Cyanoindeketene enol ethers, methods for their preparation and use in organic photovoltaic materials

Abstract

This invention discloses a cyanoindanone enol ether, its preparation method, and its application in organic photovoltaic materials. The cyanoindanone enol ether comprises at least one of the following structural formulas: R1 is selected from alkyl, aromatic ring, alkyl-substituted or halogen-substituted aromatic ring; R2-R5 are selected from hydrogen, alkyl, halogen, aromatic ring, alkyl-substituted or halogen-substituted aromatic ring. This invention also provides a method for preparing an organic photovoltaic acceptor material, comprising: performing a Knoevenagel condensation reaction on a cyanoindanone enol ether, an aromatic aldehyde, a protic acid, and a condensation reaction solvent to obtain the organic photovoltaic acceptor material. The cyanoindanone enol ether prepared by this invention exhibits excellent solubility, and the isomers show significant differences in retention time in column chromatography, enabling effective separation and purification of the isomers. This provides an effective route for isomer separation, facilitating the synthesis of high-purity organic photovoltaic acceptor materials, and ultimately, the preparation of high-efficiency organic photovoltaic devices.

Description

Technical Field

[0001] This invention relates to a cyanoindanone enol ether, specifically to a cyanoindanone enol ether and its preparation method, as well as its application in organic photovoltaic materials, belonging to the field of organic photovoltaic technology. Background Technology

[0002] Organic solar cells possess advantages such as solution-processability, flexibility, lightweight, easily tunable spectrum, and large-area fabrication, demonstrating immense application potential in building-integrated photovoltaics (BIPV) and flexible wearable devices. In recent years, benefiting from the design of high-performance donor and acceptor materials, excellent morphology control techniques, and advanced device fabrication processes, the power conversion efficiency (PCE) of organic solar cells has rapidly surpassed 19%, essentially meeting market demands. Looking back at the rapid development of organic solar cells since 2015, each breakthrough has been closely related to innovations in non-fullerene acceptors, with representative molecules including ITIC, IDIC, IT-4F, and Y6.

[0003] In non-fullerene acceptor molecules, the terminal groups, acting as electron acceptor units, are crucial for regulating molecular absorption, energy levels, and stacking. Terminal-dominated molecular stacking forms a stable three-dimensional network structure, enhancing the material's electron transport capability and making it more isotropic like a fullerene, thus facilitating electron transport to and reception by the electrode. Currently, the terminal groups used in acceptor materials for high-efficiency organic photovoltaic systems are cyanoindanone (IC) and its diffractions, due to their strong electron affinity, which enhances the intramolecular charge transfer (ICT) effect of the acceptor, lowers the energy level, and achieves efficient matching with the donor. Halogenation modification of IC terminal groups (fluorination, chlorination, bromination) can further increase their electron-withdrawing ability. Furthermore, the halogen atoms, acting as intermolecular interaction sites on the terminal groups, can significantly improve the compactness and orderliness of molecular stacking, thereby optimizing the crystalline behavior and mixed film morphology of the molecules. This contributes to achieving high current and fill factor in the device. For example, high-efficiency fused-ring small molecule acceptors (Y6, L8-BO, BTP-eC9) all employ halogenated IC terminal groups. Most cyanoindanones with functional groups are obtained by cyanohydrination of the corresponding indanedione. Because the reactivity of the two carbonyl groups is similar, when the molecule is asymmetric, two isomers, inner and outer, are easily generated. Since cyanoindanone isomers have similar properties, high polarity, and poor solubility, they are difficult to separate. Currently, cyanoindanone isomers are purified by multiple recrystallizations in different solvents, a cumbersome process with poor separation capabilities, resulting in high material costs. A simple and efficient separation method is urgently needed to reduce purification costs. Furthermore, to meet the requirements of traditional Knoevenagel condensation reactions, cyanoindanone intermediates need to retain the structure containing the carbonyl group and the active methylene group. This type of structure has few modification sites, limiting the development of its derivatives. Summary of the Invention

[0004] The main objective of this invention is to provide a cyanoindanone enol ether and its preparation method, thereby overcoming the shortcomings of the prior art.

[0005] Another object of the present invention is to provide the application of the cyanoindanone enol ether.

[0006] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0007] This invention provides a cyanoindanone enol ether comprising any one or a combination of two or more of the following structural formulas:

[0008]

[0009] Wherein, R1 is selected from alkyl, aromatic ring, alkyl-substituted aromatic ring or halogen-substituted aromatic ring, and R2, R3, R4 and R5 are selected from hydrogen, alkyl, halogen, aromatic ring, alkyl-substituted aromatic ring or halogen-substituted aromatic ring.

[0010] This invention also provides a method for preparing cyanoindanone enol ethers, comprising:

[0011] A first mixed reaction system containing a cyanoindanone intermediate, an alcohol or phenol, a catalyst, and an organic solvent that may or may not be added is subjected to an enol etherification reaction to obtain a cyanoindanone enol ether.

[0012] The cyanoindanone intermediate includes any one or a combination of two or more of the following structural formulas:

[0013]

[0014] Among them, R2, R3, R4, and R5 are selected from hydrogen, alkyl, halogen, aromatic ring, alkyl-substituted aromatic ring, or halogen-substituted aromatic ring;

[0015] The alcohol has the structural formula R1-OH, where R1 is an alkyl group; the phenol has the structural formula R1-OH, where R1 is an aromatic ring, an alkyl-substituted aromatic ring, or a halogen-substituted aromatic ring.

[0016] This invention also provides the application of the cyanoindanone enol ether in the preparation of organic photovoltaic materials or organic photovoltaic devices.

[0017] This invention also provides a method for preparing an organic photovoltaic acceptor material, comprising:

[0018] An organic photovoltaic acceptor material is prepared by subjecting a second mixed reaction system containing the cyanoindanone enol ether, aromatic aldehyde, protic acid, and condensation reaction solvent to a Knoevenagel condensation reaction.

[0019] Accordingly, embodiments of the present invention also provide organic photovoltaic acceptor materials prepared by the aforementioned preparation method.

[0020] Furthermore, embodiments of the present invention also provide an organic photovoltaic device comprising the aforementioned organic photovoltaic acceptor material.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] This invention involves enol etherification of cyanoindanone intermediates. The resulting cyanoindanone enol ethers possess excellent solubility, and the isomers exhibit significant differences in retention time during column chromatography, enabling effective separation and purification of the isomers. This provides an effective pathway for isomer separation, facilitating the synthesis of high-purity organic photovoltaic acceptor materials and ultimately leading to the fabrication of high-efficiency organic photovoltaic devices. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0024] Figure 1 It is the enol ether ICE-Br(in) prepared in Example 1 of this invention. 1 H-NMR spectrum;

[0025] Figure 2 It is the enol ether ICE-Br(out) prepared in Example 1 of this invention. 1 H-NMR spectrum;

[0026] Figure 3 This refers to the enol ether ICE-F(in) prepared in Example 2 of this invention. 1 H-NMR spectrum;

[0027] Figure 4 It is the enol ether ICE-F(out) prepared in Example 2 of this invention. 1 H-NMR spectrum;

[0028] Figure 5 It is the enol ether ICE-Pro prepared in Example 3 of this invention. 1 H-NMR spectrum;

[0029] Figure 6 It is the enol ether ICE-BO prepared in Example 4 of this invention. 1 H-NMR spectrum;

[0030] Figure 7It is the condensation product IC-DMA obtained in Example 5 of this invention. 1 H-NMR spectrum;

[0031] Figure 8 This refers to the small molecule receptor L8BO-2Br(in) prepared in Example 6 of this invention. 1 H-NMR spectrum;

[0032] Figure 9 This is a current density-voltage correlation graph of the small molecule receptor L8BO-2Br(in) prepared in Example 6 of this invention;

[0033] Figure 10 It is the small molecule receptor L8BO-2Br(out) prepared in Example 7 of this invention. 1 H-NMR spectrum;

[0034] Figure 11 This is a current density-voltage correlation graph of the small molecule receptor L8BO-2Br(out) prepared in Example 7 of this invention. Detailed Implementation

[0035] In view of the problems of the prior art, the inventors of this invention, through long-term research and extensive practice, have proposed the technical solution of this invention, which mainly involves the enol etherification reaction of cyanoindanone intermediates to obtain cyanoindanone enol ethers, which is beneficial for the synthesis of high-purity organic photovoltaic acceptor materials, and thus for the preparation of high-efficiency organic photovoltaic devices.

[0036] The following will provide a further explanation of the technical solution, its implementation process, and its principles.

[0037] As one aspect of the technical solution of the present invention, a cyanoindanone enol ether includes any one or a combination of two or more of the following structural formulas:

[0038]

[0039] R1 is selected from alkyl, aromatic ring, alkyl-substituted aromatic ring or halogen-substituted aromatic ring, etc., and R2, R3, R4 and R5 are selected from hydrogen, alkyl, halogen, aromatic ring, alkyl-substituted aromatic ring or halogen-substituted aromatic ring, etc.

[0040] Furthermore, the alkyl group may be at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, 2-methoxyethyl, 2-ethyl-1-hexyl, 2-butyl-1-octyl, etc., but is not limited thereto.

[0041] Furthermore, the aforementioned halogen can be at least one of F, Cl, Br, I, etc., preferably at least one of F and Cl.

[0042] As another aspect of the technical solution of the present invention, a method for preparing a cyanoindanone enol ether includes:

[0043] A first mixed reaction system containing a cyanoindanone intermediate, an alcohol or phenol, a catalyst, and an organic solvent that may or may not be added is subjected to an enol etherification reaction to obtain a cyanoindanone enol ether.

[0044] The cyanoindanone intermediate includes any one or a combination of two or more of the following structural formulas:

[0045]

[0046]

[0047] Among them, R2, R3, R4, and R5 are selected from hydrogen, alkyl, halogen, aromatic ring, alkyl-substituted aromatic ring, or halogen-substituted aromatic ring, etc.

[0048] The alcohol has the structural formula R1-OH, where R1 is an alkyl group; the phenol has the structural formula R1-OH, where R1 is an aromatic ring, an alkyl-substituted aromatic ring, or a halogen-substituted aromatic ring, etc. Specifically, the types of alkyl groups and halogens are as defined above.

[0049] In some embodiments, the cyanoindanone intermediate is a mixture having two or more isomers. The isomers of the cyanoindanone intermediate also have corresponding enol ether isomers. Cyanoindanone enol ethers are a new type of structure, and the differences in isomers are more easily highlighted, making them easier to separate. This invention emphasizes two or more isomers to highlight the role of cyanoindanone enol ethers in isomer separation, and that the cyanoindanone intermediate is preferably a mixture of isomers in this invention. However, the cyanoindanone enol ether structure itself is not limited to structures with isomers.

[0050] In some embodiments, the cyanoindanone intermediate may specifically include 3-(dicyanomethylene)indophenone, 5(6)-fluoro-3-(dicyanomethylene)indophenone, 5(6)-chloro-3-(dicyanomethylene)indophenone, 5(6)-bromo-3-(dicyanomethylene)indophenone, 5(6)-methyl-3-(dicyanomethylene)indophenone, 1,2-(5-bromo-6-fluoro-3-oxo-2,3-dihydro-1H-indo-1-ylidene)malonitrile, 2-(6(7)-fluoro-3- Oxo-2,3-dihydro-1H-cyclopenta[b]naphth-1-yl)malonitrile, 2-(6(7)-chloro-3-oxo-2,3-dihydro-1H-cyclopenta[b]naphth-1-yl)malonitrile, 2-(6(7)-bromo-3-oxo-2,3-dihydro-1H-cyclopenta[b]naphth-1-yl)malonitrile or 2-(6-fluoro-7-bromo-3-oxo-2,3-dihydro-1H-cyclopenta[b]naphth-1-yl)malonitrile, etc., or combinations of two or more thereof, but not limited thereto.

[0051] In some embodiments, the alcohol may include any one or a combination of two or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, hexanol, ethylene glycol monomethyl ether, 2-ethyl-1-hexanol, 2-butyl-1-octanol, etc., but is not limited thereto.

[0052] In some embodiments, the phenol includes, but is not limited to, phenol.

[0053] In some embodiments, the organic solvent may include any one or a combination of two or more of toluene, xylene, benzene, chlorobenzene, dichlorobenzene, methylchlorobenzene, etc., but is not limited thereto.

[0054] Furthermore, while ensuring the solubility of the substrate and the fluidity of the reaction system, the organic solvent can also be the aforementioned alcohol or phenol, that is, no other organic solvent is added.

[0055] In some embodiments, the catalyst may include any one or a combination of two or more of p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, 1,5-naphthalenedisulfonic acid, 2,6-naphthalenedisulfonic acid, acetic acid, propionic acid, butyric acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., but is not limited thereto.

[0056] In some embodiments, the molar ratio of the cyanoindanone intermediate, alcohol and / or phenol, and catalyst is 1:(1.0 to 3.0):(0.1 to 1.0).

[0057] In some embodiments, the enol etherification reaction is carried out at a temperature of 100–200°C for a time of 6–24 hours.

[0058] In some more preferred embodiments, the preparation method specifically includes: dissolving a cyanoindanone intermediate, an alcohol or phenol, and a catalyst in an organic solvent, stirring at 100–200°C for 6–24 h to carry out an enol etherification reaction, and precipitating the product with methanol.

[0059] In some more preferred embodiments, the preparation method further includes: after the enol etherification reaction is completed, isomers of the reaction product are separated by atmospheric pressure silica gel column chromatography and elution with a mixed solvent.

[0060] Furthermore, the silica gel used for the silica gel column chromatography purification is 200-300 or 300-400 mesh.

[0061] Furthermore, the mixed solvent used in the column chromatography purification may include at least two combinations of ethyl acetate, methanol, dichloromethane, chloroform, n-hexane, petroleum ether, etc., to ensure that the retention time difference between isomers is greater than 0.1.

[0062] Another aspect of the present invention provides cyanoindanone enol ethers prepared by the aforementioned preparation method.

[0063] Another aspect of the present invention provides the application of the aforementioned cyanoindanone enol ethers in the preparation of organic photovoltaic materials or organic photovoltaic devices.

[0064] Another aspect of the present invention provides a method for preparing an organic photovoltaic acceptor material, comprising:

[0065] The organic photovoltaic acceptor material is prepared by subjecting a second mixed reaction system containing the aforementioned cyanoindanone enol ether, aromatic aldehyde, protic acid and condensation reaction solvent to a Knoevenagel condensation reaction.

[0066] In some embodiments, the aromatic aldehyde may include 4-(dimethylamino)benzaldehyde, 4-(dibutylamino)benzaldehyde, benzaldehyde, 3,9-bis(2-butyloctyl)-12,13-bis(2-ethylhexyl)-12,12-dihydro-[1,2,5]thiadiazole[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-di Formaldehyde (L8-BO-CHO), 12,13-bis(2-ethylhexyl)-3,9-di(undecyl)-12,13-dihydro-[1,2,5]thiadiazo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-dicarboxaldehyde (Y6-CHO), or a combination of two or more of these, but not limited to these.

[0067] In some embodiments, the protic acid may include any one or a combination of two or more of trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, acetic acid, propionic acid, benzoic acid, sulfuric acid, hydrochloric acid, etc., but is not limited thereto.

[0068] In some embodiments, the condensation reaction solvent may include any one or a combination of two or more of toluene, xylene, chlorobenzene, dichlorobenzene, o-chlorotoluene, dichloromethane, chloroform, etc., but is not limited thereto.

[0069] In some embodiments, the molar ratio of the aromatic aldehyde, cyanoindanone enol ether, and protic acid is 1:(1.0-2.5):(0.2-1.0).

[0070] In some embodiments, the Knoevenagel condensation reaction is carried out at a temperature of 25–110°C for a time of 5–24 hours.

[0071] In some more preferred embodiments, the preparation method specifically includes: preparing small molecule acceptor materials by Knoevenagel condensation reaction of cyanoindanone enol ethers, wherein the condensation reaction is carried out by adding a protic acid to a solution of cyanoindanone enol ethers and aromatic aldehydes for catalysis, reacting at 25-110°C for 5-24 h, and precipitating the product with methanol.

[0072] Accordingly, another aspect of the present invention provides an organic photovoltaic acceptor material prepared by the aforementioned preparation method.

[0073] Furthermore, another aspect of the present invention provides an organic photovoltaic device comprising the aforementioned prepared organic photovoltaic acceptor material.

[0074] In summary, the cyanoindanone enol ethers provided by this invention broaden the derivative forms of cyanoindanone compounds. The excellent solubility and increased isomer differences of cyanoindanone enol ethers themselves enable the effective separation and purification of isomers. Moreover, the purification of cyanoindanone enol ether isomers provides conditions for the preparation of high-purity organic photovoltaic acceptor materials.

[0075] The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments and accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. It should be noted that the following embodiments are intended to facilitate the understanding of the present invention, and do not constitute any limitation thereof. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or according to the conditions recommended by the manufacturer. Unless otherwise specified, the experimental materials used in the embodiments below can be purchased from conventional biochemical reagent companies.

[0076] Example 1

[0077] The preparation method of cyanoindanone enol ethers in this embodiment includes the following steps:

[0078] Enol etherification reaction: 1.00 g (3.66 mmol) of 5(6)-bromo-3-(dicyanomethylene)indophenone (IC-Br) was dissolved in 10 mL of toluene. 0.17 g (3.66 mmol) of anhydrous ethanol was added to the solution, and 0.20 g (1.16 mmol) of p-toluenesulfonic acid was added with stirring at room temperature. The reaction was stirred at 100 °C for 18 h. After cooling to room temperature, methanol was used to precipitate the ether. The ether was filtered to obtain enol ether ICE-Br with two isomers in a yield of 98.9%.

[0079] Isomer separation of enol ethers: Dissolve 1.00 g of ICE-Br in 15 mL of dichloromethane, add 5.00 g of 200-300 mesh silica gel, dry by rotary evaporation, and then dry-load the solution onto a column. Elute with ethyl acetate: petroleum ether = 1:10 (v / v) to separate the two enol ether isomers ICE-Br(in) and ICE-Br(out).

[0080] The structure and corresponding proton nuclear magnetic resonance spectrum of the cyanoindanone enol ethers obtained in this embodiment are as follows: Figure 1 and Figure 2 As shown.

[0081] Example 2

[0082] The preparation method of cyanoindanone enol ethers in this embodiment includes the following steps:

[0083] Enol etherification reaction: 1.00 g (3.66 mmol) of 5(6)-fluoro-3-(dicyanomethylene)indophenone (IC-F) was dissolved in 16 mL of toluene. 0.51 g (10.98 mmol) of anhydrous ethanol was added to the solution, and 0.63 g (3.66 mmol) of p-toluenesulfonic acid was added with stirring at room temperature. The reaction was stirred at 110 °C for 24 h. After cooling to room temperature, methanol was used to precipitate the ether. The ether was filtered to obtain enol ether ICE-F with two isomers, with a yield of 97.2%.

[0084] Isomer separation of enol ethers: Dissolve 1.00 g of ICE-F in 14 mL of dichloromethane, add 5.00 g of 200-300 mesh silica gel, dry by rotary evaporation, and then dry-load the solution onto a column. Elute with ethyl acetate:petroleum ether = 1:15 (v / v) to separate the two enol ether isomers ICE-F(in) and ICE-F(out).

[0085] The structure and corresponding proton nuclear magnetic resonance spectrum of the cyanoindanone enol ethers obtained in this embodiment are as follows: Figure 3 and Figure 4 As shown.

[0086] Example 3

[0087] 1.00 g (5.04 mmol) of 3-(dicyanomethylene)indophenone (IC) was dissolved in 10 mL of xylene. 0.50 g (8.31 mmol) of n-propanol was added to the solution, followed by stirring at room temperature with 0.08 g (0.50 mmol) of benzenesulfonic acid. The reaction was carried out at 160 °C for 12 h with stirring. After cooling to room temperature, methanol was used to precipitate the solid. The solid was then dissolved in 15 mL of dichloromethane and 5.00 g of 200–300 mesh silica gel was added. After rotary evaporation and drying, the solid was loaded onto a column using a dry method. Eluent was obtained by dichloromethanol:petroleum ether = 1:2 (v / v). After rotary evaporation and drying, enol ether ICE-Pro was obtained with a yield of 87.5%.

[0088] The structure and corresponding proton nuclear magnetic resonance spectrum of the cyanoindanone enol ethers obtained in this embodiment are as follows: Figure 5 As shown.

[0089] Example 4

[0090] 1.00 g (5.04 mmol) of IC was dissolved in 2.50 g (13.41 mmol) of 2-butyl-n-octanol. 0.18 g (0.62 mmol) of 1,5-naphthalenedisulfonic acid was added with stirring at room temperature. The reaction was carried out at 200 °C for 6 h with stirring. After cooling to room temperature, methanol was used to precipitate the solid. The solid was then dissolved in 15 mL of dichloromethane, and 5.00 g of 200–300 mesh silica gel was added. After rotary evaporation to dryness, the solid was loaded onto a column using a dry method. Eluent was obtained using dichloromethanol:petroleum ether = 1:5 (v / v). After rotary evaporation to dryness, the enol ether ICE-BO was obtained in 86.1% yield.

[0091] The structure and corresponding proton nuclear magnetic resonance spectrum of the cyanoindanone enol ethers obtained in this embodiment are as follows: Figure 6 As shown.

[0092] The inventors of this case also conducted the same tests on other cyanoindanone intermediates as shown in formula (V) or formula (VI) using the methods of Examples 1-4, and the results were similar to those of Examples 1-4.

[0093] Example 5

[0094] The Knoevenagel condensation method for cyanoindanone enol ethers in this embodiment includes the following steps:

[0095] 0.10 g (0.28 mmol) of ICE-BO and 0.04 g (0.28 mmol) of 4-(dimethylamino)benzaldehyde were dissolved in 12 mL of toluene. 0.03 g (0.28 mmol) of methanesulfonic acid was added to the solution. The mixture was stirred at 25 °C for 24 h under nitrogen protection. After cooling to room temperature, methanol was used to precipitate the product. The product was purified by column chromatography after filtration, yielding IC-DMA in 90.0%.

[0096] The structure and corresponding proton nuclear magnetic resonance spectrum of the condensation product obtained in this embodiment are as follows: Figure 7 As shown.

[0097] Example 6

[0098] The preparation method of the organic photovoltaic acceptor material in this embodiment includes the following steps:

[0099] 0.10 g (0.10 mmol) of L8-BO-CHO (CAS No. 2758115-09-0) and 0.07 g (0.25 mmol) of ICE-Br(in) were dissolved in 3 mL of o-dichlorobenzene. 0.01 g (0.06 mmol) of p-toluenesulfonic acid was added to the solution. The mixture was stirred at 110 °C for 5 h under nitrogen protection. After cooling to room temperature, methanol was used to precipitate the product. The precipitate was then purified by column chromatography after filtration, yielding L8BO-2Br(in) in 92.2%.

[0100] The structure and corresponding proton nuclear magnetic resonance spectrum of the receptor material obtained in this embodiment are as follows: Figure 8 As shown.

[0101] When applied to organic photovoltaic devices and matched with the commercially available polymer donor PM6, a positively charged device was fabricated with an open-circuit voltage of 0.939V and a short-circuit current of 24.37mA. -2 The fill factor reached 75.92%, and the energy conversion efficiency reached 17.45%, as shown in the results. Figure 9 As shown.

[0102] Example 7

[0103] 0.10 g (0.10 mmol) of L8-BO-CHO and 0.05 g (0.17 mmol) of ICE-Br(out) were dissolved in 3 mL of chlorobenzene. 3.00 mg (0.02 mmol) of trifluoromethanesulfonic acid was added to the solution. The mixture was stirred at 60 °C for 12 h under nitrogen protection. After cooling to room temperature, methanol was used to precipitate the product. The product was purified by column chromatography after filtration, yielding L8BO-2Br(out) in 90.5%.

[0104] The structure and corresponding proton nuclear magnetic resonance spectrum of the receptor material obtained in this embodiment are as follows: Figure 10 As shown.

[0105] When applied to organic photovoltaic devices and matched with the commercially available polymer donor PM6, a positively charged device was fabricated with an open-circuit voltage of 0.925V and a short-circuit current of 24.64mA. -2 The fill factor reached 76.47%, and the energy conversion efficiency reached 17.42%, as shown in the results. Figure 11 As shown.

[0106] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0107] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A cyano-indenone enol ether characterized by, Includes any one or more of the following structural formulas: Wherein, R1 is selected from alkyl, aromatic ring, alkyl-substituted aromatic ring or halogen-substituted aromatic ring, and R2, R3, R4 and R5 are selected from hydrogen, alkyl, halogen, aromatic ring, alkyl-substituted aromatic ring or halogen-substituted aromatic ring.

2. The cyano indanone enol ether according to claim 1, characterized in that: The alkyl group includes at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, 2-methoxyethyl, 2-ethyl-1-hexyl, and 2-butyl-1-octyl; and / or the halogen includes at least one of F, Cl, Br, and I, preferably at least one of F and Cl.

3. A process for the preparation of a cyano indanone enol ether, characterized in that, include: A first mixed reaction system containing a cyanoindanone intermediate, an alcohol or phenol, a catalyst, and an organic solvent that may or may not be added is subjected to an enol etherification reaction to obtain a cyanoindanone enol ether. The cyanoindanone intermediate includes any one or a combination of two or more of the following structural formulas: Among them, R2, R3, R4, and R5 are selected from hydrogen, alkyl, halogen, aromatic ring, alkyl-substituted aromatic ring, or halogen-substituted aromatic ring; The alcohol has the structural formula R1-OH, where R1 is an alkyl group; the phenol has the structural formula R1-OH, where R1 is an aromatic ring, an alkyl-substituted aromatic ring, or a halogen-substituted aromatic ring.

4. The method of claim 3, wherein: The alkyl group includes at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, 2-methoxyethyl, 2-ethyl-1-hexyl, and 2-butyl-1-octyl; and / or the halogen includes at least one of F, Cl, Br, and I, preferably at least one of F and Cl; And / or, the cyanoindanone intermediates include 3-(dicyanomethylene)indophenone, 5(6)-fluoro-3-(dicyanomethylene)indophenone, 5(6)-chloro-3-(dicyanomethylene)indophenone, 5(6)-bromo-3-(dicyanomethylene)indophenone, 5(6)-methyl-3-(dicyanomethylene)indophenone, 1,2-(5-bromo-6-fluoro-3-oxo-2,3-dihydro-1H-indo-1-ylidene)malonitrile, 2-(6(7)-fluoro-3-oxo-1-ylidene)malonitrile, etc. 2-(6(7)-chloro-3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthyl)malonitrile, 2-(6(7)-bromo-3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthyl)malonitrile or any one or a combination of two or more of the following: And / or, the alcohol includes any one or a combination of two or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, hexanol, ethylene glycol monomethyl ether, 2-ethyl-1-hexanol, and 2-butyl-1-octanol. And / or, the phenol includes phenol; And / or, the organic solvent includes any one or a combination of two or more of toluene, xylene, benzene, chlorobenzene, dichlorobenzene, and methylchlorobenzene; And / or, the catalyst comprises any one or a combination of two or more of p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, 1,5-naphthalenedisulfonic acid, 2,6-naphthalenedisulfonic acid, acetic acid, propionic acid, butyric acid, benzoic acid, phthalic acid, isophthalic acid, and terephthalic acid. And / or, the molar ratio of the cyanoindanone intermediate, alcohol and / or phenol, and catalyst is 1:(1.0-3.0):(0.1-1.0); And / or, the enol etherification reaction is carried out at a temperature of 100–200°C for a time of 6–24 h; And / or, the preparation method further includes: after the enol etherification reaction is completed, separating the isomers of the reaction product by atmospheric pressure silica gel column chromatography and elution with a mixed solvent; preferably, the silica gel used for the silica gel column chromatography is 200-300 or 300-400 mesh; preferably, the mixed solvent includes at least two or more combinations of ethyl acetate, methanol, dichloromethane, trichloromethane, n-hexane, and petroleum ether.

5. A cyanoindanone enol ether prepared by any one of claims 3-4.

6. The use of the cyanoindanone enol ethers according to any one of claims 1-2 and 5 in the preparation of organic photovoltaic materials or organic photovoltaic devices.

7. A method for producing an organic photovoltaic acceptor material, characterized by, include: An organic photovoltaic acceptor material is prepared by subjecting a second mixed reaction system comprising any one of the cyanoindanone enol ethers, aromatic aldehydes, protic acids and condensation reaction solvents according to any one of claims 1-2 and 5 to a Knoevenagel condensation reaction.

8. The method of claim 7, wherein: The aromatic aldehydes include 4-(dimethylamino)benzaldehyde, 4-(dibutylamino)benzaldehyde, benzaldehyde, 3,9-bis(2-butyloctyl)-12,13-bis(2-ethylhexyl)-12,12-dihydro-[1,2,5]thiadiazole[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]in Any one or a combination of two or more of the following: indole-2,10-dicarboxaldehyde, 12,13-bis(2-ethylhexyl)-3,9-di(undecyl)-12,13-dihydro-[1,2,5]thiadiazo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-dicarboxaldehyde; And / or, the protic acid includes any one or more combinations of trifluoromethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, acetic acid, propionic acid, benzoic acid, sulfuric acid, and hydrochloric acid; And / or, the condensation reaction solvent includes any one or a combination of two or more of toluene, xylene, chlorobenzene, dichlorobenzene, o-chlorotoluene, dichloromethane, and chloroform; And / or, the molar ratio of the aromatic aldehyde, cyanoindanone enol ether to protic acid is 1:(1.0-2.5):(0.2-1.0); And / or, the temperature of the Knoevenagel condensation reaction is 25–110°C, and the time is 5–24 h.

9. An organic photovoltaic acceptor material prepared by the preparation method of claim 7 or 8.

10. An organic photovoltaic device, characterized in that, Includes the organic photovoltaic acceptor material as described in claim 9.

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