figure PCTCN2016098397-appb-000016
所示的基团且两个R1各自独立地选自式
Figure PCTCN2016098397-appb-000017
所示的基团的情况下，式(1)所述的化合物可以用以下式(1’)表示： According to the invention, each of the four R 2 is independently selected from the formula
Figure PCTCN2016098397-appb-000016
a group shown and two R 1 are each independently selected from
Figure PCTCN2016098397-appb-000017
In the case of the group shown, the compound of the formula (1) can be represented by the following formula (1'):
Figure PCTCN2016098397-appb-000018
Figure PCTCN2016098397-appb-000018
根据本发明，为了能够获得光吸收更强、电荷传输性能更高以及电子能级更为合适的基于七并稠环单元的共轭大分子，优选地，m为1-4的整数，n为0-4的整数。According to the present invention, in order to obtain a conjugated macromolecule based on a hepta-fused ring unit which is stronger in light absorption, higher in charge transport property, and more suitable in electron energy level, m is preferably an integer of 1-4, n is An integer from 0-4.
其中，n为0，可认为R1表示不存在，那么基团A与式(1)所示的化合物的七并稠环单元主体直接连接，形成共轭结构。Wherein, n is 0, and R 1 is considered to be absent, and the group A is directly bonded to the hepta-fused ring unit main body of the compound represented by the formula (1) to form a conjugated structure.
其中，在本发明的一种优选的实施方式中，各个R8均选自H，从而所得的基团A如下式所示：Wherein, in a preferred embodiment of the present invention, each of R 8 is selected from H, and the resulting group A is represented by the following formula:
Figure PCTCN2016098397-appb-000019
Figure PCTCN2016098397-appb-000019
其中，在本发明的另一种优选的实施方式中，各个R8各自独立地选自烷基、卤素、烷氧基和烷硫基，优选选自C1-C6的烷基、卤素、C1-C6的烷氧基和C1-C6的烷硫基，优选选自甲基、乙基、正丙基、异丙基、正丁基、F、Cl、Br、甲氧基、乙氧基、丙氧基、丁氧基、甲硫基(CH3-S-)、乙硫基(CH3CH2-S-)、丙硫基(CH3CH2CH2-S-)和丁硫基(CH3CH2CH2CH2-S-)。Wherein, in another preferred embodiment of the present invention, each R 8 is independently selected from the group consisting of alkyl, halogen, alkoxy and alkylthio, preferably selected from C1-C6 alkyl, halogen, C1- The alkoxy group of C6 and the alkylthio group of C1-C6 are preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, F, Cl, Br, methoxy, ethoxy, and C. Oxyl, butoxy, methylthio (CH 3 -S-), ethylthio (CH 3 CH 2 -S-), propylthio (CH 3 CH 2 CH 2 -S-) and butylthio ( CH 3 CH 2 CH 2 CH 2 -S-).
更优选地，各个R3、各个R4、各个R6和各个R7各自独立地选自H、C1-C30的烷基和C1-C30的烷氧基，R5为C6-C12的芳基。More preferably, each R 3 , each R 4 , each R 6 and each R 7 are each independently selected from the group consisting of H, a C1-C30 alkyl group and a C1-C30 alkoxy group, and R 5 is a C6-C12 aryl group. .
更进一步优选地，各个R3、各个R4、各个R6和各个R7各自独立地选自H、C1-C12的烷基和C1-C12的烷氧基，R5选自苯基或苄基。Still more preferably, each R 3 , each R 4 , each R 6 and each R 7 are each independently selected from the group consisting of H, C1-C12 alkyl and C1-C12 alkoxy, and R 5 is selected from phenyl or benzyl. base.
在本发明的一种优选的实施方式中，m为1、2或3，n为0、1、2或3，Z为C，X为O或S，Y为S；各个R3、各个R4、各个R6和各个R7各自独立地选自H和C1-C8的烷基，R5选自苯基(Ph)或苄基(Bn)，各个R8各自独立地选自H、甲基、乙基、正 丙基、异丙基、正丁基、F、Cl、Br、甲氧基、乙氧基、丙氧基、丁氧基、甲硫基(CH3-S-)、乙硫基(CH3CH2-S-)、丙硫基(CH3CH2CH2-S-)和丁硫基(CH3CH2CH2CH2-S-)。In a preferred embodiment of the present invention, m is 1, 2 or 3, n is 0, 1, 2 or 3, Z is C, X is O or S, Y is S; each R 3 , each R 4 , each R 6 and each R 7 are each independently selected from the group consisting of H and C1-C8 alkyl, R 5 is selected from phenyl (Ph) or benzyl (Bn), and each R 8 is independently selected from H, A. Base, ethyl, n-propyl, isopropyl, n-butyl, F, Cl, Br, methoxy, ethoxy, propoxy, butoxy, methylthio (CH 3 -S-), Ethylthio (CH 3 CH 2 -S-), propylthio (CH 3 CH 2 CH 2 -S-) and butylthio (CH 3 CH 2 CH 2 CH 2 -S-).
其中，C1-C8的烷基的具体实例例如可以为：甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、正戊基、正己基等。其中，C1-C6的烷基的具体实例例如可以为：甲基、乙基、丙基、异丙基、丁基、异丁基、正戊基、正己基等。C1-C6的烷氧基可以为上述C1-C6的烷基形成的烷氧基，C1-C6的烷硫基可以为上述C1-C6的烷基形成的烷硫基。其中，C1-C12的烷氧基的具体实例例如可以为：甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基等。Specific examples of the alkyl group of C1-C8 may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a n-pentyl group, a n-hexyl group or the like. Specific examples of the alkyl group of C1-C6 may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a n-pentyl group, a n-hexyl group or the like. The alkoxy group of C1-C6 may be an alkoxy group formed by the above C1-C6 alkyl group, and the C1-C6 alkylthio group may be an alkylthio group formed by the above C1-C6 alkyl group. Among them, specific examples of the alkoxy group of C1-C12 may be, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group or the like.
上述基团A优选选自以下结构：The above group A is preferably selected from the following structures:
Figure PCTCN2016098397-appb-000020
Figure PCTCN2016098397-appb-000020
本发明的基于七并稠环单元的共轭大分子中的基团A具有强拉电子效应，基团A位于七并稠环单元的两端能够使得所得的共轭大分子拥有强的可见光吸收能力、高的电荷传输性能以及合适的电子能级，适合于作为电子给体或电子受体材料应用于制备有机太阳能电池。The group A in the conjugated macromolecule based on the hepta-fused ring unit of the present invention has a strong tensile electron effect, and the group A is located at both ends of the hepta-fused ring unit to enable the obtained conjugated macromolecule to have strong visible light absorption. Capacities, high charge transport properties, and suitable electronic energy levels are suitable for use as electron donor or electron acceptor materials for the preparation of organic solar cells.
根据本发明，本发明的共轭大分子的具体实例例如可以为以下式所示的化合物中的一种：According to the present invention, a specific example of the conjugated macromolecule of the present invention may be, for example, one of the compounds represented by the following formula:
式(1-1)：A为
Figure PCTCN2016098397-appb-000021
R1不存在；R2为式
Figure PCTCN2016098397-appb-000022
所示的基团，且R3为正己基； Z为C。式(1-2)：A为
Figure PCTCN2016098397-appb-000023
R1不存在；R2为式
Figure PCTCN2016098397-appb-000024
所示的基团，且R3为正己基；Z为C。式(1-3)：A为
Figure PCTCN2016098397-appb-000025
R1不存在；R2为式
Figure PCTCN2016098397-appb-000026
所示的基团，且R3为正己基；Z为C。式(1-4)：A为
Figure PCTCN2016098397-appb-000027
R1不存在；R2为式
Figure PCTCN2016098397-appb-000028
所示的基团，且R3为正己基；Z为C。式(1-5)：A为
Figure PCTCN2016098397-appb-000029
R1不存在；R2为式
Figure PCTCN2016098397-appb-000030
所示的基团，且R3为正己基；Z为C。式(1-6)：A为
Figure PCTCN2016098397-appb-000031
R1不存在；R2为式
Figure PCTCN2016098397-appb-000032
所示的基团，且R3为正己基；Z为C。式(1-7)：A为
Figure PCTCN2016098397-appb-000033
R1不存在；R2为式
Figure PCTCN2016098397-appb-000034
所示的基团，且R3为正己基；Z为C。式(1-8)：A为
Figure PCTCN2016098397-appb-000035
R1不存在；R2为式
Figure PCTCN2016098397-appb-000036
所示的基团，且R3为正己基；Z为C。式(1-9)：A为
Figure PCTCN2016098397-appb-000037
R1不存在；R2为式
Figure PCTCN2016098397-appb-000038
所示的基团，且R3为正己基；Z为C。式(1-10)：A为
Figure PCTCN2016098397-appb-000039
R1不存在；R2为式
Figure PCTCN2016098397-appb-000040
所示的基团，且R3为正己基；Z为C。式(1-11)：A为
Figure PCTCN2016098397-appb-000041
R1不存在；R2为式
Figure PCTCN2016098397-appb-000042
所示的基团，且R3为正己基；Z为C。式(1-12)：A为
Figure PCTCN2016098397-appb-000043
R1不存在；R2为式
Figure PCTCN2016098397-appb-000044
所示的基团，且R3为正己基；Z为C。式(1-13)：A为
Figure PCTCN2016098397-appb-000045
R1不存在；R2为式
Figure PCTCN2016098397-appb-000046
所示的基团，且R3为正己基；Z为C。 Formula (1-1): A is
Figure PCTCN2016098397-appb-000021
R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000022
A group represented by and R 3 is n-hexyl group; Z is C. Equation (1-2): A is
Figure PCTCN2016098397-appb-000023
R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000024
a group shown, and R 3 is n-hexyl; Z is C. Formula (1-3): A is
Figure PCTCN2016098397-appb-000025
R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000026
A group represented by and R 3 is n-hexyl group; Z is C. Formula (1-4): A is
Figure PCTCN2016098397-appb-000027
R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000028
a group shown, and R 3 is n-hexyl; Z is C. Formula (1-5): A is
Figure PCTCN2016098397-appb-000029
R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000030
a group shown, and R 3 is n-hexyl; Z is C. Formula (1-6): A is
Figure PCTCN2016098397-appb-000031
R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000032
A group represented by and R 3 is n-hexyl group; Z is C. Formula (1-7): A is
Figure PCTCN2016098397-appb-000033
R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000034
a group shown, and R 3 is n-hexyl; Z is C. Formula (1-8): A is
Figure PCTCN2016098397-appb-000035
R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000036
A group represented by and R 3 is n-hexyl group; Z is C. Formula (1-9): A is
Figure PCTCN2016098397-appb-000037
R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000038
a group shown, and R 3 is n-hexyl; Z is C. Formula (1-10): A is
Figure PCTCN2016098397-appb-000039
R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000040
a group shown, and R 3 is n-hexyl; Z is C. Formula (1-11): A is
Figure PCTCN2016098397-appb-000041
R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000042
a group shown, and R 3 is n-hexyl; Z is C. Formula (1-12): A is
Figure PCTCN2016098397-appb-000043
R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000044
a group shown, and R 3 is n-hexyl; Z is C. Formula (1-13): A is
Figure PCTCN2016098397-appb-000045
R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000046
a group shown, and R 3 is n-hexyl; Z is C.
本发明还提供了上述基于七并稠环单元的共轭大分子的制备方法，其中，该方法包括：在碱性化合物存在下且在有机溶剂中，将下式(2)所示的化合物与式(B)所示的化合物进行脱水缩合反应，得到式(1)所示的化合物；其中，The present invention also provides a method for producing the above conjugated macromolecule based on a hepta-fused ring unit, wherein the method comprises: compounding a compound represented by the following formula (2) in the presence of a basic compound and in an organic solvent The compound represented by the formula (B) is subjected to a dehydration condensation reaction to obtain a compound represented by the formula (1);
Figure PCTCN2016098397-appb-000047
Figure PCTCN2016098397-appb-000047
式(B)选自以下化合物中的一种或多种：Formula (B) is selected from one or more of the following compounds:
Figure PCTCN2016098397-appb-000048
Figure PCTCN2016098397-appb-000048
其中，四个R2各自独立地选自式
Figure PCTCN2016098397-appb-000049
所示的基团；两个R1各自独立地选自式
Figure PCTCN2016098397-appb-000050
所示的基团；其中，各个Z各自独立地选自C或Si；各个X和各个Y各自独立地选自O、S或Se；m为1-6的整数；n为0-6的整数；各个R3、各个R4、R5、各个R6和各个R7各自独立地选自H、C1-C30的烷基、C1-C30的烷氧基和C6-C12的芳基；各个R8各自独立地选自H、烷基、卤素、烷氧基和烷硫基。Wherein the four R 2 are each independently selected from the formulas
Figure PCTCN2016098397-appb-000049
a group shown; two R 1 are each independently selected from
Figure PCTCN2016098397-appb-000050
a group shown; wherein each Z is independently selected from C or Si; each X and each Y are each independently selected from O, S or Se; m is an integer from 1 to 6; n is an integer from 0 to 6 Each R 3 , each R 4 , R 5 , each R 6 and each R 7 are each independently selected from the group consisting of H, a C1-C30 alkyl group, a C1-C30 alkoxy group, and a C6-C12 aryl group; 8 are each independently selected from the group consisting of H, alkyl, halogen, alkoxy, and alkylthio.
其中，式(2)所示的化合物与式(B)所示的化合物可以根据所需制备的式(1)所示的化合物进行选择，因此，上述取代基、各个Z、各个X和各个Y、n、m和各个R8如前文中所定义的，在此不再赘述。Wherein the compound represented by the formula (2) and the compound represented by the formula (B) can be selected according to the compound represented by the formula (1) to be produced, and therefore, the above substituent, each Z, each X and each Y , n, m, and each R 8 are as defined in the foregoing, and are not described herein again.
其中，当各个R8均为H时，式(B)可由下式表示： Wherein, when each R 8 is H, the formula (B) can be represented by the following formula:
Figure PCTCN2016098397-appb-000051
Figure PCTCN2016098397-appb-000051
作为式(2)所示的化合物的具体实例例如可以为以下式所示的化合物中的一种或多种：Specific examples of the compound represented by the formula (2) may be, for example, one or more of the compounds represented by the following formula:
式(2-1)：R1不存在；R2为式
Figure PCTCN2016098397-appb-000052
所示的基团，且R3为正己基；Z为C。式(2-2)：R1不存在；R2为式
Figure PCTCN2016098397-appb-000053
所示的基团，且R3为甲基；Z为C。式(2-3)：R1不存在；R2为式
Figure PCTCN2016098397-appb-000054
所示的基团，且R3为乙基；Z为C。式(2-4)：R1不存在；R2为式
Figure PCTCN2016098397-appb-000055
所示的基团，且R3为正丙基；Z为C。式(2-5)：R1不存在；R2为式
Figure PCTCN2016098397-appb-000056
所示的基团，且R3为正丁基；Z为C。式(2-6)：R1不存在；R2为式
Figure PCTCN2016098397-appb-000057
所示的基团，且R3为正戊基；Z为C。Formula (2-1): R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000052
a group shown, and R 3 is n-hexyl; Z is C. Formula (2-2): R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000053
Group represented by and R 3 is methyl; Z is C. Formula (2-3): R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000054
a group shown, and R 3 is ethyl; Z is C. Formula (2-4): R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000055
a group shown, and R 3 is n-propyl; Z is C. Formula (2-5): R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000056
a group shown, and R 3 is n-butyl; Z is C. Formula (2-6): R 1 does not exist; R 2 is a formula
Figure PCTCN2016098397-appb-000057
a group shown, and R 3 is n-pentyl; Z is C.
根据本发明，式(2)所示的化合物可以是市售品，也可以通过本领域常规的方法制得，例如通过丁基锂反应上醛基进行制备。According to the present invention, the compound represented by the formula (2) may be a commercially available product, or may be produced by a conventional method in the art, for example, by an aldehyde group on a butyllithium reaction.
作为式(B-8)所示的化合物的具体实例例如可以为以下式所示的化合物中的一种或多种：Specific examples of the compound represented by the formula (B-8) may be, for example, one or more of the compounds represented by the following formula:
Figure PCTCN2016098397-appb-000058
Figure PCTCN2016098397-appb-000058
作为式(B-9)所示的化合物的具体实例例如可以为以下式所示的化合物中的一种或多种：Specific examples of the compound represented by the formula (B-9) may be, for example, one or more of the compounds represented by the following formula:
Figure PCTCN2016098397-appb-000059
Figure PCTCN2016098397-appb-000059
作为式(B-10)所示的化合物的具体实例例如可以为以下式所示的化合物中的一种或多种：Specific examples of the compound represented by the formula (B-10) may be, for example, one or more of the compounds represented by the following formula:
Figure PCTCN2016098397-appb-000060
Figure PCTCN2016098397-appb-000060
根据本发明，式(B)所示的化合物可以是市售品，也可以通过本领域常规的方法制得，在此不再赘述。According to the present invention, the compound represented by the formula (B) may be a commercially available product, or may be produced by a conventional method in the art, and will not be further described herein.
根据本发明，所述式(2)所示的化合物两端连接的醛基能够与式(B)所示的化合物发生脱水缩合，从而形成式(1)所示的化合物，其中，对所述式(2)所示的化合物与式(B)所示的化合物的用量并无特别的限定，只要能够制得式(1)所示的化合物即可，优选情况下，式(2)所示的化合物与式(B)所示的化合物的摩尔比为1：2-100，更优选为1：4-10。According to the present invention, the aldehyde group attached to both ends of the compound represented by the formula (2) can be dehydrated and condensed with the compound represented by the formula (B) to form a compound represented by the formula (1), wherein The amount of the compound represented by the formula (2) and the compound represented by the formula (B) is not particularly limited as long as the compound represented by the formula (1) can be obtained, and preferably, the formula (2) is shown. The molar ratio of the compound to the compound represented by the formula (B) is from 1:2 to 100, more preferably from 1:4 to 10.
根据本发明，该反应在碱性化合物存在下进行，从而可以为反应体系提供碱性环境，所述碱性化合物例如可以为哌啶、吡啶和三乙胺中一种或多种。对碱性化合物的用量并无特别的限定，只要能够提供碱性环境并有助于所述脱水缩合反应的进行即可，例如相对于1mmol式(2)所示的化合物，所述碱性化合物的用量为0.1-1000mmol，更优选为50-100mmol。According to the present invention, the reaction is carried out in the presence of a basic compound to provide an alkaline environment for the reaction system, and the basic compound may be, for example, one or more of piperidine, pyridine and triethylamine. The amount of the basic compound to be used is not particularly limited as long as it can provide an alkaline environment and contribute to the progress of the dehydration condensation reaction, for example, with respect to 1 mmol of the compound represented by the formula (2), the basic compound The amount used is from 0.1 to 1000 mmol, more preferably from 50 to 100 mmol.
根据本发明，所述有机溶剂例如为氯仿和/或二氯甲烷。其中，相对于1mmol式(2)所示的化合物，所述有机溶剂的用量例如可以为20-200mL(优选为40-200mL)。According to the invention, the organic solvent is, for example, chloroform and/or dichloromethane. Among them, the organic solvent may be used in an amount of, for example, 20 to 200 mL (preferably 40 to 200 mL) based on 1 mmol of the compound represented by the formula (2).
根据本发明，优选情况下，所述脱水缩合反应的条件包括：温度为20-100℃(例如50-100℃)，时间为10min-48h(例如10-20h)。更优选地，所述脱水缩合反应的条件包括：温度为60-80℃，时间为10-15h。According to the present invention, preferably, the conditions of the dehydration condensation reaction include a temperature of 20 to 100 ° C (for example, 50 to 100 ° C) for a time of 10 min to 48 h (for example, 10 to 20 h). More preferably, the conditions of the dehydration condensation reaction include a temperature of 60-80 ° C and a time of 10-15 h.
为了能够保证反应的顺利进行，该方法还包括在进行反应之前，将反应体系保持在惰性气氛下，例如可以在将原料都加毕后，向反应体系通入非活泼性气体20-40min以除去空气。所述非活泼性气体例如可以为氩气、氦气、氮气等。In order to ensure the smooth progress of the reaction, the method further comprises maintaining the reaction system under an inert atmosphere before the reaction, for example, after the raw materials are added, the reaction system is introduced with an inert gas for 20-40 minutes to remove air. The inert gas may be, for example, argon gas, helium gas, nitrogen gas or the like.
根据本发明，为了能够从反应液中提取出式(1)所示的化合物，该方法还包括后处理步骤，例如将脱水缩合反应产物与甲醇(相对于100mL反应液总体积，甲醇的用量例如可以为200-500mL)混合，然后进行固液分离，将所得固相采用硅胶色谱柱(可以采用200-300目的硅胶，洗脱剂可以为体积比为1:2-3的石油醚和二氯甲烷混合液)进行层析分离。According to the present invention, in order to be able to extract the compound represented by the formula (1) from the reaction liquid, the method further comprises a post-treatment step such as dehydration condensation reaction product with methanol (relative to the total volume of the reaction liquid of 100 mL, for example, the amount of methanol, for example It can be mixed with 200-500mL), then subjected to solid-liquid separation. The obtained solid phase is a silica gel column (200-300 mesh silica gel can be used, and the eluent can be petroleum ether and dichloride in a volume ratio of 1:2-3). The methane mixture was subjected to chromatographic separation.
本发明还提供了一种上述基于七并稠环单元的共轭大分子的制备方法，其中，该方法包括：在含钯催化剂存在下且在有机溶剂中，将下式(3)所示的化合物与式(C)所示的化合物进行偶联反应，得到式(1)所示的化合物；其中，The present invention also provides a method for preparing the above conjugated macromolecule based on a hepta-fused ring unit, wherein the method comprises: in the presence of a palladium-containing catalyst and in an organic solvent, the formula (3) The compound is subjected to a coupling reaction with a compound represented by the formula (C) to obtain a compound represented by the formula (1);
Figure PCTCN2016098397-appb-000061
Figure PCTCN2016098397-appb-000061
式(C)选自以下化合物中的一种或多种： Formula (C) is selected from one or more of the following compounds:
Figure PCTCN2016098397-appb-000062
Figure PCTCN2016098397-appb-000062
其中，四个R2各自独立地选自式
Figure PCTCN2016098397-appb-000063
所示的基团；两个R1各自独立地选自式
Figure PCTCN2016098397-appb-000064
所示的基团；其中，各个Z各自独立地选自C或Si；各个X和各个Y各自独立地选自O、S或Se；各个M各自独立地选自卤素；各个R'各自独立地选自C1-C4的烷基；m为1-6的整数；n为0-6的整数；各个R3、各个R4、各个R6和各个R7各自独立地选自H、C1-C30的烷基、C1-C30的烷氧基和C6-C12的芳基；各个R8各自独立地选自H、烷基、卤素、烷氧基和烷硫基。Wherein four R 2 are each independently selected from the formula
Figure PCTCN2016098397-appb-000063
a group shown; two R 1 are each independently selected from
Figure PCTCN2016098397-appb-000064
a group; wherein each Z is independently selected from C or Si; each X and each Y are each independently selected from O, S or Se; each M is independently selected from halogen; each R' is independently An alkyl group selected from C1-C4; m is an integer from 1 to 6; n is an integer from 0 to 6; each R 3 , each R 4 , each R 6 and each R 7 are each independently selected from H, C1-C30 An alkyl group, a C1-C30 alkoxy group and a C6-C12 aryl group; each R 8 is independently selected from the group consisting of H, alkyl, halogen, alkoxy and alkylthio.
其中，式(3)所示的化合物与式(C)所示的化合物可以根据所需制备的式(1)所示的化合物进行选择，因此，上述取代基、各个Z、各个X和各个Y、n和m如前文中所定义的，在此不再赘述。其中，作为M的卤素例如可以选自：Br、I、Cl。作为R'的C1-C4的烷基例如可以选自：甲基(Me)、乙基、丙基、丁基。Among them, the compound represented by the formula (3) and the compound represented by the formula (C) can be selected according to the compound represented by the formula (1) to be produced, and therefore, the above substituent, each Z, each X and each Y are selected. , n and m are as defined in the foregoing, and are not described here. Among them, the halogen as M may be, for example, selected from the group consisting of Br, I, and Cl. The C1-C4 alkyl group as R' may be, for example, selected from the group consisting of methyl (Me), ethyl, propyl, and butyl.
其中，当各个R8均为H时，式(C)可由下式表示：Wherein, when each R 8 is H, the formula (C) can be represented by the following formula:
Figure PCTCN2016098397-appb-000065
Figure PCTCN2016098397-appb-000065
作为式(3)所示的化合物的具体实例例如可以为以下式所示的化合物中的一种或多种：Specific examples of the compound represented by the formula (3) may be, for example, one or more of the compounds represented by the following formula:
式(3-1)：R'为甲基；R1不存在；R2为式
Figure PCTCN2016098397-appb-000066
所示的基团，且R3为正己基；Z为C。式(3-2)：R'为甲基；R1不存在；R2为式
Figure PCTCN2016098397-appb-000067
所示的基团，且R3为甲基；Z为C。式(3-3)：R'为甲基；R1不存在；R2为式
Figure PCTCN2016098397-appb-000068
所示的基团，且R3为乙基；Z 为C。式(3-4)：R'为甲基；R1不存在；R2为式
Figure PCTCN2016098397-appb-000069
所示的基团，且R3为正丙基；Z为C。式(3-5)：R'为甲基；R1不存在；R2为式
Figure PCTCN2016098397-appb-000070
所示的基团，且R3为正丁基；Z为C。式(3-6)：R'为甲基；R1不存在；R2为式
Figure PCTCN2016098397-appb-000071
所示的基团，且R3为正戊基；Z为C。Formula (3-1): R' is a methyl group; R 1 is absent; R 2 is a formula
Figure PCTCN2016098397-appb-000066
a group shown, and R 3 is n-hexyl; Z is C. Of formula (3-2): R 'is methyl; R 1 absent; R 2 is a formula
Figure PCTCN2016098397-appb-000067
a group shown, and R 3 is methyl; Z is C. Formula (3-3): R' is a methyl group; R 1 is absent; R 2 is a formula
Figure PCTCN2016098397-appb-000068
a group shown, and R 3 is ethyl; Z is C. Formula (3-4): R' is a methyl group; R 1 is absent; R 2 is a formula
Figure PCTCN2016098397-appb-000069
a group shown, and R 3 is n-propyl; Z is C. Of formula (3-5): R 'is methyl; R 1 absent; R 2 is a formula
Figure PCTCN2016098397-appb-000070
a group shown, and R 3 is n-butyl; Z is C. Formula (3-6): R' is a methyl group; R 1 is absent; R 2 is a formula
Figure PCTCN2016098397-appb-000071
a group shown, and R 3 is n-pentyl; Z is C.
根据本发明，式(3)所示的化合物可以是市售品，也可以通过本领域常规的方法制得，例如通过丁基锂反应上三烷基锡的方法制备。According to the present invention, the compound represented by the formula (3) may be a commercially available product, or may be produced by a conventional method in the art, for example, by a method in which a butyllithium reaction is carried out on a trialkyltin.
作为式(C-1)所示的化合物的具体实例例如可以为：式(C-1-1)
Figure PCTCN2016098397-appb-000072
Specific examples of the compound represented by the formula (C-1) can be, for example, the formula (C-1-1)
Figure PCTCN2016098397-appb-000072
作为式(C-2)所示的化合物的具体实例例如可以为：式(C-2-1)
Figure PCTCN2016098397-appb-000073
Specific examples of the compound represented by the formula (C-2) can be, for example, the formula (C-2-1)
Figure PCTCN2016098397-appb-000073
作为式(C-3)所示的化合物的具体实例例如可以为以下式所示的化合物中的一种或多种：Specific examples of the compound represented by the formula (C-3) may be, for example, one or more of the compounds represented by the following formula:
Figure PCTCN2016098397-appb-000074
Figure PCTCN2016098397-appb-000074
作为式(C-4)所示的化合物的具体实例例如可以为以下式所示的化合物中的一种或多种：Specific examples of the compound represented by the formula (C-4) may be, for example, one or more of the compounds represented by the following formula:
Figure PCTCN2016098397-appb-000075
Figure PCTCN2016098397-appb-000075
作为式(C-5)所示的化合物的具体实例例如可以为以下式所示的化合物中的一种或多种：Specific examples of the compound represented by the formula (C-5) may be, for example, one or more of the compounds represented by the following formula:
Figure PCTCN2016098397-appb-000076
Figure PCTCN2016098397-appb-000076
根据本发明，式(C)所示的化合物可以是市售品，也可以通过本领域常规的方法制得，例如通过NBS溴化的方法进行制备。According to the present invention, the compound represented by the formula (C) may be a commercially available product, or may be produced by a conventional method in the art, for example, by a method of bromination of NBS.
根据本发明，所述式(3)所示的化合物两端连接的SnR'3能够与式(C)所示的化合物中的卤素M发生偶联反应，脱除一份子的Sn(M)R'3，从而形成式(1)所示的化合物，其中，对所述式(3)所示的化合物与式(C)所示的化合物的用量并无特别的限定， 只要能够制得式(1)所示的化合物即可，优选情况下，式(3)所示的化合物与式(C)所示的化合物的摩尔比为1：2-10，更优选为1：2-5。According to the present invention, the SnR' 3 attached at both ends of the compound represented by the formula (3) can be coupled with the halogen M in the compound represented by the formula (C) to remove a portion of Sn(M)R. ' 3 , the compound represented by the formula (1) is formed, and the amount of the compound represented by the formula (3) and the compound represented by the formula (C) is not particularly limited as long as the formula can be obtained ( 1) The compound shown may be used. Preferably, the molar ratio of the compound represented by the formula (3) to the compound represented by the formula (C) is from 1:2 to 10, more preferably from 1:2 to 5.
根据本发明，该反应在含钯催化剂存在下进行，从而可以催化所述偶联反应的进行，所述含钯催化剂例如可以为四(三苯基膦)钯和/或二(三苯基膦)二氯化钯。对所述含钯催化剂的用量并无特别的限定，只要能够催化所偶联反应的进行即可，例如相对于1mmol式(3)所示的化合物，所述含钯催化剂的用量为0.01-0.1mmol，更优选为0.03-0.08mmol。According to the invention, the reaction is carried out in the presence of a palladium-containing catalyst which catalyzes the progress of the coupling reaction, which may for example be tetrakis(triphenylphosphine)palladium and/or bis(triphenylphosphine) ) Palladium dichloride. The amount of the palladium-containing catalyst to be used is not particularly limited as long as it can catalyze the progress of the coupling reaction. For example, the palladium-containing catalyst is used in an amount of 0.01 to 0.1 with respect to 1 mmol of the compound represented by the formula (3). M, more preferably 0.03-0.08 mmol.
根据本发明，所述有机溶剂例如为甲苯和/或四氢呋喃。其中，相对于1mmol式(3)所示的化合物，所述有机溶剂的用量例如可以为40-200mL。According to the invention, the organic solvent is, for example, toluene and/or tetrahydrofuran. Among them, the organic solvent may be used in an amount of, for example, 40 to 200 mL based on 1 mmol of the compound represented by the formula (3).
根据本发明，优选情况下，所述偶联反应的条件包括：温度为70-150℃(例如90-150℃)，时间为6-50h(例如20-50h)。更优选地，所述偶联反应的条件包括：温度为100-120℃，时间为20-40h(例如30-40h)。According to the present invention, preferably, the conditions of the coupling reaction include a temperature of 70 to 150 ° C (for example, 90 to 150 ° C) and a time of 6 to 50 h (for example, 20 to 50 h). More preferably, the conditions of the coupling reaction include a temperature of 100 to 120 ° C and a time of 20 to 40 h (for example, 30 to 40 h).
为了能够保证反应的顺利进行，该方法还包括在进行反应之前，将反应体系保持在惰性气氛下，例如可以在将原料都加毕后，向反应体系通入非活泼性气体20-40min以除去空气。所述非活泼性气体例如可以为氩气、氦气、氮气等。In order to ensure the smooth progress of the reaction, the method further comprises maintaining the reaction system under an inert atmosphere before the reaction, for example, after the raw materials are added, the reaction system is introduced with an inert gas for 20-40 minutes to remove air. The inert gas may be, for example, argon gas, helium gas, nitrogen gas or the like.
根据本发明，为了能够从反应液中提取出式(1)所示的化合物，该方法还包括后处理步骤，例如将偶联反应产物与甲醇(相对于100mL反应液总体积，甲醇的用量例如可以为200-500mL)混合，然后进行固液分离，将所得固相采用硅胶色谱柱(可以采用200-300目的硅胶，洗脱剂可以为体积比为1:2-3的石油醚和二氯甲烷混合液)进行层析分离。According to the present invention, in order to be able to extract the compound represented by the formula (1) from the reaction liquid, the method further comprises a post-treatment step, for example, coupling the reaction product with methanol (relative to the total volume of the reaction liquid of 100 mL, for example, the amount of methanol, for example It can be mixed with 200-500mL), then subjected to solid-liquid separation. The obtained solid phase is a silica gel column (200-300 mesh silica gel can be used, and the eluent can be petroleum ether and dichloride in a volume ratio of 1:2-3). The methane mixture was subjected to chromatographic separation.
本发明提供了含有上述基于七并稠环单元的共轭大分子的光伏材料。The present invention provides a photovoltaic material comprising the above conjugated macromolecule based on a hepta-fused ring unit.
根据本发明，对所述光伏材料并无特别的限定，只要含有本发明的上述基于七并稠环单元的共轭大分子即可，该光伏材料优选是指太阳能电池中的光捕获的活性层中电子给体材料和/或电子受体材料。According to the present invention, the photovoltaic material is not particularly limited as long as it contains the above-mentioned conjugated macromolecule based on a hepta-fused ring unit of the present invention, and the photovoltaic material preferably refers to a light-trapping active layer in a solar cell. Medium electron donor material and/or electron acceptor material.
例如，可以将电子给体材料聚合物材料PDBT-T1和/或聚合物材料PTB7-Th与本发明提供的基于七并稠环单元的共轭大分子以重量比为0.5-4：1进行组合来作为所述光伏材料，特别是作为太阳能电池的光捕获活性层的光伏材料，其中，本发明提供的基于七并稠环单元的共轭大分子则作为电子受体材料。For example, the electron donor material polymer material PDBT-T1 and/or the polymer material PTB7-Th may be combined with the conjugated macromolecule based on the hepta-fused ring unit provided by the present invention in a weight ratio of 0.5-4:1. As the photovoltaic material, in particular, a photovoltaic material as a light-trapping active layer of a solar cell, wherein the conjugated macromolecule based on the hepta-fused ring unit provided by the present invention serves as an electron acceptor material.
其中，聚合物材料PDBT-T1和聚合物材料PTB7-Th的结构单元分别如下所示： Among them, the structural units of the polymer material PDBT-T1 and the polymer material PTB7-Th are as follows:
Figure PCTCN2016098397-appb-000077
其中，-C8H17表示正辛基，-C4H9表示正丁基。
Figure PCTCN2016098397-appb-000077
Wherein -C 8 H 17 represents n-octyl group and -C 4 H 9 represents n-butyl group.
本发明还提供了一种太阳能电池，该太阳能电池包括光捕获的活性层，其中，所述光捕获的活性层中电子给体材料和/或电子受体材料含有上述基于七并稠环单元的共轭大分子。The present invention also provides a solar cell comprising a light-trapping active layer, wherein the electron-trapping material and/or electron acceptor material in the light-trapping active layer contains the above-described hepta-fused ring unit Conjugated macromolecules.
根据本发明，本发明对太阳能电池的构造并无特别的限定，只要其光捕获的活性层中电子给体材料和/或电子受体材料含有上述基于七并稠环单元的共轭大分子即可，这样就可以有效地提高太阳能电池的光电转换效率。According to the present invention, the configuration of the solar cell of the present invention is not particularly limited as long as the electron donor material and/or the electron acceptor material in the light-trapping active layer contains the above-mentioned conjugated macromolecule based on a hepta-fused ring unit. Yes, this can effectively improve the photoelectric conversion efficiency of the solar cell.
特别是，本发明的基于七并稠环单元的共轭大分子适用于用于有机太阳能电池中，特别作为电子受体材料与其他电子给体材料组合以形成太阳能电池的光捕获的活性层。作为这样的电子给体材料例如可以为聚合物材料PDBT-T1和/或聚合物材料PTB7-Th，如上文中所定义的。In particular, the conjugated macromolecules based on hepta-fused ring units of the present invention are suitable for use in organic solar cells, particularly as an electron acceptor material in combination with other electron donor materials to form a light-trapping active layer of a solar cell. As such an electron donor material, for example, may be a polymer material PDBT-T1 and/or a polymer material PTB7-Th, as defined above.
其中，聚合物材料PDBT-T1和/或聚合物材料PTB7-Th可以与本发明提供的基于七并稠环单元的共轭大分子以重量比为0.5-4：1进行组合来形成光捕获的活性层。Wherein, the polymer material PDBT-T1 and/or the polymer material PTB7-Th can be combined with the conjugated macromolecule based on the hepta-fused ring unit provided by the present invention in a weight ratio of 0.5-4:1 to form light-trapping. Active layer.
本发明还提供了一种太阳能电池的制备方法，其中，该方法包括将含有上述基于七并稠环单元的共轭大分子的电子给体材料和/或电子受体材料用于形成光捕获的活性层。The present invention also provides a method of preparing a solar cell, wherein the method comprises using an electron donor material and/or an electron acceptor material containing the above-mentioned conjugated macromolecule based on a hepta-fused ring unit for forming light trapping. Active layer.
根据本发明，对太阳能电池的制备过程并无特别的限定，可以采用本领域常规的方法进行，例如该制备过程可以包括：According to the present invention, the preparation process of the solar cell is not particularly limited and may be carried out by a method conventional in the art. For example, the preparation process may include:
在作为阴极的导电玻璃(例如氧化铟锡玻璃，ITO)上涂覆ZnO层作为阴极修饰层(厚度例如可以为20-50nm)，干燥后，再在ZnO层上涂覆上聚合物材料PDBT-T1和/或聚合物材料PTB7-Th与本发明提供的基于七并稠环单元的共轭大分子的混合物作为活性层，干燥后，再真空蒸镀上氧化钼(厚度例如可以为5-10nm)和Ag(厚度例如可以为50-100nm)作为阳极。A ZnO layer is coated on the conductive glass (for example, indium tin oxide glass, ITO) as a cathode as a cathode modification layer (thickness may be, for example, 20 to 50 nm), and after drying, a polymer material PDBT- is coated on the ZnO layer. As a living layer, a mixture of T1 and/or polymer material PTB7-Th and a conjugated macromolecule based on a hepta-fused ring unit provided by the present invention is dried, and then vacuum-deposited with molybdenum oxide (the thickness may be, for example, 5-10 nm). And Ag (thickness may be, for example, 50-100 nm) as an anode.
本发明提供的基于七并稠环单元的共轭大分子具有较强的可见光吸收峰，例如在500-800nm的波长范围内具有强吸收峰；该共轭大分子热稳定性良好，可耐受300℃左右的温度而不分解；循环伏安法测试结果表明，其HOMO能级和LUMO能级可以与 大部分通用的电子给体材料能级匹配，且其具有较好的接受电子或空穴能力，非常利于作为太阳能电池的光伏材料，特别是电子受体和/或电子给体材料，尤其是作为电子受体材料。The conjugated macromolecule based on hepta-fused ring unit provided by the invention has strong visible light absorption peak, for example, has a strong absorption peak in a wavelength range of 500-800 nm; the conjugated macromolecule has good thermal stability and can withstand The temperature around 300 °C does not decompose; cyclic voltammetry test results show that its HOMO level and LUMO level can be Most common electron donor materials have energy level matching, and they have good ability to accept electrons or holes, which is very beneficial as a photovoltaic material for solar cells, especially electron acceptors and/or electron donor materials, especially as Electron acceptor material.
本发明提供的太阳能电池，具有较高的短路电流，例如可以达到14mA·cm-2以上，优选可达到17mA·cm-2以上；较高的开路电压，例如可达到0.8V以上，优选可达到0.85V以上；较高的填充因子，例如可达到65％以上，优选可达到68％以上；较高的光电转换率(PCE)，例如可达到8.5％以上，优选可达到10％以上。The solar cell provided by the invention has a high short-circuit current, for example, can reach 14 mA·cm -2 or more, preferably can reach 17 mA·cm -2 or more; a high open circuit voltage can reach, for example, 0.8 V or more, preferably achievable Higher than 0.85V; higher filling factor, for example, can reach more than 65%, preferably can reach more than 68%; higher photoelectric conversion rate (PCE), for example, can reach 8.5% or more, preferably can reach more than 10%.
以下将通过实施例对本发明进行详细描述。The invention will be described in detail below by way of examples.
以下实施例中：1H NMR和13C NMR是采用Bruker公司AVANCE 400型号的核磁共振仪测量的。MS(MALDI)是采用Bruker Daltonics Biflex III MALDI-TOF Analyzer型号的质谱仪进行测量的。元素分析是采用Flash EA1112elemental analyzer型号的元素分析仪进行测量的。紫外-可见吸收光谱是采用Jasco V-570spectrophotometer型号的紫外-可见分光光度计进行测量的。循环伏安曲线是采用CHI660C electrochemical workstation型号的循环伏安测试仪进行测量的。热失重曲线是采用Shimadzu thermogravimetric analyzer(Model DTG-60)型号的热重分析仪进行测量的。空间电荷限制电流曲线是采用B2912A Precision Source/Measure Unit(Agilent Technologies)型号的进行测量的。I-V曲线是通过B2912A Precision Source/Measure Unit(Agilent Technologies)测量的，从I-V曲线可以得到短路电流、开路电压、填充因子和光电转换效率等参数。In the following examples: 1 H NMR and 13 C NMR were measured using a nuclear magnetic resonance apparatus of the Bruker AVANCE 400 model. MS (MALDI) was measured using a mass spectrometer of the Bruker Daltonics Biflex III MALDI-TOF Analyzer model. Elemental analysis was performed using an elemental analyzer of the Flash EA1112elemental analyzer model. The UV-Vis absorption spectrum was measured using an ultraviolet-visible spectrophotometer of the Jasco V-570 Spectrophotometer model. The cyclic voltammetry curve was measured using a cyclic voltammetry tester of the CHI660C electrochemical workstation model. The thermogravimetric curve was measured using a thermogravimetric analyzer model Shimadzu thermogravimetric analyzer (Model DTG-60). The space charge limited current curve was measured using the B2912A Precision Source/Measure Unit (Agilent Technologies) model. The IV curve is measured by the B2912A Precision Source/Measure Unit (Agilent Technologies). Short-circuit current, open circuit voltage, fill factor, and photoelectric conversion efficiency can be obtained from the IV curve.
实施例1Example 1
本实施例用于说明本发明的基于七并稠环单元的共轭大分子及其制备方法。This example is intended to illustrate the conjugated macromolecule based on the hepta-fused ring unit of the present invention and a process for the preparation thereof.
Figure PCTCN2016098397-appb-000078
Figure PCTCN2016098397-appb-000078
如上反应式所示，将式(2-1)所示的化合物(220mg，0.2mmol；购自朔纶有机光电科技(北京)有限公司)、式(B-2)所示的化合物(200mg，1mmol；购自TCI公司)、氯仿(50mL)和吡啶(10mL，12mmol)加入到反应容器中，并通氩气30min以去除空气，而后在65℃下回流12h。然而冷却至室温(约20℃)，将反应产物倒入至200mL甲醇中，过滤，得到的沉淀用硅胶色谱柱(采用200-300目的硅胶，洗脱剂为体积比为 1:2的石油醚/二氯甲烷)进行层析分离，得到深蓝色固体(180mg，收率为62％)，即为式(1-2)所示的基于七并稠环单元的共轭大分子。1H NMR(400MHz,CDCl3):δ8.90(s,2H),8.71(d,J＝7.6Hz,2H),8.25(s,2H),7.94(d,J＝6.4Hz,2H),7.83(s,2H),7.76(m,4H),6.90(d,J＝3.2Hz,4H),7.15(d,J＝3.6Hz,4H),2.72(t,J＝7.6Hz,8H),1.64(m,8H),1.33(m,24H),0.87(m,12H).13C NMR(100MHz,CDCl3):δ188.34,160.56,155.70,152.80,147.205,146.83,146.46,143.83,141.40,140.24,140.20,138.48,137.10,136.86,136.05,135.43,134.74,126.57,125.55,124.02,123.80,123.22,122.73,118.54,114.80,114.74,69.79,57.19,37.71,31.54,30.47,29.10,22.72,14.25.MS(MALDI):m/z 1451(M+1).Anal.:Calc.for C86H74N4O2S8:C,71.14；H,5.14；N,3.86.Found:C,70.67；H,5.15；N,3.96％.The compound represented by the formula (2-1) (220 mg, 0.2 mmol; purchased from Polyene Organic Optoelectronics (Beijing) Co., Ltd.) and the compound represented by the formula (B-2) (200 mg, as shown in the above reaction formula) 1 mmol; purchased from TCI), chloroform (50 mL) and pyridine (10 mL, 12 mmol) were added to the reaction vessel, and argon gas was passed for 30 min to remove air, followed by reflux at 65 ° C for 12 h. However, it was cooled to room temperature (about 20 ° C), and the reaction product was poured into 200 mL of methanol, and filtered, and the obtained precipitate was subjected to a silica gel column (using 200-300 mesh silica gel, eluent was a petroleum ether in a volume ratio of 1:2). / dichloromethane) Chromatographic separation gave a dark blue solid (180 mg, yield 62%), which is a conjugated macromolecule based on a hepta-fused ring unit represented by formula (1-2). 1 H NMR (400MHz, CDCl 3 ): δ8.90 (s, 2H), 8.71 (d, J = 7.6Hz, 2H), 8.25 (s, 2H), 7.94 (d, J = 6.4Hz, 2H), 7.83 (s, 2H), 7.76 (m, 4H), 6.90 (d, J = 3.2 Hz, 4H), 7.15 (d, J = 3.6 Hz, 4H), 2.72 (t, J = 7.6 Hz, 8H), 1.64 (m, 8H), 1.33 (m, 24H), 0.87 (m, 12H). 13 C NMR (100MHz, CDCl 3 ): δ 188.34, 160.56, 155.70, 152.80, 147.205, 146.83, 146.46, 143.83, 141.40, 140.24 , 140.20, 138.48, 137.10, 136.86, 136.05, 135.43, 134.74, 126.57, 125.55, 124.02, 123.80, 123.22, 122.73, 118.54, 114.80, 114.74, 69.79, 57.19, 37.71, 31.54, 30.47, 29.10, 22.72, 14.25.MS (MALDI): m/z 1451 (M+1). Anal.: Calc. for C 86 H 74 N 4 O 2 S 8 : C, 71.14; H, 5.14; N, 3.86. Found: C, 70.67; , 5.15; N, 3.96%.
该式(1-2)所示的基于七并稠环单元的共轭大分子的紫外-可见吸收光谱如图1所示，其中，在500-800nm的波长范围内具有强吸收峰，最大摩尔消光系数为1.5×105M–1·cm–1，在700nm左右处吸收最强；The ultraviolet-visible absorption spectrum of the conjugated macromolecule based on the hepta-fused ring unit represented by the formula (1-2) is shown in Fig. 1, wherein a strong absorption peak and a maximum molar ratio are in the wavelength range of 500 to 800 nm. The extinction coefficient is 1.5×10 5 M –1 ·cm –1 , and the absorption is strongest at around 700 nm;
循环伏安曲线如图2所示，其HOMO能级为-5.66eV，LUMO能级为-3.93eV，表明式(1-2)所示的化合物具有较好的电子接受能力，可以与大部分通用的电子给体材料能级匹配；The cyclic voltammetry curve is shown in Figure 2. The HOMO level is -5.66 eV and the LUMO level is -3.93 eV, indicating that the compound of formula (1-2) has good electron acceptability and can be used with most General purpose electron donor material level matching;
热失重曲线如图3所示，表明式(1-2)所示的化合物具有较好的热稳定性，可至300℃无分解。The thermogravimetric curve is shown in Fig. 3, indicating that the compound represented by the formula (1-2) has good thermal stability and can be decomposed to 300 °C.
空间电荷限制电流曲线如图4所示，表明式(1-2)所示的化合物具有高的电子迁移率，即为6.1×10–4cm2·V–1·s–1。The space charge limited current curve is shown in Fig. 4, indicating that the compound represented by the formula (1-2) has a high electron mobility, that is, 6.1 × 10 -4 cm 2 · V -1 · s -1 .
实施例2Example 2
本实施例用于说明本发明的基于七并稠环单元的共轭大分子及其制备方法。This example is intended to illustrate the conjugated macromolecule based on the hepta-fused ring unit of the present invention and a process for the preparation thereof.
Figure PCTCN2016098397-appb-000079
Figure PCTCN2016098397-appb-000079
如上反应式所示，将式(3-1)所示的化合物(275mg，0.2mmol；购自朔纶有机光电科技(北京)有限公司)、式(C-1-1)所示的化合物(116mg，0.4mmol；购自苏州纳凯科技有限公司)、甲苯(50mL)和四(三苯基膦)钯(10mg，0.009mmol)加入到反应容器中，并通氩气30min以去除空气，而后在110℃下回流36h。旋干后得到的固体用硅胶色谱柱(采用200-300目的硅胶，洗脱剂为体积比为1:2的石油醚/二氯甲烷)进行层析分离，得到深蓝色固体(280mg，收率为95％)，即为式(1-8)所示的基于七并稠环单元的共轭大分子。1H-NMR(400MHz,CD2Cl2):δ8.79(s,2H),8.72(s,2H),8.67(d,J＝8 Hz,2H),7.92(d,J＝8Hz,2H),7.65(s,2H),7.16(d,J＝3.6Hz,4H),6.91(d,J＝3.6Hz,4H),2.58(m,8H),1.57(m,8H),1.29(m,24H),0.83(m,12H).13C-NMR(100MHz,CDCl3):δ154.52,154.31,151.89,150.78,147.31,146.82,143.81,142.25,139.62,136.86,136.64,133.22,130.55,128.76,127.98,125.18,123.56,121.22,117.69,114.03,113.22,81.52,63.03,35.55,31.65,31.26,29.15,22.52,14.02.MS(MALDI):m/z 1478(M).Anal.:Calc.for C81H74N8S10:C,65.73；H,5.04；N,7.57.Found:C,65.71；H,5.05；N,7.42％.The compound represented by the formula (3-1) (275 mg, 0.2 mmol; purchased from Polyene Organic Optoelectronics (Beijing) Co., Ltd.) and the compound represented by the formula (C-1-1) are shown in the above reaction formula ( 116 mg, 0.4 mmol; purchased from Suzhou Nakai Technology Co., Ltd.), toluene (50 mL) and tetrakis(triphenylphosphine)palladium (10 mg, 0.009 mmol) were added to the reaction vessel, and argon gas was passed for 30 min to remove air, and then It was refluxed at 110 ° C for 36 h. The solid obtained by spin-drying was chromatographed on a silica gel column (with 200-300 mesh silica gel, eluent eluted with petroleum ether/dichloromethane of 1:2) to give a dark blue solid (280 mg, yield It is 95%), which is a conjugated macromolecule based on a hepta-fused ring unit represented by formula (1-8). 1 H-NMR (400 MHz, CD 2 Cl 2 ): δ 8.79 (s, 2H), 8.72 (s, 2H), 8.67 (d, J = 8 Hz, 2H), 7.92 (d, J = 8 Hz, 2H) ), 7.65 (s, 2H), 7.16 (d, J = 3.6 Hz, 4H), 6.91 (d, J = 3.6 Hz, 4H), 2.58 (m, 8H), 1.57 (m, 8H), 1.29 (m) , 24H), 0.83 (m, 12H). 13 C-NMR (100MHz, CDCl 3 ): δ 154.52, 154.31, 151.89, 150.78, 147.31, 146.82, 143.81, 142.25, 139.62, 136.86, 136.64, 133.22, 130.55, 128.76, 127.98,125.18,123.56,121.22,117.69,114.03,113.22,81.52,63.03,35.55,31.65,31.26,29.15,22.52,14.02.MS(MALDI):m/z 1478(M).Anal.:Calc.for C 81 H 74 N 8 S 10: C, 65.73; H, 5.04; N, 7.57.Found: C, 65.71; H, 5.05; N, 7.42%.
该式(1-8)所示的基于七并稠环单元的共轭大分子的紫外-可见吸收光谱显示，在500-800nm的波长范围内具有强吸收峰；The ultraviolet-visible absorption spectrum of the conjugated macromolecule based on the hepta-fused ring unit represented by the formula (1-8) shows a strong absorption peak in a wavelength range of 500 to 800 nm;
循环伏安曲线表明式(1-8)所示的化合物的HOMO能级为-3.8eV，LUMO能级为-5.6eV，表明式(1-8)所示的化合物具有较好的电子接受能力，可以与大部分通用的电子给体材料能级匹配；The cyclic voltammetry curve indicates that the compound represented by the formula (1-8) has a HOMO level of -3.8 eV and a LUMO level of -5.6 eV, indicating that the compound represented by the formula (1-8) has good electron acceptability. , can match the energy level of most common electronic donor materials;
热失重曲线表明式(1-8)所示的化合物具有较好的热稳定性，可至300℃无分解。The thermogravimetric curve shows that the compound represented by the formula (1-8) has good thermal stability and can be decomposed to 300 °C.
空间电荷限制电流曲线表明式(1-8)所示的化合物具有高的电子迁移率，即为5×10–4cm2·V–1·s–1。The space charge limited current curve indicates that the compound represented by the formula (1-8) has a high electron mobility, that is, 5 × 10 -4 cm 2 ·V -1 ·s -1 .
实施例3Example 3
本实施例用于说明书本发明的太阳能电池。This embodiment is for explaining the solar cell of the present invention.
将作为阴极的氧化铟锡(ITO)玻璃(购自深圳南玻浮法玻璃有限公司)先用洗洁剂清洗，然后依次用水、去离子水、丙酮、异丙醇超声清洗，干燥后旋涂一层30nm厚的ZnO阴极修饰层，200℃下干燥30分钟，备用。Indium tin oxide (ITO) glass as cathode (purchased from Shenzhen CSG Float Glass Co., Ltd.) was first washed with detergent, then ultrasonically washed with water, deionized water, acetone and isopropanol, dried and then spin coated. A 30 nm thick ZnO cathode modification layer was dried at 200 ° C for 30 minutes for use.
1mg上述式(1-2)所示的基于七并稠环单元的共轭大分子与1mg聚合物给体材料PDBT-T1(购自朔纶有机光电科技(北京)有限)在0.1mL氯仿中进行混合得到混合液，而后将其旋涂于上述ZnO层上，干燥后即可获得光捕获活性层(有效面积为4mm2)。在活性层上真空(绝对压力为3×10-5Pa)蒸镀厚度5nm左右MoO3(购自百灵威科技有限公司)和80nm左右的金属Ag作为太阳能电池的阳极。1 mg of the conjugated macromolecule based on the hepta-fused ring unit represented by the above formula (1-2) and 1 mg of the polymer donor material PDBT-T1 (purchased from Polyene Organic Optoelectronics (Beijing) Co., Ltd.) in 0.1 mL of chloroform The mixture was mixed to obtain a mixture, which was then spin-coated on the above ZnO layer, and after drying, a light-trapping active layer (effective area: 4 mm 2 ) was obtained. On the active layer, vacuum (absolute pressure: 3 × 10 -5 Pa) was vapor-deposited with MoO 3 (purchased from BEHRINGER TECHNOLOGY CO., LTD.) and metal Ag of about 80 nm as the anode of the solar cell.
用配有AM1.5滤光片(SAN-EI ELECTRIC Co.,Ltd.的XES-70S1型号)模拟太阳光源，在100mW/cm2光强下对器件进行光伏性能测试，光强通过标准单晶硅太阳能电池(购自VLSI Standards Inc)校准。所得的I-V曲线使用B2912A Precision Source/Measure Unit(Agilent Technologies)进行测量，通过Labview软件由计算机进行控制。The solar light source was simulated with an AM1.5 filter (XES-70S1 model of SAN-EI ELECTRIC Co., Ltd.), and the device was tested for photovoltaic performance at a light intensity of 100 mW/cm 2 , and the light intensity passed through a standard single crystal. Silicon solar cells (purchased from VLSI Standards Inc) are calibrated. The resulting IV curve was measured using a B2912A Precision Source/Measure Unit (Agilent Technologies) and controlled by a computer using Labview software.
所得的I-V曲线如图5所示。通过图5所示的I-V曲线可得该太阳能电池的短路电流Jsc为17mA·cm-2，开路电压Voc为0.88V，填充因子FF为70％，光电转换效率PCE为10.5％。 The resulting IV curve is shown in Figure 5. The short-circuit current J sc of the solar cell was 17 mA·cm -2 , the open circuit voltage V oc was 0.88 V, the fill factor FF was 70%, and the photoelectric conversion efficiency PCE was 10.5%.
实施例4Example 4
根据实施例3所述的方法，不同的是，1.5mg上述式(1-2)所示的基于七并稠环单元的共轭大分子与1mg聚合物给体材料PTB7-Th(购自朔纶有机光电科技(北京)有限公司)在0.1mL邻二氯苯中进行混合得到混合液，而后将其旋涂于上述ZnO层上，干燥后即可获得光捕获活性层。According to the method described in Example 3, 1.5 mg of the conjugated macromolecule based on the hepta-fused ring unit represented by the above formula (1-2) and 1 mg of the polymer donor material PTB7-Th (purchased from hydrazine) Lun Organic Photoelectric Technology (Beijing) Co., Ltd. mixed in 0.1 mL of o-dichlorobenzene to obtain a mixed solution, which was then spin-coated on the above ZnO layer, and dried to obtain a light-trapping active layer.
所得的I-V曲线如图6所示。通过图6所示的I-V曲线可得该太阳能电池的短路电流Jsc为19mA·cm-2，开路电压Voc为0.80V，填充因子FF为68％，光电转换效率PCE为10.4％。The resulting IV curve is shown in Figure 6. The short-circuit current J sc of the solar cell was 19 mA·cm -2 , the open circuit voltage V oc was 0.80 V, the fill factor FF was 68%, and the photoelectric conversion efficiency PCE was 10.4%.
实施例5Example 5
根据实施例3所述的方法，不同的是，采用1mg上述式(1-8)所示的基于七并稠环单元的共轭大分子代替式(1-2)所示的基于七并稠环单元的共轭大分子。According to the method described in Example 3, except that 1 mg of the conjugated macromolecule based on the hepta-fused ring unit represented by the above formula (1-8) is substituted for the seven-fold thickening represented by the formula (1-2) A conjugated macromolecule of a ring unit.
所得的I-V曲线如图7所示。通过图7所示的I-V曲线可得该太阳能电池的短路电流Jsc为14.5mA·cm-2，开路电压Voc为0.90V，填充因子FF为69％，光电转换效率PCE为9.0％。The resulting IV curve is shown in Figure 7. The solar cell can be obtained by the IV curve shown in FIG. 7 of the short circuit current J sc 14.5mA · cm -2, the open circuit voltage V oc was 0.90 V, 69% fill factor FF, the photoelectric conversion efficiency of 9.0% PCE.
实施例6Example 6
根据实施例4所述的方法，不同的是，采用1.5mg上述式(1-8)所示的基于七并稠环单元的共轭大分子代替式(1-2)所示的基于七并稠环单元的共轭大分子。According to the method described in Example 4, except that 1.5 mg of the conjugated macromolecule based on the hepta-fused ring unit represented by the above formula (1-8) is used instead of the seven-parts represented by the formula (1-2) Conjugated macromolecules of fused ring units.
所得的I-V曲线如图8所示。通过图8所示的I-V曲线可得该太阳能电池的短路电流Jsc为15.6mA·cm-2，开路电压Voc为0.85V，填充因子FF为67％，光电转换效率PCE为8.9％。The resulting IV curve is shown in Figure 8. The short-circuit current J sc of the solar cell was 15.6 mA·cm -2 , the open circuit voltage V oc was 0.85 V, the fill factor FF was 67%, and the photoelectric conversion efficiency PCE was 8.9%.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present invention within the scope of the technical idea of the present invention. These simple variants All fall within the scope of protection of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。It should be further noted that the specific technical features described in the above specific embodiments may be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention has various possibilities. The combination method will not be described separately.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。 In addition, any combination of various embodiments of the invention may be made as long as it does not deviate from the idea of the invention, and it should be regarded as the disclosure of the invention.

Claims (17)

  1. 一种基于七并稠环单元的共轭大分子，其特征在于，该共轭大分子为下式(1)所示的化合物：A conjugated macromolecule based on a hepta-fused ring unit, characterized in that the conjugated macromolecule is a compound represented by the following formula (1):
    Figure PCTCN2016098397-appb-100001
    Figure PCTCN2016098397-appb-100001
    其中，两个基团A独立地选自以下结构：Wherein two groups A are independently selected from the following structures:
    Figure PCTCN2016098397-appb-100002
    Figure PCTCN2016098397-appb-100002
    四个R2各自独立地选自式
    Figure PCTCN2016098397-appb-100003
    所示的基团；两个R1各自独立地选自式
    Figure PCTCN2016098397-appb-100004
    所示的基团；其中，各个Z各自独立地选自C或Si；各个X和各个Y各自独立地选自O、S或Se；m为1-6的整数；n为0-6的整数；各个R3、各个R4、R5、各个R6和各个R7各自独立地选自H、C1-C30的烷基、C1-C30的烷氧基和C6-C12的芳基；各个R8各自独立地选自H、烷基、卤素、烷氧基和烷硫基。    Four R 2 are each independently selected from the formulas
    Figure PCTCN2016098397-appb-100003
    a group shown; two R 1 are each independently selected from
    Figure PCTCN2016098397-appb-100004
    a group shown; wherein each Z is independently selected from C or Si; each X and each Y are each independently selected from O, S or Se; m is an integer from 1 to 6; n is an integer from 0 to 6 Each R 3 , each R 4 , R 5 , each R 6 and each R 7 are each independently selected from the group consisting of H, a C1-C30 alkyl group, a C1-C30 alkoxy group, and a C6-C12 aryl group; 8 are each independently selected from the group consisting of H, alkyl, halogen, alkoxy, and alkylthio.
  2. 根据权利要求1所述的共轭大分子，其中，各个R8均选自H。The conjugated macromolecule according to claim 1, wherein each R 8 is selected from H.
  3. 根据权利要求1所述的共轭大分子，其中，各个R8各自独立地选自烷基、卤素、烷氧基和烷硫基，优选选自C1-C6的烷基、卤素、C1-C6的烷氧基和C1-C6的烷硫基， 优选选自甲基、乙基、正丙基、异丙基、正丁基、F、Cl、Br、甲氧基、乙氧基、丙氧基、丁氧基、甲硫基、乙硫基、丙硫基和丁硫基。The conjugated macromolecule according to claim 1, wherein each R 8 is independently selected from the group consisting of alkyl, halogen, alkoxy and alkylthio, preferably selected from C1-C6 alkyl, halogen, C1-C6. Alkoxy and C1-C6 alkylthio, preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, F, Cl, Br, methoxy, ethoxy, propoxy Base, butoxy, methylthio, ethylthio, propylthio and butylthio.
  4. 根据权利要求2或3所述的共轭大分子，其中，m为1-4的整数，n为0-4的整数；The conjugated macromolecule according to claim 2 or 3, wherein m is an integer of from 1 to 4, and n is an integer of from 0 to 4;
    优选地，各个R3、各个R4、各个R6和各个R7各自独立地选自H、C1-C12的烷基和C1-C12的烷氧基，R5选自苯基或苄基。Preferably, each R 3, each R 4, each R 6 and each R 7 is independently selected from H, C1-C12 alkyl groups and C1-C12 alkoxy, R 5 is selected from phenyl or benzyl.
  5. 根据权利要求2或3所述的共轭大分子，其中，m为1、2或3，n为0、1、2或3，Z为C，X为O或S，Y为S；各个R3、各个R4、各个R6和各个R7各自独立地选自H和C1-C8的烷基，R5选自苯基或苄基。The conjugated macromolecule according to claim 2 or 3, wherein m is 1, 2 or 3, n is 0, 1, 2 or 3, Z is C, X is O or S, and Y is S; each R 3 , each R 4 , each R 6 and each R 7 are each independently selected from the group consisting of H and C1-C8 alkyl, and R 5 is selected from phenyl or benzyl.
  6. 根据权利要求1-5中任意一项所述的共轭大分子，其中，所述共轭大分子为以下式所示的化合物中的一种：The conjugated macromolecule according to any one of claims 1 to 5, wherein the conjugated macromolecule is one of the compounds represented by the following formula:
    式(1-1)：A为
    Figure PCTCN2016098397-appb-100005
    R1不存在；R2为式
    Figure PCTCN2016098397-appb-100006
    所示的基团，且R3为正己基；Z为C；    Formula (1-1): A is
    Figure PCTCN2016098397-appb-100005
    R 1 does not exist; R 2 is a formula
    Figure PCTCN2016098397-appb-100006
    a group shown, and R 3 is n-hexyl; Z is C;
    式(1-2)：A为
    Figure PCTCN2016098397-appb-100007
    R1不存在；R2为式
    Figure PCTCN2016098397-appb-100008
    所示的基团，且R3为正己基；Z为C；    Equation (1-2): A is
    Figure PCTCN2016098397-appb-100007
    R 1 does not exist; R 2 is a formula
    Figure PCTCN2016098397-appb-100008
    a group shown, and R 3 is n-hexyl; Z is C;
    式(1-3)：A为
    Figure PCTCN2016098397-appb-100009
    R1不存在；R2为式
    Figure PCTCN2016098397-appb-100010
    所示的基团，且R3为正己基；Z为C；    Formula (1-3): A is
    Figure PCTCN2016098397-appb-100009
    R 1 does not exist; R 2 is a formula
    Figure PCTCN2016098397-appb-100010
    a group shown, and R 3 is n-hexyl; Z is C;
    式(1-4)：A为
    Figure PCTCN2016098397-appb-100011
    R1不存在；R2为式
    Figure PCTCN2016098397-appb-100012
    所示的基团，且R3为正己基；Z为C；    Formula (1-4): A is
    Figure PCTCN2016098397-appb-100011
    R 1 does not exist; R 2 is a formula
    Figure PCTCN2016098397-appb-100012
    a group shown, and R 3 is n-hexyl; Z is C;
    式(1-5)：A为
    Figure PCTCN2016098397-appb-100013
    R1不存在；R2为式
    Figure PCTCN2016098397-appb-100014
    所示的基团，且R3为正己基；Z为C；     Formula (1-5): A is
    Figure PCTCN2016098397-appb-100013
    R 1 does not exist; R 2 is a formula
    Figure PCTCN2016098397-appb-100014
    A group represented by and R 3 is n-hexyl diyl; Z are C;
    式(1-6)：A为
    Figure PCTCN2016098397-appb-100015
    R1不存在；R2为式
    Figure PCTCN2016098397-appb-100016
    所示的基团，且R3为正己基；Z为C；    Formula (1-6): A is
    Figure PCTCN2016098397-appb-100015
    R 1 does not exist; R 2 is a formula
    Figure PCTCN2016098397-appb-100016
    a group shown, and R 3 is n-hexyl; Z is C;
    式(1-7)：A为
    Figure PCTCN2016098397-appb-100017
    R1不存在；R2为式
    Figure PCTCN2016098397-appb-100018
    所示的基团，且R3为正己基；Z为C；    Formula (1-7): A is
    Figure PCTCN2016098397-appb-100017
    R 1 does not exist; R 2 is a formula
    Figure PCTCN2016098397-appb-100018
    A group represented by and R 3 is n-hexyl diyl; Z are C;
    式(1-8)：A为
    Figure PCTCN2016098397-appb-100019
    R1不存在；R2为式
    Figure PCTCN2016098397-appb-100020
    所示的基团，且R3为正己基；Z为C；    Formula (1-8): A is
    Figure PCTCN2016098397-appb-100019
    R 1 absent; R 2 is a formula
    Figure PCTCN2016098397-appb-100020
    a group shown, and R 3 is n-hexyl; Z is C;
    式(1-9)：A为
    Figure PCTCN2016098397-appb-100021
    R1不存在；R2为式
    Figure PCTCN2016098397-appb-100022
    所示的基团，且R3为正己基；Z为C；    Formula (1-9): A is
    Figure PCTCN2016098397-appb-100021
    R 1 does not exist; R 2 is a formula
    Figure PCTCN2016098397-appb-100022
    a group shown, and R 3 is n-hexyl; Z is C;
    式(1-10)：A为
    Figure PCTCN2016098397-appb-100023
    R1不存在；R2为式
    Figure PCTCN2016098397-appb-100024
    所示的基团，且R3为正己基；Z为C；    Formula (1-10): A is
    Figure PCTCN2016098397-appb-100023
    R 1 does not exist; R 2 is a formula
    Figure PCTCN2016098397-appb-100024
    A group represented by and R 3 is n-hexyl diyl; Z are C;
    式(1-11)：A为
    Figure PCTCN2016098397-appb-100025
    R1不存在；R2为式
    Figure PCTCN2016098397-appb-100026
    所示的基团，且R3为正己基；Z为C；    Formula (1-11): A is
    Figure PCTCN2016098397-appb-100025
    R 1 does not exist; R 2 is a formula
    Figure PCTCN2016098397-appb-100026
    a group shown, and R 3 is n-hexyl; Z is C;
    式(1-12)：A为
    Figure PCTCN2016098397-appb-100027
    R1不存在；R2为式
    Figure PCTCN2016098397-appb-100028
    所示的基团，且R3为正己基；Z为C；    Formula (1-12): A is
    Figure PCTCN2016098397-appb-100027
    R 1 does not exist; R 2 is a formula
    Figure PCTCN2016098397-appb-100028
    a group shown, and R 3 is n-hexyl; Z is C;
    式(1-13)：A为
    Figure PCTCN2016098397-appb-100029
    R1不存在；R2为式
    Figure PCTCN2016098397-appb-100030
    所示的基团，且R3为正己基；Z为C。     Formula (1-13): A is
    Figure PCTCN2016098397-appb-100029
    R 1 absent; R 2 is a formula
    Figure PCTCN2016098397-appb-100030
    a group shown, and R 3 is n-hexyl; Z is C.
  7. 权利要求1-6中任意一项所述的基于七并稠环单元的共轭大分子的制备方法，其中，该方法包括：The method for preparing a conjugated macromolecule based on a hepta-fused ring unit according to any one of claims 1 to 6, wherein the method comprises:
    在碱性化合物存在下且在有机溶剂中，将下式(2)所示的化合物与式(B)所示的化合物进行脱水缩合反应，得到式(1)所示的化合物；其中，a compound represented by the following formula (2) and a compound represented by the formula (B) are subjected to a dehydration condensation reaction in the presence of a basic compound in an organic solvent to obtain a compound represented by the formula (1);
    Figure PCTCN2016098397-appb-100031
    Figure PCTCN2016098397-appb-100031
    式(B)选自以下化合物中的一种或多种：Formula (B) is selected from one or more of the following compounds:
    Figure PCTCN2016098397-appb-100032
    Figure PCTCN2016098397-appb-100032
    其中，四个R2各自独立地选自式
    Figure PCTCN2016098397-appb-100033
    所示的基团；两个R1各自独立地选自式
    Figure PCTCN2016098397-appb-100034
    所示的基团；其中，各个Z各自独立地选自C或Si；各个X和各个Y各自独立地选自O、S或Se；m为1-6的整数；n为0-6的整数；各个R3、各个R4、R5、各个R6和各个R7各自独立地选自H、C1-C30的烷基、C1-C30的烷氧基和C6-C12的芳基；各个R8各自独立地选自H、烷基、卤素、烷氧基和烷硫基。    Wherein four R 2 are each independently selected from the formula
    Figure PCTCN2016098397-appb-100033
    A group represented by; two R 1 are each independently selected from the formulas
    Figure PCTCN2016098397-appb-100034
    a group shown; wherein each Z is independently selected from C or Si; each X and each Y are each independently selected from O, S or Se; m is an integer from 1 to 6; n is an integer from 0 to 6 Each R 3 , each R 4 , R 5 , each R 6 and each R 7 are each independently selected from the group consisting of H, a C1-C30 alkyl group, a C1-C30 alkoxy group, and a C6-C12 aryl group; 8 are each independently selected from the group consisting of H, alkyl, halogen, alkoxy, and alkylthio.
  8. 根据权利要求7所述的方法，其中，式(2)所示的化合物与式(B)所示的化合物的摩尔比为1：2-100。The method according to claim 7, wherein the molar ratio of the compound represented by the formula (2) to the compound represented by the formula (B) is from 1:2 to 100.
  9. 根据权利要求7或8所述的方法，其中，所述脱水缩合反应的条件包括：温度 为20-100℃，时间为10min-48h。The method according to claim 7 or 8, wherein the conditions of the dehydration condensation reaction include: temperature It is 20-100 ° C and the time is 10 min - 48 h.
  10. 根据权利要求7-9中任意一项所述的方法，其中，所述碱性化合物为哌啶、吡啶和三乙胺中一种或多种；优选地，相对于1mmol式(2)所示的化合物，所述碱性化合物的用量为0.1-1000mmol；The method according to any one of claims 7 to 9, wherein the basic compound is one or more of piperidine, pyridine and triethylamine; preferably, relative to 1 mmol of the formula (2) a compound, the basic compound is used in an amount of 0.1 to 1000 mmol;
    优选地，所述有机溶剂为氯仿和/或二氯甲烷。Preferably, the organic solvent is chloroform and/or dichloromethane.
  11. 权利要求1-6中任意一项所述的基于七并稠环单元的共轭大分子的制备方法，其中，该方法包括：The method for preparing a conjugated macromolecule based on a hepta-fused ring unit according to any one of claims 1 to 6, wherein the method comprises:
    在含钯催化剂存在下且在有机溶剂中，将下式(3)所示的化合物与式(C)所示的化合物进行偶联反应，得到式(1)所示的化合物；其中，Coupling a compound of the following formula (3) with a compound of the formula (C) in the presence of a palladium-containing catalyst in an organic solvent to obtain a compound of the formula (1);
    Figure PCTCN2016098397-appb-100035
    Figure PCTCN2016098397-appb-100035
    式(C)选自以下化合物中的一种或多种：Formula (C) is selected from one or more of the following compounds:
    Figure PCTCN2016098397-appb-100036
    Figure PCTCN2016098397-appb-100036
    其中，四个R2各自独立地选自式
    Figure PCTCN2016098397-appb-100037
    所示的基团；两个R1各自独立地选自式
    Figure PCTCN2016098397-appb-100038
    所示的基团；其中，各个Z各自独立地选自C或Si；各个X和各个Y各自独立地选自O、S或Se；各个M各自独立地选自卤素；各个R'各自独立地选自C1-C4的烷基；m为1-6的整数；n为0-6的整数；各个R3、各个R4、各个R6和各个R7各自独立地选自H、C1-C30的烷基、C1-C30的烷氧基和C6-C12的芳基；各个R8各自独立地选自H、烷基、卤素、烷氧基和烷硫基。     Wherein the four R 2 are each independently selected from the formulas
    Figure PCTCN2016098397-appb-100037
    a group shown; two R 1 are each independently selected from
    Figure PCTCN2016098397-appb-100038
    a group; wherein each Z is independently selected from C or Si; each X and each Y are each independently selected from O, S or Se; each M is independently selected from halogen; each R' is independently An alkyl group selected from C1-C4; m is an integer from 1 to 6; n is an integer from 0 to 6; each R 3 , each R 4 , each R 6 and each R 7 are each independently selected from H, C1-C30 An alkyl group, a C1-C30 alkoxy group and a C6-C12 aryl group; each R 8 is independently selected from the group consisting of H, alkyl, halogen, alkoxy and alkylthio.
  12. 根据权利要求11所述的方法，其中，式(3)所示的化合物与式(C)所示的化合物的摩尔比为1：2-5。The method according to claim 11, wherein the molar ratio of the compound represented by the formula (3) to the compound represented by the formula (C) is 1:2-5.
  13. 根据权利要求11或12所述的方法，其中，所述偶联反应的条件包括：温度为70-150℃，时间为6-50h。The method according to claim 11 or 12, wherein the conditions of the coupling reaction comprise a temperature of 70 to 150 ° C and a time of 6 to 50 h.
  14. 根据权利要求11-13中任意一项所述的方法，其中，所述含钯催化剂为四(三苯基膦)钯和/或二(三苯基膦)二氯化钯；优选地，相对于1mmol式(3)所示的化合物，所述含钯催化剂的用量为0.01-0.1mmol；The method according to any one of claims 11 to 13, wherein the palladium-containing catalyst is tetrakis(triphenylphosphine)palladium and/or bis(triphenylphosphine)palladium dichloride; preferably, relatively The compound represented by the formula (3), the palladium-containing catalyst is used in an amount of 0.01-0.1 mmol;
    优选地，所述有机溶剂为甲苯和/或四氢呋喃。Preferably, the organic solvent is toluene and/or tetrahydrofuran.
  15. 一种含有权利要求1-6中任意一项所述的基于七并稠环单元的共轭大分子的光伏材料。A photovoltaic material comprising a conjugated macromolecule based on a hepta-fused ring unit according to any one of claims 1 to 6.
  16. 一种太阳能电池，该太阳能电池包括光捕获的活性层，其中，所述光捕获的活性层中电子给体材料和/或电子受体材料含有权利要求1-6中任意一项所述的基于七并稠环单元的共轭大分子。A solar cell comprising a light-trapping active layer, wherein the electron-trapping material and/or electron acceptor material in the light-capturing active layer comprises the formula based on any one of claims 1-6 A conjugated macromolecule of a heptolipid ring unit.
  17. 一种太阳能电池的制备方法，其中，该方法包括将含有权利要求1-6中任意一项所述的基于七并稠环单元的共轭大分子的电子给体材料和/或电子受体材料用于形成光捕获的活性层。 A method of producing a solar cell, wherein the method comprises an electron donor material and/or an electron acceptor material comprising a conjugated macromolecule based on a hepta-fused ring unit according to any one of claims 1 to 6. An active layer for forming light trapping.
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