CN113429383A - Non-fullerene acceptor material, preparation method and application thereof - Google Patents

Non-fullerene acceptor material, preparation method and application thereof Download PDF

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CN113429383A
CN113429383A CN202110665697.4A CN202110665697A CN113429383A CN 113429383 A CN113429383 A CN 113429383A CN 202110665697 A CN202110665697 A CN 202110665697A CN 113429383 A CN113429383 A CN 113429383A
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independently
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heteroaromatic
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CN113429383B (en
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李维实
薛中鑫
许子文
刘丽娜
张翟
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Shanghai Institute of Organic Chemistry of CAS
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    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
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Abstract

The invention discloses a non-fullerene acceptor material, a preparation method and application thereof. The non-fullerene acceptor material has a structure shown in formula (I). The non-fullerene acceptor material provided by the invention can have a non-condensed ring structure, and can keep the planarity of a molecular main body while ensuring the solubility, so that organic photovoltaic material molecules can be flexibly constructed by using non-condensed ring structure units, the material solubility is good, the light absorption range can be expanded to a near infrared region, the electron mobility is high, and the development of novel efficient acceptor materials is facilitated.

Description

Non-fullerene acceptor material, preparation method and application thereof
Technical Field
The invention relates to a non-fullerene acceptor material, a preparation method and application thereof.
Background
In order to solve the increasingly sharp problem of energy, scientific and efficient use of clean energy such as solar energy is an important subject of research, and organic solar cells have the advantages of light weight, flexibility and easy processing as one of effective ways of using solar energy, and have gradually received wide attention from the scientific and industrial fields in recent years.
At present, the high-efficiency organic solar cell in the field generally adopts a bulk heterojunction type structure, and an active layer of the organic solar cell is formed by mixing donor and acceptor materials. The donor material is a p-type organic/polymeric semiconductor material, and the system is rich in electrons and has the ability to donate electrons and transport holes. The acceptor material is an n-type organic semiconductor material having the ability to accept and transfer electrons. In recent years, the invention of a large amount of high photovoltaic polymer and small molecular donor materials and the improvement of the preparation technology of a battery device are benefited, the optimal efficiency of the organic solar battery breaks through 18 percent, and the bright application prospect is shown.
The receptor materials which are mainstream nowadays are mainly novel non-fullerene receptors, and compared with the traditional fullerene receptor materials, the fullerene receptor materials are generally simpler and more convenient to synthesize, have wider and stronger absorption in a visible light region, and can meet different energy level requirements through relatively free structural design.
The existing efficient non-fullerene acceptor materials are generally structurally composed of a conjugated main body part consisting of a fused ring structure and long flexible side chains. The conjugated main body of the condensed ring ensures the planarity and the conjugation of the molecular main body, and is beneficial to the absorption of light and the transmission of carriers, but the condensed ring structure is usually synthesized more complexly, and the subsequent structure adjustment is relatively difficult. The long flexible side chain improves the solubility of the material, ensures the processing performance of the material, and is widely used in various organic semiconductor materials, but the side chain does not directly participate in the photoelectric conversion process.
Disclosure of Invention
The invention aims to solve the technical problems that the synthesis of a non-fullerene receptor material is complex and the structure adjustment is difficult in the prior art, so that the invention provides the non-fullerene receptor material, and a preparation method and application thereof.
The invention solves the problems through the following technical scheme:
the invention provides a non-fullerene acceptor material, which has a structure shown in a formula (I):
Figure BDA0003117299010000021
wherein, ring Ar1And ring Ar1′Independently an aromatic ring or a heteroaromatic ring independently having 1, 2, 3, or 4 heteroatoms independently selected from N, O and S;
ring Ar2And ring Ar2′Independently an aromatic ring, a heteroaromatic ring, substituted with one or more RaSubstituted aromatic rings, or by one or more RaA substituted heteroaromatic ring independently having 1, 2, 3, or 4 heteroatoms independently selected from S, O and Se;
Raindependently alkyl, alkoxy or alkylthio;
R1、R2、R1′and R2′Independently is-C (R)b)(Rc)(Rd)，Rb、RcAnd RdIndependently is H or alkyl;
R1and R2Are each in ring Ar2Adjacent positions of (a);
R1′and R2′Are each in ring Ar2′Adjacent positions of (a);
R3and R3′Independently is H, alkyl or alkoxy;
m and m′Independently 0, 1, 2, 3 or 4;
the mark end in the structure shown in the formula (I) is connected with an extended conjugated structure, and the extended conjugated structure is used for adjusting the band gap and the energy level distribution of the acceptor material.
In bookIn one embodiment of the invention, the extended conjugated structure may have formula (II) or (II)′) The structure represented by the formula (II) and the ring Ar in the structure represented by the formula (I)2Are connected to the formula (II)′) The structure shown and the ring Ar in the structure shown in the formula (I)2′The connection is carried out in a connecting way,
Figure BDA0003117299010000022
wherein ring A and ring A' are independently absent, aromatic, heteroaromatic, substituted with one or more ReSubstituted aromatic rings, or by one or more ReA substituted heteroaromatic ring independently having 1, 2, 3, or 4 heteroatoms or heteroatom groups independently selected from N, O, S and C (═ O);
Reindependently alkyl, alkoxy or alkylthio;
b and B' are independently
Figure BDA0003117299010000031
X is independently H, halogen, C1-C4Alkyl or C1-C4An alkoxy group;
r is independently H or alkyl.
In one embodiment of the present invention, ring Ar1And ring Ar1′Wherein the aromatic ring may independently be C6-C12Aromatic rings, such as benzene rings or naphthalene, and benzene rings, for example.
In one embodiment of the present invention, ring Ar1And ring Ar1′The heteroaromatic ring may be independently a 5-to 12-membered heteroaromatic ring, such as a 5-to 6-membered monocyclic heteroaromatic ring or an 8-to 12-membered fused heteroaromatic ring, and may be pyridine.
In one embodiment of the present invention, ring Ar2And ring Ar2′Wherein the aromatic ring may independently be C6-C12Aromatic rings, such as benzene rings or naphthalene, and benzene rings, for example.
In the present inventionIn a certain embodiment of the invention, ring Ar2And ring Ar2′The heteroaromatic ring may be independently a 5-to 12-membered heteroaromatic ring, such as a 5-to 6-membered monocyclic heteroaromatic ring or an 8-to 12-membered fused heteroaromatic ring, and further such as a 5-to 6-membered monocyclic heteroaromatic ring. The heteroaryl ring may independently have 1, 2 or 3 heteroatoms, for example 1. The heteroatoms may independently be independently selected from S and Se, e.g. S.
In one embodiment of the present invention, ring Ar2And ring Ar2′Wherein the 5-to 6-membered monocyclic heteroaromatic ring may be independently thiophene
Figure BDA0003117299010000032
Or selenene
Figure BDA0003117299010000033
Such as thiophene. The 8-12 fused heteroaromatic rings can be independently a benzodithiophene
Figure BDA0003117299010000034
Benzodithiophene
Figure BDA0003117299010000035
And trithiophene
Figure BDA0003117299010000036
Or dithienocyclopentadienes
Figure BDA0003117299010000037
In one embodiment of the present invention, ring Ar2And ring Ar2′In, RaAnd may be independently 1, 2 or 3.
In one embodiment of the present invention, RaWherein the alkyl group may be independently C1～C25Alkyl radicals, e.g. C1～C12Alkyl radicals, also e.g. C1～C4Alkyl (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl).
In one embodiment of the present invention, RaWherein the alkoxy group may be independentGround is C1～C25Alkoxy radicals, e.g. C1～C12Alkoxy radicals, e.g. C1～C4Alkoxy (methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy).
In one embodiment of the present invention, RaWherein said alkylthio may independently be C1～C25Alkylthio radicals, e.g. C1～C12Alkylthio radicals, e.g. C1～C4Alkylthio (methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio or tert-butylthio).
In one embodiment of the present invention, Rb、RcAnd RdWherein the alkyl group may be independently C1～C25Alkyl radicals, e.g. C1～C12Alkyl radicals, also e.g. C1～C4Alkyl (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl), for example methyl.
In one embodiment of the present invention, R1、R2、R1′And R2′In (1), the-C (R)b)(Rc)(Rd) And may independently be methyl, ethyl, isopropyl or tert-butyl, such as methyl or isopropyl, and also for example isopropyl.
In one embodiment of the present invention, R3And R3′Wherein the alkyl group may be independently C1～C25Alkyl radicals, e.g. C1～C12Alkyl radicals, also e.g. C1～C4Alkyl (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl), for example also methyl or isopropyl.
In one embodiment of the present invention, R3And R3′Wherein said alkoxy group may be independently C1～C25Alkoxy radicals, e.g. C1～C12Alkoxy radicals, e.g. C1～C4Alkoxy (methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy).
In one embodiment of the present invention, in ring A and ring A', the aromatic rings may independently be C6-C12Aromatic rings, such as benzene rings or naphthalene, and benzene rings, for example.
In one embodiment of the present invention, in the ring A and the ring A', the heteroaromatic rings may be independently 5-to 12-membered heteroaromatic rings, for example, 5-to 6-membered monocyclic heteroaromatic rings or 8-to 12-membered fused heteroaromatic rings. The heteroaryl ring may independently have 1, 2 or 3 heteroatoms, for example 3. The heteroatoms may be independently selected from N and S.
In a certain embodiment of the present invention, in ring a and ring a', the 5-to 6-membered single heteroaromatic ring may be independently thiophene, furan, pyrrole, imidazole, pyrazole, oxazole, pyridine or pyrazine. The 8-12 fused heteroaromatic rings can be independently benzothiophene, benzodithiophene, benzothiadiazole, benzodithiadiazole, thienothiadiazole, or thienopyrazine, such as 2,1, 3-benzothiadiazole.
In one embodiment of the present invention, R in ring A and ring A', ReAnd may be independently 1, 2 or 3.
In one embodiment of the present invention, ReWherein the alkyl group may be independently C1～C25Alkyl radicals, e.g. C1～C12Alkyl radicals, also e.g. C1～C4Alkyl (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl).
In one embodiment of the present invention, ReWherein said alkoxy group may be independently C1～C25Alkoxy radicals, e.g. C1～C12Alkoxy radicals, e.g. C1～C4Alkoxy (methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy).
In one embodiment of the present invention, ReWherein said alkylthio may independently be C1～C25Alkylthio radicals, e.g. C1～C12Alkylthio radicals, e.g. C1～C4Alkylthio (methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio orTert-butylthio).
In one embodiment of the present invention, in X, the halogen may be independently F, Cl, Br or I, such as F or Cl.
In one embodiment of the present invention, in X, C is1-C4Alkyl groups may independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl.
In one embodiment of the present invention, in X, C is1-C4Alkoxy groups may independently be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy, for example methoxy.
In one embodiment of the present invention, the alkyl group in R may be independently C1～C25Alkyl radicals, e.g. C1～C12Alkyl radicals, also e.g. C1～C4Alkyl (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl).
In one aspect of the present invention, in B and B', the
Figure BDA0003117299010000051
Can independently be
Figure BDA0003117299010000052
Figure BDA0003117299010000053
In one embodiment of the present invention, ring Ar1And ring Ar1′Independently an aromatic ring.
In one embodiment of the present invention, ring Ar2And ring Ar2′Independently a heteroaromatic ring.
In one embodiment of the present invention, R3And R3′Independently an alkyl group.
In one embodiment of the invention, m and m' are independently 1.
In one embodiment of the invention, ring a and ring a' are independently a non-or heteroaromatic ring.
In one embodiment of the invention, B and B' are independently
Figure BDA0003117299010000054
In one embodiment of the invention, X is independently H or halogen.
In one aspect of the present invention, the structural unit
Figure BDA0003117299010000055
Can be that
Figure BDA0003117299010000056
And can be
Figure BDA0003117299010000057
For example
Figure BDA0003117299010000058
Also for example
Figure BDA0003117299010000059
In one aspect of the present invention, the structural unit
Figure BDA00031172990100000510
Can be that
Figure BDA00031172990100000511
And can be
Figure BDA00031172990100000512
For example
Figure BDA0003117299010000061
Also for example
Figure BDA0003117299010000062
In one aspect of the present invention, the structural unit
Figure BDA0003117299010000063
Can be that
Figure BDA0003117299010000064
In one aspect of the present invention, the structure represented by the formula (I) may be a structure represented by the formula (I-1)
Figure BDA0003117299010000065
In one aspect of the present invention,
Figure BDA0003117299010000066
can be independently absent,
Figure BDA0003117299010000067
Figure BDA0003117299010000068
Figure BDA0003117299010000069
E.g. none or
Figure BDA00031172990100000610
In some embodiments of the invention, the structure of formula (I) may be
Figure BDA00031172990100000611
Figure BDA00031172990100000612
In one aspect of the present invention, the structure represented by the formula (II) and the formula (II)′) The structures shown may independently be
Figure BDA0003117299010000071
Figure BDA0003117299010000072
In some embodiments of the invention, the non-fullerene acceptor material may have any one of the following structures:
Figure BDA0003117299010000073
the invention provides a compound shown as a formula (III),
Figure BDA0003117299010000081
wherein each group is as defined in any of the embodiments of the present invention.
In some embodiments of the invention, the compound of formula (III) may have any one of the following structures:
Figure BDA0003117299010000082
the invention provides a preparation method of the compound shown in the formula (III), which comprises the following steps: the compound represented by the formula (IV) may be reacted with the compound H-B and the compound H-B' in the presence of an organic base (e.g., pyridine) in an organic solvent (e.g., chloroform) as shown below,
Figure BDA0003117299010000091
wherein each group is as defined in any of the embodiments of the present invention.
The invention provides a compound shown as a formula (IV):
Figure BDA0003117299010000092
wherein each group is as defined in any of the embodiments of the present invention.
In one aspect of the present invention, the compound represented by formula (IV) may have any one of the following structures:
Figure BDA0003117299010000093
the invention provides an application of the non-fullerene acceptor material or the compound shown in the formula (III) as a solar cell material.
The invention provides an organic solar cell device, wherein an acceptor material of the organic solar cell device is the non-fullerene acceptor material or the compound shown in the formula (III).
In one aspect of the invention, the organic solar cell device comprises an anode, a hole transport layer, a layer of a blend of the above non-fullerene acceptor material or the above compound of formula (III) with a donor polymer PM6, an electron transport layer and a cathode.
Preferably, the material of the anode is Indium Tin Oxide (ITO); the hole transport layer is PEDOT PSS; the electron transport layer is made of PFN-Br; the cathode is made of aluminum (Al).
Unless otherwise specified, the terms in the present invention have the following meanings:
in the present invention, "alkyl" means a straight-chain or branched alkyl group having the specified number of carbon atoms.
In the present invention, "alkoxy" means a group-O-RXWherein R isXIs an alkyl group as defined above.
In the present invention, "alkylthio" means the group-S-RXWherein R isXIs an alkyl group as defined above.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the non-fullerene acceptor material provided by the invention can have a non-condensed ring structure, and can keep the planarity of a molecular main body while ensuring the solubility, so that organic photovoltaic material molecules can be flexibly constructed by using non-condensed ring structure units, the material solubility is good, the light absorption range can be expanded to a near infrared region, the electron mobility is high, and the development of novel efficient acceptor materials is facilitated.
Drawings
FIG. 1 shows the UV-visible absorption spectra of chloroform solutions of compounds i-Pr-BT, i-Pr-BT-F, and i-Pr-IC.
FIG. 2 shows the UV-VIS absorption spectra of the thin film states of compounds i-Pr-BT, i-Pr-BT-F, and i-Pr-IC.
FIG. 3 is a graph of current density and voltage of organic solar cell devices of compounds i-Pr-BT, i-Pr-BT-F, i-Pr-IC and PM 6.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1: synthesis of Compound Me-BT
Figure BDA0003117299010000111
Step 1: synthesis of Compound 2-1
Magnesium turnings (2.92g, 120mmol) were added to a 250mL three-necked flask, argon was purged three times, and one pellet of iodine was added to the flask under argon flow followed by 30mL of anhydrous tetrahydrofuran. Dissolving mesitylene (23.89g, 120mmol) in 60mL of anhydrous tetrahydrofuran, adding 20mL of solution into a reaction system, heating to initiate reaction until the reaction solution becomes colorless, continuing to dropwise add the rest solution while keeping a slightly boiling state, heating and refluxing after dropwise addition is finished to completely react magnesium, and cooling for later use. Another 250mL three-necked flask was added with palladium acetate (269.4mg, 1.2mmol) and 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (2.29g, 4.8mmol) and argon was purged three times, then 3-bromothiophene (12.95g, 80mmol) and 40mL tetrahydrofuran were added, and the prepared Grignard reagent was added dropwise and heated under reflux. The reaction was monitored by thin layer chromatography with petroleum ether as the developing agent. After the reaction was completed, the reaction was quenched with saturated ammonium chloride, extracted with dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. Separating by column chromatography using petroleum ether as eluent to obtain compound 2-1 as white solid 15.02g with yield 92.7%.
1H NMR(400MHz,CDCl3)δ:7.38(dd,J1＝2.9Hz,J2＝4.9Hz,1H),7.01(dd,J1＝1.2Hz,J2＝2.9Hz,1H),6.93(s,2H),6.92(dd,J1＝1.2Hz,J2＝4.9Hz,1H),2.32(s,3H),2.05(s,6H).MS(EI)m/z:202(M+).
Step 2: synthesis of Compound 2-2
In a 250mL three-necked flask, compound 2-1(10.74g, 53.1mmol) was added, 36mL of chloroform and 36mL of acetic acid were added, and N-bromosuccinimide (9.92g, 55.7mmol) was added thereto in portions with stirring, and the reaction was continued at room temperature until the reaction solution turned into a pale yellow clear solution. The reaction solution was neutralized with NaOH to near neutral, extracted with dichloromethane, washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate, concentrated, and the resulting crude product was recrystallized from ethanol to isolate compound 2-2 as a white solid 10.92g, in 73.1% yield.
1H NMR(400MHz,CDCl3)δ:7.33(d,J＝5.8Hz,1H),6.94(s,2H),6.76(d,J＝5.8Hz,1H),2.32(s,3H),2.02(s,6H).MS(EI)m/z:282(M+).
And step 3: synthesis of Compounds 2-3
Magnesium turnings (365mg, 15mmol) were added to a 50mL three-necked flask, argon was purged three times, and one iodine pellet was added to the flask under argon flow followed by 5mL of anhydrous tetrahydrofuran. Dissolving the compound 2-2(4.22g, 15mmol) in 10mL of anhydrous tetrahydrofuran, adding 3mL of the solution into a reaction bottle, heating to initiate reaction until the reaction solution becomes colorless, keeping a slightly boiling state, continuously dropwise adding the rest solution, heating to reflux after dropwise adding is finished until magnesium completely reacts, and cooling for later use. Another 100mL three-necked flask was taken, and the compound 2-2(2.81g, 10mmol), palladium acetate (34mg, 0.15mmol) and 2-dicyclohexylphosphino-2' - (N, N-dimethylamine) -biphenyl (236mg, 0.6mmol) were added thereto, argon was evacuated three times, 20mL of anhydrous tetrahydrofuran was added, the prepared grignard reagent was added dropwise, and heating and reflux reaction were performed. The reaction was monitored by thin layer chromatography with petroleum ether as the developing agent. Quenching the reaction by using a saturated ammonium chloride solution after the reaction is completed, extracting by using dichloromethane, washing by using a saturated sodium chloride solution, drying by using anhydrous sodium sulfate, concentrating, and separating by using column chromatography, wherein an eluent is petroleum ether: dichloromethane 10: 1, compound 2-3 was isolated as a white solid, 2.53g, 62.9% yield.
1H NMR(400MHz,CDCl3)δ:7.06(d,J＝5.1Hz,1H),6.97(s,2H),6.67(d,J＝5.1Hz,1H),2.38(s,3H),1.98(s,6H).MS(EI)m/z:402(M+).
And 4, step 4: synthesis of Compounds 2-4
Adding 2-3(2.53g, 6.28mmol) of a compound into a 250mL three-necked bottle, pumping argon for three times, adding 100mL of anhydrous tetrahydrofuran, dropwise adding 8.8mL of a 2.5mol/L n-butyllithium solution at room temperature, continuing to stir at room temperature for 1h after dropwise adding, adding 15.1mL of a 1mol/L trimethyltin chloride solution into the reaction bottle, and stirring at room temperature for reaction for 12 h. The reaction is quenched with water, extracted with dichloromethane, washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated to obtain a yellow solid. The crude product was recrystallized from ethyl acetate to give 2.93g of compound 2-4 as a pale yellow solid with a yield of 64.0%.
1H NMR(400MHz,CDCl3)δ:6.85(s,2H),6.67(s,1H),2.33(s,3H),1.84(s,6H),0.25(s,9H).MS(EI)m/z:728.1(M+).
And 5: synthesis of Compounds 2-5
A100 mL three-necked flask was charged with compound 2-4(2.93g, 4.02mmol), 4-bromo-7-carboxaldehyde-2, 1, 3-benzothiadiazole (2.45g, 10.1mmol) and palladium tetratriphenylphosphine (92.9mg, 0.08mmol), argon was purged three times, and 40mL of redistilled toluene was added. And performing liquid nitrogen freezing-air extraction-thawing circulation for three times, removing dissolved oxygen in the solvent, and performing heating reflux reaction. The reaction was monitored by TLC and the developing solvent was dichloromethane. After the reaction is completed, dichloromethane is used for extraction reaction, saturated sodium chloride solution is used for washing, anhydrous sodium sulfate is used for drying, concentration and column chromatography separation are carried out, dichloromethane is used as eluent, and the compound 2-5 deep red solid 1.95g is obtained through separation, and the yield is 66.7%.
1H NMR(400MHz,CDCl3)δ:10.59(s,1H),8.15(d,J＝7.2Hz,1H),8.14(s,1H),7.69(d,J＝7.2Hz,1H),7.15(s,2H),2.44(s,3H),2.10(s,6H).MS(EI)m/z:727.1(M+H+)
Step 6: synthesis of Compound Me-BT
In a 250mL three-necked flask, compound 2-5(1.09g, 1.5mmol), 120mL chloroform, and 5mL pyridine were added. The reaction flask was placed in a low temperature thermostat and the temperature was reduced to-40 ℃. 3- (dicyanomethylene) indolone (1.17g, 6mmol) was added in portions to the reaction flask, stirred for 10min, and then heated to-15 ℃ to continue the reaction. The reaction was monitored by TLC and the developing solvent was dichloromethane. After completion of the reaction, the reaction mixture was poured into 300mL of methanol, and the precipitate was collected by filtration. Excess compound 3- (dicyanomethylene) indolone and pyridine were removed by washing with methanol, followed by washing with 15mL of n-hexane, diethyl ether and acetone in sequence three times each, and the resulting solid was added to ethyl acetate at 100mL and heated under reflux for about 1h, filtered while hot, and the precipitate was collected as 842.6mg of Me-BT dark blue solid, 52.1% yield.
1H NMR(400MHz,CDCl3)δ:9.54(s,1H),9.16-9.13(m,1H),8.73(d,J＝8.0Hz,1H),8.20(s,1H),7.97-7.94(m,1H),7.86-7.77(m,2H),7.72(d,J＝8.0Hz,1H),7.13(s,2H),2.51(s,3H),2.13(s,6H).HRMS(MALDI)m/z:1078.2(M+).Element Anal.Calcd for C64H38N8O2S4:C 71.2％H 3.55％N 10.38％Found C 69.9％,H 4.02％,N 9.85％.
Example 2: synthesis of compound i-Pr-BT
Figure BDA0003117299010000141
Step 1: synthesis of Compounds 2-6
Triisopropylbromobenzene (14.16g, 50mmol), 3-thiopheneboronic acid (12.80g, 100mmol), potassium phosphate (21.23g, 100mmol), tris (dibenzylideneacetone) dipalladium (458mg, 0.5mmol) and 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (821mg, 2mmol) were charged into a 500mL three-necked flask, argon was evacuated three times, 100mL of anhydrous toluene and 100mL of anhydrous tetrahydrofuran were added as solvents, three liquid nitrogen freeze-pump-thaw cycles were performed, dissolved oxygen in the solvent was removed, and heating and refluxing were performed. The reaction was monitored by TLC and the developing solvent was petroleum ether. Extracting with dichloromethane, washing with saturated sodium chloride solution, drying with anhydrous sodium sulfate, concentrating, separating with column chromatography to obtain compound 2-6 as white solid 14.10g with 98.4% yield, and eluting with petroleum ether.
1H NMR(400MHz,CDCl3)δ:7.35(dd,J1＝2.9Hz,J2＝4.8Hz,1H),7.04(s,2H),7.01(dd,J1＝1.2Hz,J2＝2.9Hz,1H),6.94(dd,J1＝1.2Hz,J2＝4.8Hz,1H),2.92(m,J＝6.8Hz,1H),2.66(m,J＝6.8Hz,2H),1.29(d,J＝6.8Hz,6H),1.09(d,J＝6.8Hz,6H),1.08(d,J＝6.8Hz,6H).MS(EI)m/z:286(M+).
Step 2: synthesis of Compounds 2-7
In a 250mL three-necked flask, compound 2-6(13.28g, 46.4mmol) was added, 30mL of chloroform and 30mL of acetic acid were added, and N-bromosuccinimide (8.66g, 48.7mmol) was added thereto in portions with stirring, and the reaction was continued at room temperature until the reaction solution turned into a pale yellow clear solution. Neutralizing the reaction liquid with NaOH to be nearly neutral, extracting with dichloromethane, washing with saturated sodium chloride solution, drying with anhydrous sodium sulfate, concentrating, taking a small amount of the solution in batches, and separating by column chromatography, wherein the used eluent is petroleum ether to obtain 7.51g of a compound 2-7 white solid, and the yield is 44.3%.
1H NMR(400MHz,CDCl3)δ:7.30(d,J＝5.4Hz,1H),7.04(s,2H),6.78(d,J＝5.4Hz,1H),2.93(m,J＝6.9Hz,1H),2.56(m,J＝6.9Hz,2H),1.29(d,J＝6.9Hz,6H),1.16(d,J＝6.9Hz,6H),1.05(d,J＝6.9Hz,6H).MS(EI)m/z:364(M+).
And step 3: synthesis of Compounds 2 to 8
Magnesium turnings (237mg, 9.75mmol) were added to a 50mL three-necked flask, argon was purged three times, and one iodine pellet was added to the flask under argon flow followed by 4mL of anhydrous tetrahydrofuran. Dissolving the compound 2-7(3.56g, 9.75mmol) in 8mL of anhydrous tetrahydrofuran, adding 3mL of the solution into a reaction bottle, heating to initiate reaction until the reaction solution becomes colorless, keeping a slightly boiling state, continuously dropwise adding the rest solution, heating to reflux after dropwise adding is finished until magnesium completely reacts, and cooling for later use. Another 100mL three-necked flask was taken, added with compound 2-7(2.37g, 6.5mmol), tris-dibenzylideneacetone dipalladium (22.5mg, 0.10mmol) and 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (160.1mg, 0.39mmol), argon was evacuated three times, added with 16mL of anhydrous tetrahydrofuran, added dropwise with the prepared Grignard reagent, and heated under reflux for reaction. The reaction was monitored by TLC and the developing solvent was petroleum ether. Quenching the reaction by using a saturated ammonium chloride solution after the reaction is completed, extracting by using dichloromethane, washing by using a saturated sodium chloride solution, drying by using anhydrous sodium sulfate, concentrating, and separating by using column chromatography, wherein an eluent is petroleum ether: dichloromethane 10: 1, compound 2-8 was isolated as a white solid, 3.49g, 94.0% yield.
1H NMR(400MHz,CDCl3)δ:7.08(s,2H),6.98(d,J＝5.0Hz,1H),6.67(d,J＝5.0Hz,1H),2.98(m,J＝6.9Hz,1H),2.62(m,J＝6.9Hz,2H),1.33(d,J＝6.9Hz,6H),1.06(d,J＝6.9Hz,6H),1.02(d,J＝6.9Hz,6H).MS(EI)m/z:571.3(M+).
And 4, step 4: synthesis of Compounds 2-9
Adding 2-8(3.40g, 5.96mmol) of a compound into a 250mL three-necked bottle, pumping argon for three times, adding 80mL of anhydrous tetrahydrofuran, dropwise adding 8.4mL of a 2.5mol/L n-butyllithium solution at room temperature, continuing to stir and react for 1h at room temperature after dropwise adding, adding 14.4mL of a 1mol/L trimethyltin chloride solution into the reaction bottle, and stirring and reacting for 12h at room temperature. The reaction is quenched with water, extracted with dichloromethane, washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated to obtain a yellow solid. The crude product was recrystallized from ethyl acetate to give 3.24g of compound 2-9 as a pale yellow solid with a yield of 60.7%.
1H NMR(400MHz,CDCl3)δ:7.06(s,2H),2.96(m,J＝7.0Hz,1H),2.56(m,J＝7.0Hz,2H),1.32(d,J＝7.0Hz,6H),1.01(d,J＝7.0Hz,6H),1.00(d,J＝7.0Hz,6H),1.84(s,6H),0.17(s,9H).MS(EI)m/z:897.3(M+).
And 5: synthesis of Compounds 2-10
Adding compounds 2-9(1.62g, 1.81mmol), 4-bromo-7-aldehyde-2, 1, 3-benzothiadiazole ((1.10g, 4.53mmol) and palladium (41.8mg, 0.04mmol) of tetratriphenylphosphine into a 100mL three-necked flask, pumping argon for three times, adding 20mL of anhydrous toluene, performing three cycles of liquid nitrogen freezing-pumping-thawing, removing dissolved oxygen in the solvent, heating and refluxing, monitoring the reaction by TLC, using dichloromethane as a developing agent, performing extraction reaction by dichloromethane after the reaction is completed, washing by a saturated sodium chloride solution, drying by anhydrous sodium sulfate, concentrating, separating by column chromatography, using dichloromethane as an eluent, and separating to obtain 859mg of a compound 2-10 dark red solid with the yield of 53.0%.
1H NMR(400MHz,CDCl3)δ:10.67(s,1H),8.24(s,1H),8.11(d,J＝7.5Hz,1H),7.61(d,J＝7.5Hz,1H),7.25(s,2H),3.10(m,J＝6.9Hz,1H),2.77(m,J＝6.9Hz,2H),1.44(d,J＝6.9Hz,6H),1.17(d,J＝6.9Hz,6H),1.15(d,J＝6.9Hz,6H).MS(EI)m/z:895.3(M+H+).
Step 6: synthesis of compound i-Pr-BT
In a 100mL three-necked flask, compound 2-10(357.7mg, 0.40mmol), 40mL of chloroform, and 2.4mL of pyridine were added. The reaction flask was placed in a low temperature thermostat and the temperature was reduced to-40 ℃. 3- (dicyanomethylene) indolone (310.7mg, 1.60mmol) was added in portions to the reaction flask, stirred for 10min, and then heated to-15 ℃ to continue the reaction. The reaction was monitored by TLC and the developing solvent was dichloromethane. After completion of the reaction, the reaction mixture was poured into 200mL of methanol, and the precipitate was collected by filtration. Washing with methanol to remove excessive compounds 2-5 and pyridine, sequentially washing with 10mL of n-hexane, diethyl ether and acetone for three times respectively, adding 40mL of the obtained solid into ethyl acetate, heating and refluxing for about 1h, filtering while hot, and collecting precipitate which is 302.5mg of i-Pr-BT dark blue solid with the yield of 60.7%.
1H NMR(400MHz,CDCl3)δ:9.51(s,1H),9.09-9.07(m,1H),8.73(d,J＝8.2Hz,1H),8.21(s,1H),7.96-7.94(m,1H),7.86-7.77(m,2H),7.67(d,J＝8.2Hz,1H),7.26(s,2H),3.11(m,J＝6.9Hz,1H),2.77(m,J＝6.9Hz,2H),1.44(d,J＝6.9Hz,6H),1.18(d,J＝6.9Hz,6H),1.14(d,J＝6.9Hz,6H).HRMS(MALDI)m/z:1246.4(M+).Element Anal.Calcd for C76H62N8O2S4:C 73.2％H 5.10％N 8.98％Found C 72.6％,H 5.26％,N 8.77％.
Example 3: synthesis of Compounds i-Pr-IC and i-Pr-IC-F
Figure BDA0003117299010000171
Step 1: synthesis of Compounds 2-11
In a 100mL three-necked flask, compound 2-8(1.14g, 2mmol), 30mL of 1, 2-dichloroethane and 1.9mL of phosphorus oxychloride were added, 1.6mL of N, N-dimethylformamide was added dropwise, and the reaction was heated under reflux for 24 hours. After the reaction is completed, extracting by dichloromethane, washing by saturated sodium chloride solution, drying by anhydrous sodium sulfate, concentrating, and separating by column chromatography, wherein the used eluent is petroleum ether: 1-dichloromethane: 1, compound 2-11 was isolated as a yellow solid 970.0mg, 77.4% yield.
1H NMR(400MHz,CDCl3)δ:9.74(s,1H),7.39(s,1H),7.14(s,2H),3.00(p,J＝6.9Hz,1H),2.48(p,J＝6.9Hz,2H),1.35(d,J＝6.9Hz,6H),1.05(t,J＝6.8Hz,12H).MS(EI)m/z:627.3(M+H+).
Step 2: synthesis of Compounds i-Pr-IC and i-Pr-IC-F
In a 100mL three-necked flask, compound 2-11(200m g, 0.32mmol), 30mL chloroform, and 1.9mL pyridine were added. The reaction flask was cooled in an ice bath and 3- (dicyanomethylene) indolone (248.6mg, 1.28mmol) was added portionwise and the reaction monitored by TLC using dichloromethane as the developing solvent. After the reaction is completed, the solvent is removed under reduced pressure, and column chromatography separation is carried out, wherein dichloromethane is used as eluent, and the compound i-Pr-IC dark red solid 203.5mg is obtained through separation, and the yield is 64.9%.
1H NMR(400MHz,CDCl3)δ:8.68–8.63(m,1H),8.62(s,1H),7.80(dd,J＝7.0,1.9Hz,1H),7.77–7.67(m,3H),7.23(s,2H),3.04(p,J＝6.9Hz,1H),2.55(p,J＝6.9Hz,2H),1.39(d,J＝6.9Hz,6H),1.14(d,J＝6.8Hz,6H),1.10(d,J＝6.8Hz,6H).MS(MALDI)m/z:978.4(M+)
In a 100mL three-necked flask, compound 2-11(200mg, 0.32mmol), 30mL of chloroform, and 1.9mL of pyridine were added. The reaction flask was cooled in an ice bath and 5, 6-difluoro-3- (dicyanomethylene) indolone (294.6mg, 1.28mmol) was added in portions and the reaction monitored by TLC using dichloromethane as the developing solvent. After the reaction is completed, the solvent is removed under reduced pressure, and column chromatography separation is carried out, wherein dichloromethane is used as eluent, and the compound i-Pr-IC-F dark red solid 172.1mg is obtained through separation, and the yield is 51.2%.
1H NMR(400MHz,CDCl3)δ:8.62(s,1H),8.50(dd,J＝9.9,6.4Hz,1H),7.72(s,1H),7.56(t,J＝7.5Hz,1H),7.22(s,2H),3.04(p,J＝6.8Hz,1H),2.51(p,J＝6.8Hz,3H),1.39(d,J＝6.9Hz,6H),1.13(d,J＝6.8Hz,6H),1.09(d,J＝6.8Hz,6H).MS(MALDI)m/z:1050.4(M+).
Example 4: synthesis of Compounds i-Pr-BT-F and i-Pr-BT-Cl
In a 100mL three-necked flask, compound 2-10(500.0mg, 0.56mmol), 50mL of chloroform, and 3.3mL of pyridine were added. The reaction flask was placed in a low temperature thermostat and the temperature was reduced to-40 ℃.5, 6-difluoro-3- (dicyanomethylene) indolone (514.7mg, 2.24mmol) was added portionwise to the reaction flask, stirred for 10min, and then warmed to room temperature to continue the reaction. The reaction was monitored by TLC and the developing solvent was dichloromethane. After completion of the reaction, the reaction mixture was poured into 200mL of methanol, and the precipitate was collected by filtration. Excess compound 5, 6-difluoro-3- (dicyanomethylene) indone and pyridine are removed by washing with methanol, then washing with 10mL of n-hexane, ethyl ether and acetone respectively for three times, and separating by column chromatography, wherein the used eluent is acetone and chloroform in turn, and i-Pr-BT-F dark blue solid 372.2mg is collected, and the yield is 50.4%.
1H NMR(400MHz,CDCl3)δ:9.54(s,1H),9.08(d,J＝7.9Hz,1H),8.57(dd,J＝9.8,6.4Hz,1H),8.23(s,1H),7.72(t,J＝7.4Hz,1H),7.67(d,J＝8.0Hz,1H),7.26(s,2H),3.11(p,J＝6.8Hz,1H),2.75(p,J＝6.8Hz,2H),1.44(d,J＝6.9Hz,6H),1.17(d,J＝6.8Hz,6H),1.14(d,J＝6.8Hz,6H).MS(MALDI)m/z:1318.3(M+)
In a 100mL three-necked flask, compound 2-10(500.0mg, 0.56mmol), 50mL of chloroform, and 3.3mL of pyridine were added. The reaction flask was placed in a low temperature thermostat and the temperature was reduced to-40 ℃.5, 6-dichloro-3- (dicyanomethylene) indolone (514.7mg, 2.24mmol) was added portionwise to the reaction flask, stirred for 10min, and then warmed to room temperature to continue the reaction. The reaction was monitored by TLC and the developing solvent was dichloromethane. After completion of the reaction, the reaction mixture was poured into 200mL of methanol, and the precipitate was collected by filtration. Excess compound 5, 6-dichloro-3- (dicyanomethylene) indolone and pyridine are removed by washing with methanol, then washing with 10mL of n-hexane, ether and acetone respectively for three times, and separating by column chromatography, wherein the used eluent is acetone and chloroform in turn, and the i-Pr-BT-Cl dark blue solid 170.1mg is collected, and the yield is 21.9%.
1H NMR(400MHz,CDCl3)δ:9.57(s,1H),9.11(d,J＝8.0Hz,1H),8.81(s,1H),8.24(s,1H),7.99(s,1H),7.68(d,J＝8.0Hz,1H),7.26(s,2H),3.11(p,J＝6.8Hz,1H),2.76(p,J＝6.6Hz,2H),1.45(d,J＝6.9Hz,6H),1.17(d,J＝6.8Hz,6H),1.14(d,J＝6.8Hz,6H).MS(MALDI)m/z:1384.1(M+)
Example 5: characterization of absorption spectra of small molecule receptor materials
Dissolving small molecule receptor materials i-Pr-BT, i-Pr-BT-F and i-Pr-IC in trichloromethane to prepare 10-5And testing the ultraviolet-visible spectrum of the solution state by using the mol/L solution, wherein the tested spectrum is shown in figure 1. Dissolving i-Pr-BT, i-Pr-BT-F and i-Pr-IC in chloroform to prepare 10mg/mL, spin-coating on a quartz glass plate to obtain a receptor material film, and measuring the ultraviolet-visible spectrum in the film state, wherein the measured spectrum is shown in figure 2.
Example 6:
the organic micromolecule acceptor material and the donor polymer PM6 are used as active layers of the organic solar cell device, and the bulk heterojunction organic solar cell device can be obtained. The device structure is as follows: ITO/PEDOT PSS/active layer/PFN-Br/Al. Wherein the ITO is an indium tin oxide conductive glass substrate layer; PSS is a hole transport layer; the active layer is a blending layer of a donor material PM6 and an acceptor material i-Pr-BT or i-Pr-IC or i-Pr-BT-F, the blending mass ratio is PM6: 1:1.6, PFN-Br is an electron transport layer, and Al is a cathode.
Preparing an organic solar cell: and ultrasonically cleaning the ITO glass twice in deionized water, acetone and isopropanol solution, drying the ITO glass, performing ultraviolet-ozone treatment on the ITO glass for 30min, then spin-coating PEDOT (PSS) on the ITO glass at the spin-coating speed of 4000rpm for 60s, and then performing annealing treatment at 150 ℃ for 10 min. Will be provided withAnd dripping the prepared precursor solution of the active layer onto PEDOT (PSS), spin-coating at the rotation speed of 4000rpm for 30s, thermally annealing at the temperature of 100 ℃ for 5min, and spin-coating an electron transport layer PFN-Br solution at 3500rpm for 30 s. Followed by evaporation of the aluminum electrode. The current density-voltage curve (J-V) of the device is AM 1.5G (100 mW/cm) in a sunlight simulation system2) Obtained by the following test.
The current density and voltage curve of the i-Pr-BT based organic solar cell device is shown in FIG. 3, and the short-circuit current density of the device is 16.32mA/cm2The open circuit voltage was 0.68V, and the energy conversion efficiency was 7.57%.
The current density and voltage curve of the i-Pr-IC-based organic solar cell device is shown in FIG. 3, and the short-circuit current density of the device is 13.48mA/cm2The open circuit voltage was 0.79V, and the energy conversion efficiency was 7.52%.
The current density and voltage curve of the i-Pr-BT-F-based organic solar cell device is shown in FIG. 3, and the short-circuit current density of the device is 15.76mA/cm2The open circuit voltage was 0.46V, and the energy conversion efficiency was 3.71%.

Claims (13)

1. A non-fullerene acceptor material, wherein the non-fullerene acceptor material has a structure according to formula (I):
Figure FDA0003117299000000011
wherein, ring Ar1And ring Ar1′Independently an aromatic ring or a heteroaromatic ring independently having 1, 2, 3, or 4 heteroatoms independently selected from N, O and S;
ring Ar2And ring Ar2′Independently an aromatic ring, a heteroaromatic ring, substituted with one or more RaSubstituted aromatic rings, or by one or more RaA substituted heteroaromatic ring independently having 1, 2, 3, or 4 heteroatoms independently selected from S, O and Se;
Raindependently alkyl, alkoxy or alkylthio;
R1、R2、R1′and R2′Independently is-C (R)b)(Rc)(Rd)；
Rb、RcAnd RdIndependently is H or alkyl;
R1and R2Are each in ring Ar2Adjacent positions of (a);
R1′and R2′Are each in ring Ar2′Adjacent positions of (a);
R3and R3′Independently is H, alkyl or alkoxy;
m and m' are independently 0, 1, 2, 3 or 4;
the mark end in the structure shown in the formula (I) is connected with an extended conjugated structure, and the extended conjugated structure is used for adjusting the band gap and the energy level distribution of the acceptor material.
2. The non-fullerene acceptor material according to claim 1, wherein the extended conjugated structure has a structure of formula (II) or (II'), wherein the structure of formula (II) and the ring Ar in the structure of formula (I) are2The structure represented by the formula (II') and the ring Ar in the structure represented by the formula (I) are connected2′The connection is carried out in a connecting way,
Figure FDA0003117299000000012
wherein ring A and ring A' are independently absent, aromatic, heteroaromatic, substituted with one or more ReSubstituted aromatic rings, or by one or more ReA substituted heteroaromatic ring independently having 1, 2, 3, or 4 heteroatoms or heteroatom groups independently selected from N, O, S and C (═ O);
Reindependently alkyl, alkoxy or alkylthio;
b and B' are independently
Figure FDA0003117299000000021
X is independently H, halogen, C1-C4Alkyl or C1-C4An alkoxy group;
r is independently H or alkyl.
3. The non-fullerene acceptor material according to claim 1 or 2,
ring Ar1And ring Ar1′Wherein said aromatic ring is independently C6-C12Aromatic rings such as benzene rings or naphthalene;
and/or, ring Ar1And ring Ar1′Wherein the heteroaromatic ring is independently a 5-12 membered heteroaromatic ring, such as a 5-6 membered monocyclic heteroaromatic ring or an 8-12 fused heteroaromatic ring, and is, for example, pyridine;
and/or, ring Ar2And ring Ar2′Wherein said aromatic ring is independently C6-C12Aromatic rings such as benzene rings or naphthalene;
and/or, ring Ar2And ring Ar2′Wherein the heteroaromatic ring is independently a 5-to 12-membered heteroaromatic ring, such as a 5-to 6-membered monocyclic heteroaromatic ring or an 8-to 12-membered fused heteroaromatic ring, and such as a 5-to 6-membered monocyclic heteroaromatic ring;
and/or, ring Ar2And ring Ar2′Wherein the heteroaryl ring independently has 1, 2 or 3 heteroatoms, for example 1;
and/or, ring Ar2And ring Ar2′Wherein the heteroatom is independently selected from S and Se, e.g. S;
and/or, ring Ar2And ring Ar2′In, RaIndependently 1, 2 or 3;
and/or, RaWherein said alkyl is independently C1～C25Alkyl radicals, e.g. C1～C12Alkyl radicals, also e.g. C1～C4An alkyl group;
and/or, RaWherein said alkoxy is independently C1～C25Alkoxy radicals, e.g. C1～C12Alkoxy radicals, e.g. C1～C4Alkoxy radicalA group;
and/or, RaWherein said alkylthio is independently C1～C25Alkylthio radicals, e.g. C1～C12Alkylthio radicals, e.g. C1～C4An alkylthio group;
and/or, Rb、RcAnd RdWherein said alkyl is independently C1～C25Alkyl radicals, e.g. C1～C12Alkyl radicals, also e.g. C1～C4Alkyl groups such as methyl;
and/or, R3And R3′Wherein said alkyl is independently C1～C25Alkyl radicals, e.g. C1～C12Alkyl radicals, also e.g. C1～C4An alkyl group;
and/or, R3And R3′Wherein said alkoxy is independently C1～C25Alkoxy radicals, e.g. C1～C12Alkoxy radicals, e.g. C1～C4An alkoxy group;
and/or, in ring A and ring A', the aromatic rings are independently C6-C12Aromatic rings such as benzene rings or naphthalene;
and/or, in ring A and ring A', the heteroaromatic rings are independently 5-12 membered heteroaromatic rings, such as 5-6 membered monocyclic heteroaromatic rings or 8-12 fused heteroaromatic rings;
and/or, in ring a and ring a', the heteroaromatic ring independently has 1, 2 or 3 heteroatoms, for example 3;
and/or, in ring a and ring a', the heteroatoms are independently selected from N and S;
and/or, in ring A and ring A', ReIndependently 1, 2 or 3;
and/or, ReWherein said alkyl is independently C1～C25Alkyl radicals, e.g. C1～C12Alkyl radicals, also e.g. C1～C4An alkyl group;
and/or, ReWherein said alkoxy is independently C1～C25Alkoxy radicals, e.g. C1～C12Alkoxy radicals, e.g. C1～C4An alkoxy group;
and/or, ReWherein said alkylthio is independently C1～C25Alkylthio radicals, e.g. C1～C12Alkylthio radicals, e.g. C1～C4An alkylthio group;
and/or, in X, the halogen is independently F, Cl, Br or I;
and/or, in X, the C1-C4Alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl, such as methyl;
and/or, in X, the C1-C4Alkoxy is independently methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or tert-butoxy, for example methoxy;
and/or, in R, the alkyl is independently C1～C25Alkyl radicals, e.g. C1～C12Alkyl radicals, also e.g. C1～C4An alkyl group.
4. The non-fullerene acceptor material according to claim 1 or 2,
ring Ar1And ring Ar1′Wherein the aromatic rings are independently benzene rings;
and/or, ring Ar2And ring Ar2′Wherein the 5-6 membered monocyclic heteroaromatic ring is independently thiophene or selenene, such as thiophene;
and/or, ring Ar2And ring Ar2′Wherein the 8-12 fused heteroaromatic rings are independently a benzodithiophene, a trithiophene, or a dithienocyclopentadiene;
and/or, R1、R2、R1′And R2′In (1), the-C (R)b)(Rc)(Rd) Independently methyl, ethyl, isopropyl or tert-butyl, such as methyl or isopropyl;
and/or, R3And R3′Wherein said alkyl is independently methyl or isopropyl;
and/or in ring A and ring A', the 5-6 membered single heteroaromatic ring is independently thiophene, furan, pyrrole, imidazole, pyrazole, oxazole, pyridine or pyrazine;
and/or in ring a and ring a', the 8-12 fused heteroaromatic rings are independently benzothiophene, benzodithiophene, benzothiadiazole, benzodithiadiazole, thienothiadiazole, or thienopyrazine, such as 2,1, 3-benzothiadiazole;
and/or, in X, the halogen is independently F or Cl.
5. The non-fullerene acceptor material according to claim 1 or 2,
in the case of B and B', the reaction mixture,
Figure FDA0003117299000000041
independently is
Figure FDA0003117299000000042
And/or, structural units
Figure FDA0003117299000000043
Is composed of
Figure FDA0003117299000000044
For example
Figure FDA0003117299000000045
Also for example
Figure FDA0003117299000000046
Figure FDA0003117299000000047
And/or, structural units
Figure FDA0003117299000000048
Is composed of
Figure FDA0003117299000000049
For example
Figure FDA00031172990000000410
Also for example
Figure FDA00031172990000000411
Figure FDA00031172990000000412
And/or, structural units
Figure FDA00031172990000000413
Is composed of
Figure FDA00031172990000000414
6. The non-fullerene acceptor material according to claim 1 or 2,
ring Ar1And ring Ar1′Independently an aromatic ring;
and/or, ring Ar2And ring Ar2′Independently a heteroaromatic ring;
and/or, R3And R3′Independently is an alkyl group;
and/or, m and m' are independently 1;
and/or, ring a and ring a' are independently a non-or heteroaromatic ring;
and/or, B and B' are independently
Figure FDA00031172990000000415
And/or, X is independently H or halogen.
7. The non-fullerene acceptor material according to claim 1 or 2, wherein the structure of formula (I) is a structure of formula (I-1)
Figure FDA0003117299000000051
For example
Figure FDA0003117299000000052
And/or the structures shown in the formulas (II) and (II') are independently
Figure FDA0003117299000000053
Figure FDA0003117299000000054
8. The non-fullerene acceptor material according to claim 1 or 2, wherein the non-fullerene acceptor material has any one of the following structures:
Figure FDA0003117299000000055
Figure FDA0003117299000000061
9. a compound of formula (III),
Figure FDA0003117299000000062
wherein, ring Ar1Ring Ar1′Ring Ar2Ring Ar2′、R1、R2、R3、R1′、R2′、R3′M, m ', ring a ', B and B ' are as defined in any one of claims 1 to 8.
10. A process for the preparation of a compound of formula (III) according to claim 9, comprising the steps of: in an organic solvent, the compound represented by the formula (IV) is reacted with a compound H-B and a compound H-B' in the presence of an organic base as shown below,
Figure FDA0003117299000000063
wherein, the ring Ar1Ring Ar1′Ring Ar2Ring Ar2′、R1、R2、R3、R1′、R2′、R3′M, m ', ring a ', B and B ' are as defined in any one of claims 1 to 8.
11. A compound of formula (IV),
Figure FDA0003117299000000071
wherein, the ring Ar1Ring Ar1′Ring Ar2Ring Ar2′、R1、R2、R3、R1′、R2′、R3′M, m ', ring a and ring a' are as defined in any one of claims 1 to 8;
preferably, the compound of formula (IV) has any one of the following structures:
Figure FDA0003117299000000072
12. use of a non-fullerene acceptor material according to any one of claims 1 to 8 or a compound of formula (III) according to claim 9 as a material for a solar cell.
13. An organic solar cell device, characterized in that the acceptor material of the organic solar cell device is a non-fullerene acceptor material according to any one of claims 1 to 8 or a compound of formula (III) according to claim 9;
preferably, the organic solar cell device comprises an anode, a hole transport layer, a layer of a blend of the above non-fullerene acceptor material or the above compound of formula (III) with a donor polymer PM6, an electron transport layer and a cathode;
more preferably, the material of the anode is indium tin oxide; the hole transport layer is PEDOT PSS; the electron transport layer is made of PFN-Br; the cathode is made of aluminum.
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