WO2021174532A1 - Acceptor material of nitrogen-containing heterocyclic trapezoidal fused ring, and preparation method therefor and application thereof - Google Patents

Abstract

An acceptor material of a nitrogen-containing heterocyclic trapezoidal fused ring, and a preparation method therefor and an application thereof. According to the material, a conjugated system electron cloud density is increased by introducing a nitrogen atom to the center of the fused ring, so that the lowest unoccupied molecular orbital energy level of a target fullerene-free acceptor material is improved, the absorption spectrum of the material is broadened, and a high open circuit voltage and a large short circuit current can be simultaneously obtained in a solar cell; second, the fullerene-free acceptor prevents use of an SP ³ hybridized carbon atom having excessive steric hindrance, which promotes π-π stacking between molecular skeletons, and improves the current carrier transmission performance of the target acceptor material; moreover, by introducing two branched-chain-containing alkyl groups to each of the two sides of a nitrogen bridge and the central benzene ring for increasing certain steric hindrance, excessive accumulation of the target acceptor material in a mixed membrane is inhibited, and a good solubility property of the material is ensured.

Description

Receptor material containing nitrogen trapezoid fused ring, preparation method and application thereof Technical field

The present application relates to a small molecule acceptor material containing a nitrogen-containing trapezoidal fused ring, a preparation method thereof, and an application in an electron acceptor material of an organic solar cell, and belongs to the technical field of organic solar cell material preparation.

Background technique

An organic solar cell is a battery device that uses organic semiconductor materials to collect and convert solar energy. This type of battery has the characteristics of abundant raw materials, low cost, simple preparation process, etc., and has obvious advantages in large-scale industrial production, so it has become a research hotspot in the photovoltaic field.

The research of traditional organic solar cells mainly focuses on the electron acceptor of fullerene derivatives. However, the defects of this type of material itself, such as weak absorption in the visible light region and difficulty in controlling electronic energy levels and optical band gaps, have limited the further improvement of the efficiency of organic solar cells to a certain extent. At present, the efficiency of fullerene binary organic solar cells is still lower than 12% (Zhao et al, Nature Energy, 2016, 1, 15027). In order to solve the above problems, many new non-fullerene small molecule receptor materials have been developed one after another. Battery devices based on non-fullerene acceptor materials generally have a wider spectral absorption range and lower energy loss, and therefore have higher device conversion efficiency. For example, a single-cell non-fullerene solar cell still obtains a conversion efficiency of 9.5% under the condition of an energy loss as low as 0.5 eV (Ma et al, Chemistry of Materials, 2017, 29, 9775).

In order to further improve the photoelectric conversion efficiency of organic solar cells to meet the needs of commercial applications, it is necessary to design and synthesize new high-efficiency non-fullerene small molecule acceptor materials. It is generally believed that the introduction of SP ³ hybrid carbon atoms is a necessary condition for obtaining high-performance non-fullerene small molecule acceptor materials. The ^{introduction of alkyl side chains on the SP 3} carbon atoms can increase the solubility of the material while inhibiting the excessive aggregation of the target acceptor material in the mixed film, thereby obtaining an ideal active layer morphology. Therefore, the current research on non-fullerene small molecule acceptor materials is mainly focused on trapezoidal fused ring molecular material systems ^{containing SP 3 carbon bridges.} In contrast, ^{non-fullerene small molecule acceptor materials with SP 2} hybrid nitrogen atoms as bridges are rarely reported. Compared with SP ³ carbon atoms, ^{the introduction of SP 2} nitrogen atoms can enhance the electron-pushing ability of the electron-rich intermediate nucleus of the fused ring, thereby broadening the absorption spectrum of the acceptor material. However, the excellent rigid planar structure of this type of acceptor material makes it strong The self-aggregation tendency of the active layer leads to a larger phase separation in the active layer, which ultimately leads to poor device performance. How to achieve precise control of the aggregation state of conjugated fused ring molecules in a fused ring system containing SP ^{2 nitrogen atoms is a challenge in the field of organic photovoltaics.}

Summary of the invention

In view of the above problems, the first object of the present invention is to provide an acceptor material containing a nitrogen-containing hetero trapezoidal fused ring, which has a wide absorption spectrum, suitable molecular packing performance and high carrier transport performance.

How to achieve precise control of the aggregation state of conjugated fused ring molecules in a fused ring system containing SP ^{2 nitrogen atoms is a challenge in the field of organic photovoltaics.} In the present invention, it is proposed for the first time to use the steric hindrance of adjacent side chains on the conjugated fused ring molecular skeleton to control the molecular behavior of the polymer. In the process of realizing the present invention, the inventor unexpectedly discovered that when the adjacent side chains are linear alkyl groups with small steric hindrance, the material molecules have good crystallization and serious aggregation, and the photovoltaic performance of the material is poor; and when the adjacent side chains are When the chains are all branched alkyl groups with large steric hindrance, the crystallinity of the material molecules is reduced, the serious aggregation is significantly improved, and the photovoltaic performance of the material is greatly improved. The inventors have obtained an appropriate side chain optimization scheme through a large number of experiments, and can obtain a non-fullerene small molecule acceptor material with a suitable phase separation size from the donor polymer. Compared with ^{the trapezoidal fused ring molecular acceptor material containing SP 3} carbon atoms, this new type of nitrogen-containing hetero trapezoidal fused ring acceptor material has higher carrier migration performance, and thus has better photovoltaic performance.

The acceptor material of the nitrogen-containing trapezoidal fused ring has at least one of the structures shown in formula I and formula II:

in:

X ₁ , X ₂ , X ₃ , and X _{4 are} independently selected from O, S or Se;

R ₁ and R _{2 are} independently selected from the group consisting of C3～C30 branched alkoxy groups, C3～C30 branched fluorinated alkoxy groups, C3～C30 branched alkylthio groups, and C3～C30 branched alkoxy groups. Chain fluorinated alkylthio group, C3～C30 branched alkyl group, C3～C30 branched chain fluorinated alkyl group, C1～C28 linear alkoxy group, C1～C28 linear fluorinated alkoxy group , C1～C28 linear alkylthio, C1～C28 linear fluorinated alkylthio, C1～C28 linear alkyl, C1～C28 linear fluorinated alkyl, C1～C20 alkyl aromatic Group, C1～C20 fluorinated alkyl aromatic group, C1～C20 alkoxy aryl group, C1～C20 fluorinated alkoxy aryl group, C1～C20 alkylthio aryl group, C1～C20 fluorine Any one of alkylthio aryl groups, C1-C20 aromatic groups, and C1-C20 fluorinated aromatic groups;

Ar ₁ and Ar _{2 are} independently selected from any one of groups containing 1 to 5 thiophene rings. The group containing 1 to 5 thiophene rings may be substituted or unsubstituted thienyl groups, or A substituted or unsubstituted condensed ring formed by 2 to 5 thiophene rings;

A ₁ and A _{2 are} selected from any one of the groups of the chemical formulas shown in formulas III-1 to III-17:

_{Wherein, R 51, R 52, R} 53, R 54, R 61, R 62 are independently selected from hydrogen, halo, cyano, C ₁ ~ C ₂₀ alkyl group is, C ₁ ~ C ₂₀ alkoxy group, and Any one of a C ₁ to C ₂₈ alkylthio group, a C ₁ to C ₂₀ carbonyl group, and a C ₁ to C ₂₀ ester group, and the dotted line is the double bond connection position.

Optionally, R ₁ and R _{2 are} independently selected from the group consisting of C3～C30 branched alkoxy groups, C3～C30 branched fluorinated alkoxy groups, C3～C30 branched alkylthio groups, C3～C30 a branched fluorinated alkyl group of C30, C3 ~ C30 branched-chain alkyl group containing, C3 ~ C30 fluorinated alkyl group-containing branched chain, any one of C ₁ ~ C ₂₀ alkyl aryl group; X is =S; Ar ₁ , Ar _{2 are} independently selected from the formula

Any one of the structures shown; wherein R7 and R8 are independently selected from hydrogen atoms, C1-C20 alkyl groups, C1-C20 alkoxy groups, C1-C20 alkylthio groups, C1-C20 ester groups For any of them, the dotted line is the connection position of the group.

A ₁ and A _{2 are} selected from any one of the groups of formula III-1 to III-5 and formula III-9.

The second aspect of the present application provides a method for preparing the above-mentioned nitrogen-containing heterotrapezoidal fused ring acceptor material with the structure of formula I, which at least includes the following steps:

(1) Compound C is obtained by catalytic coupling reaction of compound A and compound B:

Wherein, Ar' is selected from at least one of _{Ar 1} and Ar _2;

(2) The compound C obtained in step (1) and the alkylamine R ₂ NH ₂ are subjected to catalytic debromination ring closure reaction to obtain compound D:

(3) The compound D obtained in step (2) is subjected to a formylation reaction to obtain compound E:

(4) The compound E and A group donor obtained in step (3) are subjected to condensation reaction under alkaline conditions to obtain a structure compound as shown in formula I, and the A group donor provides A1 group and/or A2 group compound. Optionally, the A group donor is a compound containing a group represented by formula III-1 to III-17.

Optionally, the solvent for catalyzing the coupling reaction in step (1) is selected from at least one of diethyl ether, tetrahydrofuran, and n-hexane;

The catalyst for catalyzing the coupling reaction in step (1) is [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride, and the added amount of the catalyst is the molar amount of the compound A 1%～10% of

The molar ratio of the compound A to the compound B in step (1) is 1:2.2-4; the reaction temperature of the catalytic coupling reaction in step (1) is 30-50°C, and the reaction time is 12-48 Hour.

Optionally, the solvent for catalyzing the debromination ring-closure reaction in step (2) is selected from at least one of toluene, dioxane, and benzene;

In step (2), the catalyst for catalyzing the debromination ring-closure reaction is bis-dibenzylideneacetone palladium and bis-diphenylphosphine ferrocene;

The molar ratio of bisdibenzylidene acetone palladium and bisdiphenylphosphine ferrocene in step (2) is 1:3.5-4.5, and the added amount of bisdibenzylidene acetone palladium is obtained in step (1) 0.9% to 10% of the molar amount of compound C;

In step (2), the deprotonation reagent that catalyzes the debrominated ring-closure reaction is sodium tert-butoxide;

In step (2), the molar ratio of compound C, sodium tert-butoxide, and alkylamine R ₂ NH ₂ is 1:10-20:2-8;

In step (2), the reaction temperature of the catalytic debromination ring-closure reaction is 60-110°C, and the reaction time is 3-12 hours.

Optionally, the solvent for the formylation reaction in step (3) is selected from at least one of 1,2-dichloroethane, chloroform, and dichloromethane;

The formylation reagent for the formylation reaction in step (3) is N,N-dimethylformamide and phosphorus oxychloride;

The molar ratio of compound D, phosphorus oxychloride, and N,N-dimethylformamide in step (3) is 1:15-20:15-20;

The reaction temperature of the formylation reaction in step (3) is 60-85°C, and the reaction time is 12-36 hours.

Optionally, the solvent for the condensation reaction in step (4) is selected from at least one of chloroform, chlorobenzene, and 1,2-dichloroethane;

The acid binding agent for the condensation reaction in step (4) is pyridine;

The molar ratio of the compound E to the A group donor in step (4) is 1:5-12;

The reaction temperature of the condensation reaction in step (4) is 60-70°C, and the reaction time is 8-24 hours;

_{The A 1} and A ₂ group donors in step (4) are selected from 5,6-difluoro-3-(dicyanomethylene)indigo (formula III-1, R ₅₁ ＝R ₆₁ ＝F) , 6-Fluoro-3-(dicyanomethylene) indigo (formula III-1, R ₅₁ ＝H, R ₆₁ ＝F), 5,6-dichloro-3-(dicyanomethylene) ) At least one of indigo (formula III-1, R ₅₁ =R ₆₁ =Cl) and 3-(dicyanomethylene)indigo (formula III-4).

The third aspect of the present application provides a method for preparing a nitrogen-containing hetero trapezoidal fused ring acceptor material having a structure of formula II, which at least includes the following steps:

(1) Compound H is obtained by catalytic coupling reaction of compound F and compound G:

Wherein, Ar" is selected from at least one of _{Ar 1} and Ar _2;

(2) The compound H obtained in step (1) and the alkylamine R ₂ NH ₂ are subjected to catalytic debromination ring closure reaction to obtain compound I:

(3) The compound I obtained in step (2) is subjected to a formylation reaction to obtain compound J:

(4) The compound J and A group donors obtained in step (3) are subjected to condensation reaction under alkaline conditions to obtain a structure compound as shown in formula II, and the A group donor provides A ₁ group and/ Or A ₂ group compound; alternatively, the A group donor is a compound containing a group represented by formula III-1 to III-17.

Optionally, the solvent for catalyzing the coupling reaction in step (1) is selected from at least one of diethyl ether, tetrahydrofuran, and n-hexane;

The catalyst for catalyzing the coupling reaction in step (1) is [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride, and the added amount of the catalyst is the molar amount of the compound A 1%～10% of

The molar ratio of the compound F to the compound G in step (1) is 1:2.2-4;

The reaction temperature of the catalytic coupling reaction in step (1) is 30-50°C, and the reaction time is 24-48 hours.

Optionally, the solvent for catalyzing the debromination ring-closure reaction in step (2) is selected from at least one of toluene, dioxane, and benzene;

In step (2), the catalyst for catalyzing the debromination ring-closure reaction is bis-dibenzylideneacetone palladium and bis-diphenylphosphine ferrocene;

In step (2), the molar ratio of bisdibenzylidene acetone palladium and bisdiphenylphosphine ferrocene is 1:4, and the added amount of bisdibenzylidene acetone palladium is the compound obtained in step (1) 1%～10% of the molar amount of H;

In step (2), the deprotonation reagent that catalyzes the debrominated ring-closure reaction is sodium tert-butoxide;

In step (2), the molar ratio of compound H, sodium tert-butoxide, and alkylamine R ₂ NH ₂ is 1:10-20:2-8;

In step (2), the reaction temperature of the catalytic debromination ring-closure reaction is 60-110°C, and the reaction time is 3-12 hours.

Optionally, the solvent for the formylation reaction in step (3) is selected from at least one of 1,2-dichloroethane, chloroform, and dichloromethane;

The formylation reagent for the formylation reaction in step (3) is N,N-dimethylformamide and phosphorus oxychloride;

The molar ratio of compound I, phosphorus oxychloride, and N,N-dimethylformamide in step (3) is 1:15-20:15-20;

The reaction temperature of the formylation reaction in step (3) is 60-85°C, and the reaction time is 12-36 hours.

Optionally, the solvent for the condensation reaction in step (4) is selected from at least one of chloroform, chlorobenzene, and 1,2-dichloroethane;

The acid binding agent for the condensation reaction in step (4) is pyridine;

In step (4), the molar ratio of the compound J to the A group donor is 1:5-12;

The reaction temperature of the condensation reaction in step (4) is 60-70°C, and the reaction time is 8-24 hours;

The group A donor in step (4) is selected from 5,6-difluoro-3-(dicyanomethylene)indigo (formula III-1, R ₅₁ ＝R ₆₁ ＝F), 6-fluoro -3-(dicyanomethylene)indigo (formula III-1, R ₅₁ ＝H, R ₆₁ ＝F), 5,6-dichloro-3-(dicyanomethylene)indigo ( Formula III-1, R ₅₁ =R ₆₁ =Cl), at least one of 3-(dicyanomethylene)indigo (formula III-4).

The fourth aspect of the present application provides a semiconductor material containing at least one of the acceptor material described in any one of the above and the acceptor material prepared by the method described in any one of the above.

The fifth aspect of the present application provides a solar cell device containing at least one of the acceptor material described in any one of the above and the acceptor material prepared by the method described in any one of the above.

Optionally, the solar cell device includes a substrate, an anode, an anode modification layer, a photoactive layer, a cathode modification layer, and a cathode.

In a preferred solution, the substrate is glass or polyethylene terephthalate (PET), the anode is indium tin oxide (ITO); the anode modification layer is poly 3,4-ethylene dioxythiophene: Polystyrene sulfonate (PEDOT: PSS); the cathode modification layer is 2,9-bis(3-dimethylaminopropyl)isoquinolo[4',5',6':6,5,10 ]Anthra[2,1,9-def]isoquinoline-1,3,8,10(2H,9H)-tetraketone (PDIN); cathode is Al.

The photoactive layer is prepared by blending the nitrogen-containing trapezoidal fused ring acceptor material and the electron donor material, wherein the electron donor material is at least one of PBDB-T and PM6;

The mass ratio of the electron donor to the electron acceptor in the photoactive layer is 1:1 to 1.5, and the solvent used in the photoactive layer is toluene, xylene, trimethylbenzene, chloroform, chlorobenzene, dichlorobenzene and trichloro At least one of benzene, the concentration of the electron donor material in the photoactive layer may be 1mg/mL～20mg/mL, preferably 5mg/mL～10mg/mL, and the concentration of the electron acceptor may be 1.5mg/mL～ 30 mg/mL, preferably 5 mg/mL to 15 mg/mL.

The photoactive layer is annealed at a temperature of 50-150°C, and the annealing time is 1-30 minutes.

In this application, all conditions related to the numerical range can be independently selected from any point value within the selected value range, including the end value of the range.

In this application, “C ₁ ～C ₂₀ ”, “C ₁ ～C ₂₈ ”, “C ₃ ～C ₃₀ ”, etc. all refer to the number of carbon atoms contained in the group. For example, a C ₁ ～C ₂₈ alkoxy group means An alkoxy group having 1 to 28 carbon atoms;

In this application, C ₃ ～C ₃₀ branched alkoxy groups, C ₃ ～C ₃₀ branched fluorinated alkoxy groups, C ₃ ～C ₃₀ branched alkylthio groups, C ₃ ～C ₃₀ Branched fluorinated alkylthio groups, C ₃ ～C ₃₀ branched alkyl groups, C ₃ ～C ₃₀ branched fluorinated alkyl groups all mean that the alkyl group has at least one or more branched chains, branched The position of can be anywhere from C ₁ to C ₂₉ ;

In this application, "alkyl" refers to a group formed by the loss of any one hydrogen atom of an alkane compound, and the alkane compound includes straight-chain alkanes, branched-chain alkanes, and cycloalkanes;

In this application, "fluorinated alkyl" refers to a group formed by replacing at least one hydrogen atom on an alkyl group with a fluorine atom;

In this application, "aromatic group" refers to a group formed by the loss of any hydrogen atom on the aromatic ring in the molecule of an aromatic compound; the aromatic compound includes a compound containing an aromatic ring, and at least one hydrogen atom on the aromatic ring is substituted by an alkyl group. compound of;

In this application, "fluorinated aromatic group" refers to a group in which at least one hydrogen atom on the aromatic group is replaced by a fluorine atom;

In this application, "alkyl aryl group" refers to a group in which at least one hydrogen atom on an aryl group is substituted by an alkyl group;

In this application, "fluorinated alkyl aryl group" refers to a group in which at least one hydrogen atom on the alkyl aryl group is replaced by a fluorine atom;

In this application, "alkoxy" refers to a group formed after losing a hydrogen atom on a hydroxyl group in an alkyl alcohol molecule;

In this application, "fluorinated alkoxy" refers to a group in which at least one hydrogen atom in an alkoxy group is replaced by a fluorine atom;

In this application, "alkylthio" refers to a group formed after losing one hydrogen atom on a mercapto group in an alkyl mercaptan molecule;

In this application, "fluorinated alkylthio" refers to a group in which at least one hydrogen atom in an alkylthio group is replaced by a fluorine atom;

In this application, "alkoxy aryl group" refers to a group in which at least one hydrogen atom on the aryl group is replaced by an alkoxy group;

In this application, "fluorinated alkoxy aromatic group" refers to a group in which at least one hydrogen atom on the alkoxy group of the alkoxy aromatic group is replaced by a fluorine atom;

In this application, "alkylthio aryl" refers to a group in which at least one hydrogen atom on the aryl group is substituted by an alkylthio group;

In the present application, "fluorinated alkylthio aryl group" refers to a group in which at least one hydrogen atom of the alkyl thio group is replaced by a fluorine atom in the alkylthio aryl group.

In this application, "ester group" refers to the functional group of the ester in the carboxylic acid derivative, and the structural formula is -COOR, where R is an alkyl group and other non-H groups.

The beneficial effects of the present invention include but are not limited to:

The present invention provides a new type of non-fullerene acceptor material containing nitrogen heterocyclic trapezoidal fused ring, which increases the electron cloud density of the conjugated system by introducing a nitrogen atom in the center of the fused ring, thereby improving the target non-fullerene acceptor material The lowest unoccupied molecular orbital energy level and broaden the absorption spectrum of the material, which is conducive to obtaining high open-circuit voltage and large short-circuit current in solar cells; secondly, the non-fuller acceptor avoids the use of excessive steric hindrance The SP ³ hybridized carbon atoms, which can promote the π-π stacking between the molecular frameworks and improve the carrier transport performance of the target acceptor material; again, by simultaneously introducing two alkyl chains on the nitrogen bridge and the central benzene ring Increasing a certain steric hindrance can prevent excessive aggregation of the target receptor material in the mixed film while ensuring good solubility of the material.

The non-fullerene small molecule acceptor material provided by the present invention has good film-forming properties, a narrow optical band gap (E ^g _opt ≤1.41eV), a shallower LUMO energy level (≥-3.85eV), and High electron mobility (≥10 ^-4 cm ² V ^-1 s ^-1 ). The material is used in solar cells. After device fabrication and optimization, the conversion efficiency can reach more than 15%, and the open circuit voltage of the battery is higher than 0.93 volts, the short-circuit current is higher than 22mA cm ^-2 .

Description of the drawings

^{FIG. 1 is a 1} H NMR spectrum of the acceptor material M3 prepared in Example 1.

^{2 is a 1} H NMR spectrum of the acceptor material M32 prepared in Example 2.

^{FIG. 3 is a 1} H NMR spectrum of the acceptor material M8 prepared in Example 3. FIG.

^{4 is a 1} H NMR spectrum of the acceptor material M1 prepared in Example 4.

^{5 is a 1} H NMR spectrum of the acceptor material M2 prepared in Example 5.

^{6 is a 1} H NMR spectrum of the acceptor material M4 prepared in Example 6.

^{FIG. 7 is a 1} H NMR spectrum of the acceptor material M5 prepared in Example 7. FIG.

^{8 is a 1} H NMR spectrum of the acceptor material M6 prepared in Example 8.

^{9 is a 1} H NMR spectrum of the acceptor material M31 prepared in Example 9.

^{10 is a 1} H NMR spectrum of the acceptor material M34 prepared in Example 10.

^{11 is a 1} H NMR spectrum of the acceptor material M35 prepared in Example 11.

^{12 is a 1} H NMR spectrum of the acceptor material M36 prepared in Example 12.

^{FIG. 13 is a 1} H NMR spectrum of the acceptor material M37 prepared in Example 13.

^{14 is a 1} H NMR spectrum of the acceptor material M40 prepared in Example 14.

Fig. 15 is a current-voltage (J-V) curve diagram of solar cell devices prepared with M1, M2, M3, M4, M5, M6, and M8 as active layer materials.

Fig. 16 is a current-voltage (J-V) curve diagram of solar cell devices prepared with M31, M32, M34, M35, M36, and M37 as active layer materials.

Fig. 17 is a transmission electron microscope image of a mixed film of M3 and a donor material PM6, and a mixed film of M32 and a donor material PM6.

Figure 18 is a grazing incidence X-ray wide-angle scattering spectrum of single-component M3 and M32 films.

Fig. 19 is a graph of electron mobility of a mixed film of M3 and a donor material PM6, and a mixed film of M32 and a donor material PM6.

20 is a graph of hole mobility of a mixed film of M3 and a donor material PM6, and a mixed film of M32 and a donor material PM6.

Detailed ways

In order to better illustrate the content of the present invention, the following specific examples are used to further illustrate the technical solution of the present invention, which specifically include material synthesis and characterization, device preparation and performance testing.

The raw materials, catalysts and other chemical reagents involved in the examples of this application are all commercially available products without special instructions.

^{The 1} H NMR spectrum of the obtained material was tested with a Bruker AVANCE-400 nuclear magnetic resonance instrument;

A Fourier transform mass spectrometer of IonSpec 4.7T model from IonSpec of the United States was used to test the mass spectra.

Example 1: In formula I, R ₁ is 2-ethylhexyloxy, R ₂ is 2-hexyldecyl, X ₁ and X ₂ are both S atoms, and A ₁ and A ₂ are both

When, the synthetic route of acceptor material M3 is as follows:

(1) Compound 1a and (3-bromo-2-thiophene) zinc chloride are catalyzed by [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride through Negishi coupling reaction to obtain the compound 2a;

In a 100mL two-necked round bottom flask, add 2,3-dibromothiophene (2.42g, 10mmol) and 30mL of dry ether, slowly add n-butyllithium (2.5M, 4mL) at -78℃, and react after the addition is complete The solution was maintained at -78°C for 1 hour, another ZnCl ₂ (1M, 10 mL) was added slowly, and then the temperature was raised to 0°C and maintained for 1 hour. After that, take 2,3,6,7-tetrabromo-4,8-bis((2-ethylhexyl)oxy)benzodithiophene (2.28g, 3mmol) and [1,1'-bis(two Phenylphosphino)ferrocene]palladium dichloride (0.22g, 0.3mmol) was quickly added at once, and the mixture was heated to 50°C under the protection of nitrogen and refluxed for 12 hours. After cooling to room temperature, the reaction was quenched by adding water, extracted with ether, and the solvent was spin-dried to obtain a crude product, which was separated and purified by silica gel column chromatography to obtain a pale yellow solid 2a (2.24 g, yield 80%). ¹ H NMR (400MHz, CDCl ₃ , ppm): δ7.50 (d, J = 5.2 Hz, 2H), 7.13 (d, J = 5.2 Hz, 2H), 4.10 (d, J = 6.4 Hz, 4H), 2.05 (m, 2H), 1.35-1.69 (m, 16H), 0.98 (t, J = 7.2 Hz, 6H), 0.89 (t, J = 7.2 Hz, 6H). HRMS (MALDI) m/z: calculated C ₃₄ H ₃₈ Br ₄ O ₂ S ₄ , 921.8488; experimental value: 921.8496.

(2) The compound 2a obtained in step 1 and 2-hexyldecyl-1-amine are formed by bis-dibenzylidene acetone palladium and bis-diphenylphosphine ferrocene to obtain the ring-closure compound through the Buchwald-Hartwig reaction under the catalytic system 3a;

In a 100mL two-necked round bottom flask, add compound 2a (3.00g, 3.26mmol), sodium tert-butoxide (6.26g, 65.2mmol) and 30mL of dry toluene. After bubbling with nitrogen for 0.5 hours, add bisdibenzylideneacetone palladium ( 0.18g, 0.32mmol) and bisdiphenylphosphinoferrocene (0.72g, 1.30mmol), then continue to bubble for 0.5 hours, and then add 2-hexyldecyl-1-amine (3.93g, 16.3mmol). The mixed solution was refluxed for 12 hours at 115°C under nitrogen protection. After cooling to room temperature, the reaction was quenched by adding water, extracted with dichloromethane, and the solvent was spin-dried to obtain a crude product, which was separated and purified by silica gel column chromatography to obtain a pale yellow oily product 3a (1.09 g, yield 31%). ¹ H NMR (400MHz, CDCl ₃ , ppm): δ7.18 (d, J = 5.2 Hz, 2H), 7.06 (d, J = 5.2 Hz, 2H), 4.69 (m, 4H), 4.03 (d, J = 7.2 Hz, 4H), 2.02 (m, 4H), 1.80-0.84 (m, 76H), 0.81 (t, J = 6.8 Hz, 6H), 0.75 (t, J = 6.8 Hz, 6H). HRMS (MALDI) m/z: calculated for C ₆₆ H ₁₀₄ N ₂ O ₂ S ₄ , 1084.6975; experimental value: 1084.7002.

(3) Compound 4a is obtained from compound 3a through Vilsmeier-Haack reaction;

In a 100 mL two-necked round bottom flask, compound 3a (1.00 g, 0.92 mmol), 30 mL of dry 1,2-dichloroethane and DMF (1.34 g, 18.4 mmol) were added. Phosphorus oxychloride (2.87g, 18.4mmol) was added all at once. After the addition, the reaction solution was stirred for 1 hour, and then heated to 60°C for 12 hours. After cooling to room temperature, the reaction was quenched by adding water, extracted with dichloromethane, and the solvent was spin-dried to obtain a crude product, which was separated and purified by silica gel column chromatography to obtain a yellow solid product 4a (0.95 g, yield 91%). ¹ H NMR (400MHz, CDCl ₃ , ppm): δ9.94 (s, 2H), 7.71 (s, 2H), 4.75 (m, 4H), 3.99 (d, J = 6.8 Hz, 4H), 2.05 (m , 2H), 1.97 (m, 2H), 1.73-0.86 (m, 76H), 0.80 (t, J = 7.2 Hz, 6H), 0.75 (t, J = 7.2 Hz, 6H). The high resolution mass spectrum is HRMS (DART Positive) m/z: [M+H] ⁺ calculation: C ₆₈ H ₁₀₅ N ₂ O ₄ S ₄ , 1141.6952; experimental value: 1141.6996.

(4) Compound 4a and 5,6-difluoro-3-(dicyanomethylene)indigo are reacted by Knoevenagel to obtain acceptor material M3:

In a 250mL round bottom flask, compound 4a (0.1g, 0.088mmol) and 5,6-difluoro-3-(dicyanomethylene)indigo (0.161g, 0.70mmol) were dissolved in 20mL of chloroform, 0.2mL pyridine was added, the mixture was refluxed for 12 hours at 65°C under the protection of nitrogen, cooled to room temperature, poured into 100mL of anhydrous methanol, and filtered to obtain the crude product, which was separated and purified by silica gel column chromatography to obtain a dark blue solid M3 (0.12g, yield 88%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of the acceptor material M3: δ8.95 (s, 2H), 8.53 (dd, J = 6.4 Hz, 2H), 7.90 (s, 2H), 7.68 (t, J =7.6Hz,2H),4.73(d,J=7.6Hz,4H),4.01(m,4H),2.07(m,2H),1.99(m,2H),1.77-0.88(m,76H),0.82 -0.70(m,12H). The high resolution mass spectrum is (DART Positive) m/z: [M+H] ⁺ calculation: C ₉₂ H ₁₀₉ N ₆ O ₄ F ₄ S ₄ , 1565.7324; experimental value: 1565.7357. Elemental analysis (%), calculation: C ₉₂ H ₁₀₈ N ₆ O ₄ F ₄ S ₄ : C, 70.56; H, 6.95; N, 5.37; experimental value: C, 70.69; H, 6.84; N, 5.31.

Example 2: In formula I, R ₁ is 2-ethylhexyloxy, R ₂ is hexadecyl, X ₁ and X ₂ are both S atoms, and A ₁ and A ₂ are both

When the acceptor material M32 is synthesized. The synthetic route is similar to Example 1, except that in Example 2, when the Buchwald-Hartwig ring closure reaction occurs, hexadecylamine is used. For the specific synthetic route, please refer to Example 1.

(1) Synthesis of compound 3b: specifically refer to the synthesis step of compound 3a (1.23 g, yield 35%). ¹ H NMR (400MHz, CDCl ₃ , ppm): δ7.20 (d, J = 5.2 Hz, 2H), 7.08 (d, J = 5.2 Hz, 2H), 4.73 (m, 4H), 4.03 (d, J ＝6.8Hz,4H),2.05(m,2H),1.80-1.15(m,68H),1.01(t,J＝7.2Hz,6H),0.92(t,J＝6.8Hz,6H),0.86(t , J=6.8Hz, 6H). HRMS (MALDI) m/z: calculated: C ₆₆ H ₁₀₄ N ₂ O ₂ S ₄ , 1084.6975; experimental value: 1084.6987.

(2) Synthesis of compound 4b: specifically refer to the synthesis procedure of compound 4a (yield 88%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of compound 4a: δ 9.94 (s, 2H), 7.74 (s, 2H), 4.78 (m, 4H), 4.05 (d, J = 7.2 Hz, 4H), 2.05(m,2H),1.81-1.07(m,72H),1.02(t,J=7.2Hz,6H),0.93(t,J=7.2Hz,6H),0.85(t,J=7.2Hz,6H ). HRMS (DART Positive) m/z: [M+H] ⁺ calculated C ₆₈ H ₁₀₅ N ₂ O ₄ S ₄ , 1141.6952; experimental value: 1141.6932.

(3) Synthesis of acceptor material M32: specifically refer to the synthesis steps of acceptor material M3 (0.11 g, yield 88%). ¹ H NMR (CDCl ₃ , 400MHz, ppm) of the acceptor material M32: 8.95 (s, 2H), 8.52 (dd, J = 6.4 Hz, 2H), 7.87 (s, 2H), 7.68 (t, J = 7.6 Hz, 2H), 4.78 (t, J = 6.8 Hz, 4H), 4.06 (m, 4H), 2.07 (m, 2H), 1.87-1.10 (m, 72H), 1.04 (t, J = 7.6 Hz, 6H ), 0.97 (t, J = 7.2 Hz, 6H), 0.84 (t, J = 7.2 Hz, 6H). High resolution mass spectrum, calculated: C ₉₂ H ₁₀₉ N ₆ O ₄ F ₄ S ₄ , 1565.7324; experimental value: 1565.7312. Elemental analysis (%), calculation: C ₉₂ H ₁₀₈ N ₆ O ₄ F ₄ S ₄ : C, 70.56; H, 6.95; N, 5.37; experimental value: C, 70.70; H, 7.01; N, 5.42.

Example 3: In formula I, R ₁ is 2-ethylhexyloxy, R ₂ is 2-butyloctyl, X ₁ and X ₂ are both O atoms, and A ₁ and A ₂ are both

Time, the synthesis of acceptor material M8.

(1) 4,8-bis(2-ethylhexyloxy)benzodifuran (BDF) is brominated with liquid bromine to obtain the tetrabromo-substituted compound 1b.

In a 100mL two-necked round bottom flask, add BDF (4.14g, 10mmol) and 30mL dry chloroform, and slowly add bromine (9.60g, 60mmol) at 0℃. After the addition, the reaction solution is reacted at 60℃ for 12 hours . After cooling to room temperature, the _{reaction was quenched by adding NaHSO 3} aqueous solution, extracted with dichloromethane, and the solvent was spin-dried to obtain a crude product, which was separated and purified by silica gel column chromatography to obtain pale white solid 1b (5.11 g, yield 70%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of compound 1b: δ 4.24 (d, J = 6.4 Hz, 4H), 2.12 (m, 2H), 1.35-1.69 (m, 16H), 0.98 (t, J = 7.2 Hz, 6H), 0.89 (t, J = 7.2 Hz, 6H).

(2) Compound 1b and (3-bromo-2-thiophene) zinc chloride are catalyzed by [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride through Negishi coupling reaction to obtain the compound 2b.

For details, refer to the synthetic procedure of compound 2a (3.56 g, yield 81%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of compound 2b: δ7.06 (d, J = 5.6 Hz, 2H), 7.01 (d, J = 5.6 Hz, 2H), 4.50 (d, J = 6.4 Hz, 4H), 2.12 (m, 2H), 1.35-1.69 (m, 16H), 0.98 (t, J = 7.2 Hz, 6H), 0.89 (t, J = 7.2 Hz, 6H).

(3) The compound 2b obtained in step 2 and 2-butyloctyl-1-amine are closed by the Buchwald-Hartwig reaction under the catalytic system composed of bisdibenzylideneacetone palladium and bisdiphenylphosphine ferrocene Compound 3c;

For details, refer to the synthesis step of compound 3a (0.89 g, yield 38%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of compound 3c: δ7.08 (d, J = 5.6 Hz, 2H), 7.03 (d, J = 5.6 Hz, 2H), 4.50-4.44 (m, 8H), 2.06-1.94 (m, 4H), 1.62-0.75 (m, 72H).

(4) Compound 4c is obtained from compound 3c through Vilsmeier-Haack reaction;

For details, refer to the synthetic procedure of compound 4a (0.78 g, yield 83%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of compound 4c: δ 9.89 (s, 2H), 7.65 (s, 2H), 4.56-4.52 (m, 8H), 2.06-1.97 (m, 4H), 1.63 -1.11 (m, 54H), 1.01 (t, J = 7.2 Hz, 6H), 0.92 (t, J = 7.2 Hz, 6H), 77 (t, J = 7.2 Hz, 6H).

(5) Compound 4c and 5,6-difluoro-3-(dicyanomethylene)indigo are reacted by Knoevenagel to obtain acceptor material M8:

For details, refer to the synthesis procedure of acceptor material M3 (0.12 g, yield 87%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of the acceptor material M8: δ8.76 (s, 2H), 8.43 (dd, J = 6.4 Hz, 2H), 7.70 (s, 2H), 7.68 (t, J =7.6 Hz, 2H), 4.69-4.57 (m, 8H), 2.06 (m, 4H), 1.80-1.03 (m, 60H), 0.84-0.76 (m, 12H).

Example 4: In formula I, R ₁ is 2-ethylhexyloxy, R ₂ is 2-ethylhexyl, X ₁ and X ₂ are both S atoms, and A ₁ and A ₂ are both

When the acceptor material M1 is synthesized.

For details, refer to the synthesis procedure of acceptor material M3 (0.12 g, yield 87%). ¹ H NMR (CDCl ₃ , 400MHz, ppm) of the acceptor material M1: δ8.97 (s, 2H), 8.68 (dd, J = 7.6Hz, 2H), 7.91 (m, 4H), 7.73 (m, 4H) ), 4.75 (d, J=4.4 Hz, 4H), 4.06 (m, 4H), 2.08-1.95 (m, 4H), 1.62-0.95 (m, 44H), 0.78-0.69 (m, 12H).

Example 5: In formula I, R ₁ is 2-ethylhexyloxy, R ₂ is 2-ethylhexyl, X ₁ and X ₂ are both S atoms, and A ₁ and A ₂ are both

When the acceptor material M2 is synthesized.

For details, refer to the synthesis procedure of acceptor material M3 (0.10 g, yield 83%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of the acceptor material M2: δ8.94 (s, 2H), 8.51 (dd, J = 5.6 Hz, 2H), 7.88 (s, 2H), 7.68 (t, J =7.2Hz,2H),4.75(d,J=7.6Hz,4H),4.01(m,4H),2.07(m,2H),1.99(m,2H),1.74-0.95(m,44H),0.77 -0.69(m,12H).

Example 6: In formula I, R ₁ is 2-ethylhexyloxy, R ₂ is 2-hexyldecyl, X ₁ and X ₂ are both S atoms, and A ₁ and A ₂ are both

When the acceptor material M4 is synthesized.

For details, refer to the synthesis procedure of acceptor material M3 (0.13 g, yield 88%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of the acceptor material M4: δ 8.89 (s, 2H), 8.35 (s, 2H), 7.93 (s, 2H), 7.87 (s, 2H), 4.71 (d , J=7.6Hz, 4H), 4.00 (m, 4H), 2.08 (m, 2H), 1.98 (m, 2H), 1.62-0.95 (m, 76H), 0.80-0.73 (m, 12H).

Example 7: In formula I, R ₁ is 2-ethylhexyloxy, R ₂ is 2-hexyldecyl, X ₁ and X ₂ are S atoms, and A ₁ and A ₂ are both

Time, the synthesis of acceptor material M5.

For details, refer to the synthesis procedure of acceptor material M3 (0.11 g, yield 86%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of the acceptor material M5: 8.97 (s, 2H), 8.75 (s, 2H), 7.95 (m, 4H), 4.73 (d, J = 6.8 Hz, 4H), 4.01 (m, 4H), 2.08 (m, 2H), 2.00 (m, 2H), 1.61-0.96 (m, 76H), 0.80-0.73 (m, 12H).

Example 8: In formula I, R ₁ is 2-ethylhexyloxy, R ₂ is 2-hexyldecyl, X ₁ and X ₂ are S atoms, and A ₁ and A ₂ are both

Time, the synthesis of acceptor material M6.

For details, refer to the synthesis procedure of acceptor material M3 (0.12 g, yield 87%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of the acceptor material M6: δ8.97(s,2H), 8.67(d,J=6.8Hz,2H), 7.92(m,4H), 7.73(m,4H) ), 4.73(d,J=7.6Hz,4H),4.01(m,4H),2.10(m,2H),2.00(m,2H),1.64-0.95(m,76H),0.80-0.73(m, 12H).

Example 9: In formula I, R ₁ is octyloxy, R ₂ is 2-hexyldecyl, X ₁ and X ₂ are both S atoms, and A ₁ and A ₂ are both

When the acceptor material M31 was synthesized.

For details, refer to the synthesis procedure of acceptor material M3 (0.12 g, yield 87%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of the acceptor material M31: δ8.93 (s, 2H), 8.49 (dd, J = 5.6Hz, 2H), 7.87 (s, 2H), 7.68 (m, 2H) ), 4.73 (d, J=7.6 Hz, 4H), 4.20 (m, 4H), 2.01 (m, 6H), 1.64-0.90 (m, 74H), 0.81-0.73 (m, 12H).

Example 10: In formula I, R ₁ is 2-ethylhexyloxy, R ₂ is 2-butyloctyl, X ₁ and X ₂ are S atoms, and A ₁ and A ₂ are both

When the acceptor material M34 is synthesized.

For details, refer to the synthesis procedure of acceptor material M3 (0.12 g, yield 87%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of the acceptor material M34: δ8.97 (s, 2H), 8.53 (t, J = 6.4 Hz, 2H), 7.93 (s, 2H), 7.71 (d, J =7.2Hz,2H), 4.80(d,J=7.6Hz,4H),4.08(m,4H),2.15-2.03(m,4H),1.79-0.98(m,52H),0.80-0.72(m, 12H).

Example 11: In formula I, R ₁ is 2-butyloctyloxy, R ₂ is 2-ethylhexyl, X ₁ and X ₂ are S atoms, and A ₁ and A ₂ are both

Time, the synthesis of acceptor material M35.

For details, refer to the synthesis procedure of acceptor material M3 (0.11 g, yield 84%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of the acceptor material M35: δ8.95 (s, 2H), 8.52 (t, J = 6.4 Hz, 2H), 7.88 (s, 2H), 7.68 (t, J =7.2Hz,2H),4.74(d,J=7.6Hz,4H),4.01(m,4H),2.11-1.92(m,4H),1.63-0.90(m,52H),0.79-0.71(m, 12H).

Example 12: In formula I, R ₁ is 2-butyloctyloxy, R ₂ is 2-butyloctyl, X ₁ and X ₂ are S atoms, and A ₁ and A ₂ are both

When the acceptor material M36 is synthesized.

For details, refer to the synthesis procedure of acceptor material M3 (0.12 g, yield 85%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of the acceptor material M36: δ 8.98 (s, 2H), 8.52 (dd, J = 6.0 Hz, 2H), 7.92 (s, 2H), 7.71 (t, J =6.8Hz,2H),4.78(d,J=7.6Hz,4H),4.06(m,4H),2.18-2.02(m,4H),1.69-0.93(m,72H),0.79-0.71(m, 12H).

Example 13: In formula I, R ₁ is 2-hexyldecyloxy, R ₂ is 2-hexyldecyl, X ₁ and X ₂ are S atoms, and A ₁ and A ₂ are both

When the acceptor material M37 is synthesized.

For details, refer to the synthesis procedure of acceptor material M3 (0.11 g, yield 84%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of the acceptor material M37: δ 8.98 (s, 2H), 8.55 (dd, J = 6.8 Hz, 2H), 7.93 (s, 2H), 7.71 (t, J =6.0Hz,2H),4.76(d,J=7.6Hz,4H),4.05(m,4H),2.14-2.02(m,4H),1.68-0.91(m,84H),0.84-0.78(m, 12H).

Example 14: In formula I, R ₁ is 2-butyloctyloxy, R ₂ is 2-butyloctyl, X ₁ and X ₂ are both S atoms, and A ₁ is

A ₂ is

When, the synthetic route of acceptor material M40 is as follows:

In a 100 ml round-bottom flask, the dialdehyde-based compound (0.114g, 0.1mmol), 3-(dicyanomethylene)thiophenindone (0.022g, 0.11mmol) and 5,6-difluoro-3 -(Dicyanomethylene) indigo ketone (0.023g, 0.10mmol) and dissolved in 20mL chloroform, add 0.01mL pyridine, the mixture is refluxed for 12 hours at 65°C under the protection of nitrogen, cooled to room temperature, and poured into The crude product was obtained by suction filtration in 100 mL of anhydrous methanol, and was separated and purified by silica gel column chromatography to obtain a dark blue solid M40 (0.046 g, yield 37%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of the acceptor material M40: δ 8.95 (s, 1H), 8.90 (s, 1H), 8.52 (dd, J = 9.6, 6.4 Hz, 1H), 8.36 (d ,J=2.4Hz,1H),7.93(d,J=2.4Hz,1H),7.89(s,1H),7.87(s,1H),7.68(t,J=7.2Hz,1H),4.73(m , 4H), 4.00 (d, J=6.4 Hz, 4H), 2.10-1.98 (m, 4H), 1.64-0.88 (m, 76H), 0.76-0.67 (m, 12H). The high resolution mass spectrum is calculated as (DART Positive): C ₉₀ H ₁₀₈ F ₂ N ₆ O ₄ S ₅ , 1534.7004; experimental value: 1534.7037. Elemental analysis (%), calculation: C ₉₀ H ₁₀₈ F ₂ N ₆ O ₄ S ₅ : C, 70.37; H, 7.09; N, 5.47; experimental value: C, 70.60; H, 6.94; N, 5.39.

Example 15: In formula I, R ₁ is 2-hexyldecyloxy, R ₂ is 2-hexyldecyl, X ₁ is O atom, X ₂ is S atom, A ₁ and A ₂ are both

When the acceptor material M41 was synthesized.

(1) 4,8-bis(2-ethylhexyloxy)thienobenzofuran (U0) is reacted in liquid bromine to obtain the tetrabromo-substituted compound U1;

For details, refer to the synthesis procedure of compound 1b (yield 83%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of compound U1: δ 4.34 (d, J = 5.6 Hz, 2H), 4.23 (d, J = 5.6 Hz, 2H), 1.85-1.75 (m, 2H), 1.66-1.52 (m, 8H), 1.38-1.28 (m, 8H), 0.99 (t, J=7.6 Hz, 6H), 0.95-0.86 (m, 6H).

(2) Compound U1 and (3-bromo-2-thiophene) zinc chloride are catalyzed by [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride through Negishi coupling reaction to obtain the compound U2;

For details, refer to the synthesis step of compound 2b (3.56 g, yield 81%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of compound U2: δ 7.50 (d, J = 5.6 Hz, 1H), 7.13 (d, J = 5.6 Hz, 1H), 7.08 (d, J = 5.2 Hz, 1H), 7.02 (d, J = 5.2 Hz, 1H), 4.34 (d, J = 5.6 Hz, 2H), 4.23 (d, J = 5.6 Hz, 2H), 1.85-1.75 (m, 2H), 1.65- 1.52 (m, 8H), 1.39-1.26 (m, 8H), 0.98 (t, J = 7.6 Hz, 6H), 0.95-0.84 (m, 6H).

(3) The compound U2 obtained in step 2 and 2-butyloctyl-1-amine are closed by the Buchwald-Hartwig reaction under the catalytic system composed of bisdibenzylideneacetone palladium and bisdiphenylphosphine ferrocene Compound U3;

For details, refer to the synthesis procedure of compound 3a (yield 36%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of compound U3:, δ7.18(d,J=5.6Hz,1H), 7.10(d,J=5.6Hz,1H), 7.06(d,J=5.2Hz ,1H),7.03(d,J=5.2Hz,1H),4.58-4.40(m,8H),2.08-1.94(m,4H),1.62-0.74(m,

72H).

(4) Compound U4 is obtained from compound U3 through Vilsmeier-Haack reaction;

For details, refer to the synthetic procedure of compound 4a (0.78 g, yield 85%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of compound U4: δ 9.94 (s, 1H), 9.89 (s, 1H), 7.71 (s, 1H), 7.64 (s, 1H), 4.56-4.52 (m ,8H),2.06-1.97(m,4H),1.60-1.12(m,54H),1.01(t,J=7.2Hz,6H),0.91(t,J=7.2Hz,6H),0.76(t, J=7.2Hz, 6H).

(5) Compound U4 and 5,6-difluoro-3-(dicyanomethylene)indigo are reacted by Knoevenagel to obtain acceptor material M41:

For details, refer to the synthesis steps of the acceptor material M3 (yield 88%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of the acceptor material M41: δ8.97(s,1H), 8.76(s,1H), 8.68(dd,J=6.8Hz,1H), 8.43(dd,J =6.8Hz, 1H), 7.91 (m, 1H), 7.73-7.70 (m, 2H), 7.68-7.65 (m, 2H), 4.69-4.57 (m, 8H), 2.06 (m, 4H), 1.80- 1.03 (m, 60H), 0.84-0.76 (m, 12H). High resolution mass spectrum, calculated: C ₈₄ H ₉₂ F ₄ N ₆ O ₅ S ₃ , 1436.6227; experimental value: 1436.6203. Elemental analysis (%), calculation: C ₈₄ H ₉₂ F ₄ N ₆ O ₅ S ₃ : C, 70.17; H, 6.45; N, 5.84; experimental value: C, 70.02; H, 6.34; N, 5.68.

Example 16: In formula II, R ₁ is 2-ethylhexyloxy, R ₂ is 2-butyloctyl, X ₁ , X ₂ , X ₃ , and X ₄ are all S atoms, and A is

When the acceptor material M51 was synthesized.

(1) 4,8-bis(2-ethylhexyloxy)benzodithienothiophene is reacted in liquid bromine to obtain the tetrabromo compound 1d;

In a 100 mL round bottom flask, F0 (5.59 g, 10 mmol) and 30 mL of dry chloroform were added, and liquid bromine (9.60 g, 60 mmol) was slowly added at 0°C. After the addition, the reaction solution was reacted at 60°C for 24 hours. After cooling to room temperature, the _{reaction was quenched by adding aqueous NaHSO 3} solution, extracted with dichloromethane, and the solvent was spin-dried to obtain a crude product, which was separated and purified by silica gel column chromatography to obtain a pale yellow solid F1 (5.66 g, yield 65%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of compound F1: δ 4.26 (d, J = 6.4 Hz, 4H), 2.01 (m, 2H), 1.35-1.69 (m, 16H), 1.07 (t, J = 7.2 Hz, 6H), 0.98 (t, J = 7.2 Hz, 6H).

(2) Tetrabromo compound F1 and (3-bromo-2-thiophene) zinc chloride are coupled by Negishi under the catalysis of [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride The reaction obtains compound H1;

Specific reference is made to the synthesis procedure of compound 2a (yield 75%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of compound H1: δ 7.58 (d, J = 5.6 Hz, 2H), 7.20 (d, J = 5.6 Hz, 2H), 4.26 (d, J = 6.4 Hz, 4H), 2.01 (m, 2H), 1.35-1.69 (m, 16H), 1.07 (t, J = 7.2 Hz, 6H), 0.98 (t, J = 7.2 Hz, 6H).

(3) The compound H1 obtained in step 2 and 2-butyloctyl-1-amine are closed by the Buchwald-Hartwig reaction under the catalytic system composed of bisdibenzylideneacetone palladium and bisdiphenylphosphine ferrocene Compound I1;

Specific reference is made to the synthesis procedure of compound 3a (yield 25%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of compound I1: δ 7.52 (d, J = 5.6 Hz, 2H), 7.15 (d, J = 5.6 Hz, 2H), 4.50-4.44 (m, 8H), 2.06-1.94 (m, 4H), 1.62-0.98 (m, 72H).

(4) Compound J1 is obtained from compound I1 through Vilsmeier-Haack reaction;

For details, refer to the synthetic procedure of compound 4a (0.78 g, yield 83%). ¹ H NMR (400MHz, CDCl ₃ , ppm) of compound J1: δ9.90 (s, 2H), 7.62 (s, 2H), 4.52-4.44 (m, 8H), 2.06-1.94 (m, 4H), 1.62 -0.96(m,72H).

(4) Compound J1 and 5,6-difluoro-3-(dicyanomethylene)indigo are reacted by Knoevenagel to obtain acceptor material M51:

For details, refer to the synthesis procedure of acceptor material M3 (0.20 g, yield 76%). ¹ H NMR(CDCl ₃ ,400MHz,ppm):δ8.99(s,2H),8.56(dd,J=6.4Hz,2H),7.91(s,2H),7.76(t,J=7.6Hz,2H ), 4.78 (t, J = 6.8 Hz, 4H), 4.06 (m, 4H), 2.06-1.94 (m, 4H), 1.62-0.96 (m, 72H). High resolution mass spectrum, calculated: C ₈₈ H ₉₂ F ₄ N ₆ O ₄ S ₆ , 1564.5440; experimental value: 1564.5403. Elemental analysis (%), calculation: C ₈₈ H ₉₂ F ₄ N ₆ O ₄ S ₆ : C, 67.49; H, 5.92; N, 5.37; experimental value: C, 67.70; H, 6.01; N, 5.41.

In the foregoing embodiments of the present application, the reactants/groups/synthesis conditions that are not specifically described are the same as those in the referenced embodiments.

Example 17: The nitrogen bridge trapezoidal fused ring acceptor material obtained in the above Example 1 was used to prepare a solar cell and test it.

The solar cell device adopts an upright device structure:

Glass substrate/ITO/PEDOT:PSS/active layer/PDIN/aluminum. Among them, the ITO layer is attached to the glass substrate, and then the ITO and the glass substrate are collectively referred to as ITO glass. The ITO glass is washed with detergent, water, acetone, and isopropanol under ultrasound for 30 minutes each. It was then dried in an oven at 90°C overnight. After the ITO glass was treated with UV ozone for 15 minutes, spin-coated PEDOT:PSS on the ITO layer, heated in an oven at 140°C for 15 minutes, and then quickly transferred to the glove box for later use. The polymer donor PM6 (purchased from Shuolun Organic Photoelectric Technology (Beijing) Co., Ltd.) and the non-fullerene acceptor material M3 (PM6:M3) obtained in Example 1 were dissolved in chloroform at a weight ratio of 1:1, and added 0.5% by volume 1-chloronaphthalene as an additive, the total concentration of the solution is 16mg/mL, the solution is stirred at 50℃ for 4 hours, and then the solution is spin-coated on the PEDOT:PSS film as the active layer, the thickness is about 150nm . In order to improve the efficiency of electron injection, a methanol solution of PDIN (1.5 mg/mL containing acetic acid with a mass concentration of 0.2%) was spin-coated on the active layer. Finally, the negative electrode of the battery is completed by thermal evaporation of 100nm aluminum electrode under the condition of a ^{vacuum degree of about 5×10 -5 Pa.} The area of the device is 4mm ² .

The structure of PM6 is as follows:

Example 18

Same as embodiment 17, the only difference is that the active layers are PBDB-T and M2;

The structure of PBDB-T is as follows:

Example 19

Same as Example 17, except that the active layer is PM6:M1.

Example 20

Same as Example 17, except that the active layer is PBDB-T: M4.

Example 21

Same as Example 17, except that the active layer is PM6:M5.

Example 22

Same as Example 17, except that the active layer is PBDB-T: M6.

Example 23

Same as Example 17, except that the active layer is PM6:M31.

Example 24

Same as Example 17, except that the active layer is PM6:M32.

Example 25

Same as Example 17, except that the active layer is PM6:M34.

Example 26

Same as Example 17, except that the active layer is PM6:M35.

Example 27

Same as Example 17, except that the active layer is PM6:M36.

Example 28

Same as Example 17, except that the active layer is PM6:M37.

Example 29

Same as Example 17, except that the active layer is PM6:M8.

Example 30

Same as Example 17, except that the active layer is PM6:M40.

Example 31

Same as Example 17, except that the active layer is PM6:M41.

Example 32

Same as Example 17, except that the active layer is PM6:M51.

Perform performance tests on the devices obtained in Examples 17 to 32:

^{The test of the device is measured under the light of AM 1.5G (100mW/cm 2} ) simulated by Oriel sol3A (Newport) solar simulator using Keithley 2400 digital source meter tester.

The parameters of the solar cell devices obtained in Examples 17 to 32 are summarized in Table 1, and the corresponding current-voltage curves are shown in Figs. 14-15.

Table 1. Parameters of solar cell devices prepared based on the acceptor material

Active layer	V oc (V)	J sc (mA cm -2 )	FF(%)	PCE(%)
PM6: M3	0.93	22.42	74.05	15.44
PBDB-T:M2	0.90	17.62	55.48	8.80
PM6: M1	0.90	11.74	62.93	6.66
PBDB-T:M4	0.90	19.68	55.05	9.77
PM6: M5	0.88	22.34	64.97	12.77
PBDB-T:M6	0.93	18.15	53.34	9.01
PM6: M31	0.92	19.70	64.50	11.69
PM6: M32	0.96	11.34	51.96	5.67
PM6: M34	0.91	23.29	71.01	15.04
PM6: M35	0.86	22.84	70.38	13.82
PM6: M36	0.90	23.67	64.10	13.61
PM6: M37	0.91	23.37	64.38	13.65
PM6: M40	0.90	20.01	70.10	12.62
PM6: M41	0.85	21.10	68.80	12.33
PM6: M51	0.84	24.37	69.60	14.24

In Example 33, the receptor materials provided in Examples 1-16 were tested for molecular aggregation characteristics, molecular packing orientation characteristics, and carrier migration performance.

The typical representatives are M32 and M3, and the performance of the receptor material provided in other embodiments is similar to that of M3.

The test methods include: using the field emission transmission electron microscope of the American FEI company (TECNAI G2 F20) to test the acceptor material M3 and the donor material PM6 mixed film (denoted as M3: PM6), and the mixed film of M32 and PM6 (denoted as M32: PM6) Observe the aggregate morphology. The grazing incidence X-ray wide-angle scattering patterns of pure acceptor materials M3 and M32 were tested by synchrotron radiation through a light source to investigate the molecular stacking orientation. In addition, a semiconductor analyzer (Agilent 4155C) and the space charge limitation method were used to test the electron and hole mobility of the mixed film of the acceptor material M3 and the donor material PM6, and the mixed film of M32 and PM6. Wherein, the weight ratio of the donor material to the acceptor material in the mixed film is 1:1, and the method of preparing the film is the same as that used in Example 17.

The transmission electron microscope topography, X-ray wide-angle scattering diagram and voltage-current curve in Example 33 are shown in Figs. 17-20, and the mobility test results are summarized in Table 2.

Figure 17a) is a transmission electron microscope image of M32:PM6, and Figure 17b) is a transmission electron microscope image of M32:PM6. It can be seen that the M32:PM6 mixed film has an obvious large-scale aggregation phase. The phase separation size of the M3:PM6 hybrid membrane is smaller and more uniform, which is conducive to charge separation and transfer;

Figure 18a) is the grazing incidence X-ray wide-angle scattering map of the acceptor material M3, Figure 18b) is the grazing incidence X-ray wide-angle scattering map of the acceptor material M32, Figure 18c is a schematic diagram of the structure of the acceptor material M3, and Figure 18d is the receptor Schematic diagram of the structure of material M32. It can be seen that because the side chain steric hindrance of the acceptor material M3 is greater than that of M32, the acceptor material M3 is more inclined to "face-on" accumulation mode, and M32 is inclined to "side-up". "Upward" ("edge-on") stacking method. In the application of photovoltaic devices, the "face-up" stacking method is conducive to efficient carrier transmission and thus improves the photoelectric conversion efficiency, so the efficiency of solar cells based on M3 is better.

Table 2. Carrier mobility data based on the mixed membrane PM6:M3 and PM6:M32

The above are only a few embodiments of the application, and do not limit the application in any form. Although the application is disclosed as above with preferred embodiments, it is not intended to limit the application. Anyone familiar with the profession, Without departing from the scope of the technical solution of the present application, making some changes or modifications using the technical content disclosed above is equivalent to an equivalent implementation case and falls within the scope of the technical solution.

Claims (15)

1. A nitrogen-containing trapezoidal fused ring acceptor material, characterized in that the nitrogen-containing trapezoidal fused ring acceptor material has at least one of the structures shown in formula I and formula II:

   

   in:

   X ₁ , X ₂ , X ₃ , and X _{4 are} independently selected from O, S or Se;

   R ₁ and R _{2 are} independently selected from the group consisting of C ₃ ～C ₃₀ branched alkoxy groups, C ₃ ～C ₃₀ branched fluorinated alkoxy groups, C ₃ ～C ₃₀ branched alkylthio groups, C ₃ ～C ₃₀ containing branched fluorinated alkylthio group, C ₃ ～C ₃₀ containing branched chain alkyl group, C ₃ ～C ₃₀ containing branched chain fluorinated alkyl group, C ₁ ～C ₂₈ straight chain alkyl group Oxy, C ₁ to C ₂₈ linear fluorinated alkoxy, C ₁ to C ₂₈ linear alkylthio, C ₁ to C ₂₈ linear fluorinated alkylthio, C ₁ to C ₂₈ straight Alkyl group, C ₁ ～C ₂₈ linear fluorinated alkyl group, C ₁ ～C ₂₀ alkyl aryl group, C ₁ ～C ₂₀ fluorinated alkyl aryl group, C ₁ ～C ₂₀ alkoxy group Aromatic groups, C ₁ ～C ₂₀ fluorinated alkoxy aryl groups, C ₁ ～C ₂₀ alkylthio aryl groups, C ₁ ～C ₂₀ fluorinated alkylthio aryl groups, C ₁ ～C _{20 aromatic groups} Any one of the fluorinated aromatic groups of C ₁ ～C _20;

   Ar ₁ and Ar _{2 are} independently selected from any one of groups containing 1 to 5 thiophene rings;

   A ₁ and A _{2 are} independently selected from any one of the groups of the chemical formulas shown in formulas III-1 to III-17:

   

   _{Wherein, R 51, R 52, R} 53, R 54, R 61, R 62 are independently selected from hydrogen, halo, cyano, C ₁ ~ C ₂₀ alkyl group is, C ₁ ~ C ₂₀ alkoxy group, and For any one of C ₁ to C ₂₈ alkylthio groups and C ₁ to C ₂₀ ester groups, the dotted line is the double bond connection position.
2. The acceptor material containing nitrogen hetero trapezoidal fused ring according to claim 1, characterized in that:

   R ₁ and R _{2 are} independently selected from C3～C30 branched alkoxy groups, C3～C30 branched fluorinated alkoxy groups, C3～C30 branched alkylthio groups, and C3～C30 branched alkoxy groups. Any one of a chain fluorinated alkylthio group, a C3-C30 branched alkyl group, a C3-C30 branched fluorinated alkyl group, and a C _{1 -20 alkyl aryl group;}

   Ar ₁ , Ar _{2 are} independently selected from the formula

   

   Any one of the structures shown;

   Wherein, R ₇ and R _{8 are} independently selected from hydrogen atoms, C ₁ ～C ₂₀ alkyl groups, C ₁ ～C ₂₀ alkoxy groups, C ₁ ～C ₂₀ alkylthio groups, C ₁ ～C ₂₀ esters For any of the groups, the dotted line is the connection position of the group.

   A ₁ and A _{2 are} independently selected from any one of the groups of the chemical formulas represented by formulas III-1 to III-17.
3. The method for preparing a nitrogen-containing heterotrapezoidal fused ring acceptor material with the structure of formula I according to claim 1 or 2, characterized in that it comprises at least the following steps:

   (1) Compound C is obtained by catalytic coupling reaction of compound A and compound B:

   

   Wherein, Ar' is selected from at least one of _{Ar 1} and Ar _2;

   (2) The compound C obtained in step (1) and the alkylamine R ₂ NH ₂ are subjected to catalytic debromination ring closure reaction to obtain compound D:

   

   (3) The compound D obtained in step (2) is subjected to a formylation reaction to obtain compound E:

   

   (4) The compound E obtained in step (3) and the A group donor are subjected to a condensation reaction under alkaline conditions to obtain a structure compound as shown in formula I, and the A group donor provides A ₁ group and/ Or A ₂ group compound.
4. The preparation method according to claim 3, characterized in that:

   The solvent for catalyzing the coupling reaction in step (1) is selected from at least one of diethyl ether, tetrahydrofuran or n-hexane;

   The catalyst for catalyzing the coupling reaction in step (1) is [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride, and the added amount of the catalyst is the molar amount of the compound A 1%～10% of

   The molar ratio of the compound A to the compound B in step (1) is 1:2.2-4.0;

   The reaction temperature of the catalytic coupling reaction in step (1) is 30-50°C, and the reaction time is 12-48 hours.
5. The preparation method according to claim 3, characterized in that:

   The solvent for catalyzing the debromination ring-closure reaction in step (2) is selected from at least one of toluene, dioxane and benzene;

   In step (2), the catalyst for catalyzing the debromination ring-closure reaction is bis-dibenzylideneacetone palladium and bis-diphenylphosphine ferrocene;

   The molar ratio of bisdibenzylidene acetone palladium and bisdiphenylphosphine ferrocene in step (2) is 1:3.5-4.5, and the added amount of bisdibenzylidene acetone palladium is obtained in step (1) 0.9% to 10% of the molar amount of compound C;

   In step (2), the deprotonation reagent that catalyzes the debrominated ring-closure reaction is sodium tert-butoxide;

   In step (2), the molar ratio of compound C, sodium tert-butoxide, and alkylamine R ₂ NH ₂ is 1:10-20:2-8;

   In step (2), the reaction temperature of the catalytic debromination ring-closure reaction is 60-110°C, and the reaction time is 3-12 hours.
6. The preparation method according to claim 3, characterized in that:

   The solvent for the formylation reaction in step (3) is selected from at least one of 1,2-dichloroethane, dichloromethane, and chloroform;

   The formylation reagent for the formylation reaction in step (3) is N,N-dimethylformamide and phosphorus oxychloride;

   The molar ratio of compound D, phosphorus oxychloride, and N,N-dimethylformamide in step (3) is 1:15-20:15-20;

   The reaction temperature of the formylation reaction in step (3) is 60-85°C, and the reaction time is 12-36 hours.
7. The preparation method according to claim 3, characterized in that: the solvent for the condensation reaction in step (4) is selected from at least one of chloroform, chlorobenzene, and 1,2-dichloroethane;

   The acid binding agent for the condensation reaction in step (4) is pyridine;

   The molar ratio of the compound E to the A group donor in step (4) is 1:5-12;

   The reaction temperature of the condensation reaction in step (4) is 60-70°C, and the reaction time is 8-24 hours;

   Step (4) said A group donor is selected from 5,6-difluoro-3-(dicyanomethylene)indigo, 6-fluoro-3-(dicyanomethylene)indigo, At least one of 5,6-dichloro-3-(dicyanomethylene)indigo and 3-(dicyanomethylene)indigo.
8. The method for preparing an acceptor material with a nitrogen-containing hetero trapezoidal fused ring having a structure of formula II according to claim 1 or 2, characterized in that it comprises at least the following steps:

   (1) Compound H is obtained by catalytic coupling reaction of compound F and compound G:

   

   Wherein, Ar" is selected from at least one of _{Ar 1} and Ar _2;

   (2) The compound H obtained in step (1) and the alkylamine R ₂ NH ₂ are subjected to catalytic debromination ring closure reaction to obtain compound I:

   

   

   (3) The compound I obtained in step (2) is subjected to a formylation reaction to obtain compound J:

   

   (4) The compound J and A group donors obtained in step (3) are subjected to condensation reaction under alkaline conditions to obtain a structure compound as shown in formula II, and the A group donor provides A ₁ group and/ Or A ₂ group compound.
9. The preparation method according to claim 8, characterized in that:

   The solvent for catalyzing the coupling reaction in step (1) is selected from at least one of diethyl ether, tetrahydrofuran, and n-hexane;

   The catalyst for catalyzing the coupling reaction in step (1) is [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride, and the added amount of the catalyst is the molar amount of the compound F 1%～10% of

   The molar ratio of the compound F to the compound G in step (1) is 1:2.2-4;

   The reaction temperature of the catalytic coupling reaction in step (1) is 30-50°C, and the reaction time is 12-48 hours.
10. The preparation method according to claim 8, characterized in that:

    The solvent for catalyzing the debromination ring-closure reaction in step (2) is toluene, dioxane or benzene;

    In step (2), the catalyst for catalyzing the debromination ring-closure reaction is bis-dibenzylideneacetone palladium and bis-diphenylphosphine ferrocene;

    In step (2), the molar ratio of bisdibenzylidene acetone palladium and bisdiphenylphosphine ferrocene is 1:3.5-4.5, and the added amount of bisdibenzylidene acetone palladium is obtained in step (1) 0.9% to 10% of the molar amount of compound H;

    The reagent for catalyzing the debrominated ring-closure reaction in step (2) is sodium tert-butoxide;

    In step (2), the molar ratio of compound H, sodium tert-butoxide, and alkylamine R ₂ NH ₂ is 1:10-20:2-8;

    In step (2), the reaction temperature of the catalytic debromination ring-closure reaction is 60-110°C, and the reaction time is 3-12 hours.
11. The preparation method according to claim 8, characterized in that:

    The solvent for the formylation reaction in step (3) is selected from at least one of 1,2-dichloroethane, chloroform, and dichloromethane;

    The formylation reagent for the formylation reaction in step (3) is N,N-dimethylformamide and phosphorus oxychloride;

    The molar ratio of compound I, phosphorus oxychloride, and N,N-dimethylformamide in step (3) is 1:15-20:15-20;

    The reaction temperature of the formylation reaction in step (3) is 60-85°C, and the reaction time is 12-36 hours.
12. The preparation method according to claim 8, characterized in that:

    The solvent for the condensation reaction in step (4) is selected from at least one of chloroform, chlorobenzene, and 1,2-dichloroethane;

    The acid binding agent for the condensation reaction in step (4) is pyridine;

    In step (4), the molar ratio of the compound J to the A group donor is 1:5-12;

    The reaction temperature of the condensation reaction in step (4) is 60-70°C, and the reaction time is 8-24 hours;

    Step (4) said A group donor is selected from 5,6-difluoro-3-(dicyanomethylene)indigo, 6-fluoro-3-(dicyanomethylene)indigo, At least one of 5,6-dichloro-3-(dicyanomethylene)indigo and 3-(dicyanomethylene)indigo.
13. A semiconductor material, characterized in that it contains at least one of the acceptor material according to claim 1 or 2 and the acceptor material prepared by the method according to any one of claims 3 to 12.
14. A solar cell device characterized by containing at least one of the acceptor material according to claim 1 or 2 and the acceptor material prepared according to any one of claims 3 to 12.
15. The solar cell device according to claim 14, characterized by comprising an anode, an anode modified layer, a photoactive layer, a cathode modified layer, and a cathode, the photoactive layer comprising the nitrogen-containing hetero trapezoidal fused ring acceptor material With the electron donor material, the mass ratio of the nitrogen-containing hetero trapezoidal fused ring acceptor material to the electron donor material is 1:1 to 1.5.

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