A fluoroboron-coordinated non-fullerene electron acceptor material, preparation method and application

Abstract

The application discloses a fluorine-boron coordination type non-fullerene electron acceptor material, a preparation method and application, relates to the technical field of organic photovoltaic devices, and takes fluorine-boron dipyrrin with strong light emission characteristics as a core structural unit of a molecular skeleton, performs conformation locking by introducing a fluorine-boron coordination bond into a non-fullerene acceptor skeleton, reasonably designs a coordination configuration of the molecule, locks the molecular skeleton into a highly coplanar conformation by using B-N coordination, significantly enhances the rigidity of the molecular skeleton, and reduces recombination energy of exciton dissociation; by using the high fluorescence quantum yield characteristics of the fluorine-boron dipyrrin core unit, in combination with rigid conformation locking, non-radiation recombination of photo-generated carriers is further inhibited, and non-radiation energy loss of the device is effectively reduced. The application realizes the synergistic improvement of high open-circuit voltage and efficient charge transport, and provides a new material design scheme for constructing an organic solar cell with extremely low energy loss and high efficiency.

Description

Technical Field

[0001] This invention relates to the field of organic photovoltaic device technology, and in particular to a fluorine-boron coordinated non-fullerene electron acceptor material, its preparation method, and its application. Background Technology

[0002] Organic solar cells (OSCs) have become a research hotspot in the field of novel photovoltaic technology due to their outstanding advantages such as low cost, tunability, lightweight, and the ability to be fabricated into flexible devices. In recent years, the rapid development of non-fullerene acceptor materials has driven the photoelectric conversion efficiency (PCE) of organic solar cells to exceed 20%, demonstrating enormous potential for commercial applications.

[0003] However, despite continuous improvements in device efficiency, the significant energy loss prevalent in organic solar cells remains a core bottleneck limiting further efficiency breakthroughs. Research indicates that energy loss primarily originates from non-radiative recombination, which directly limits the device's open-circuit voltage (Vo). oc The improvement of fluorescence quantum yield (PLQY) is crucial. Most current non-fullerene acceptor materials exhibit low PLQY and possess a degree of molecular backbone flexibility, leading to significant non-radiative energy loss due to the easy dissipation of excited-state energy through intramolecular vibrations and rotations. To address these shortcomings, researchers have introduced rigid fused-ring structures or non-covalent interactions to lock the molecular conformation, which enhances molecular coplanarity to some extent. However, most acceptor materials still lack strong luminescence properties, making it difficult to fundamentally suppress non-radiative recombination. Fluoroboron dipyrrole groups and their derivatives are widely used in fluorescent probes and dyes due to their excellent chemical stability, high extinction coefficient, and extremely high PLQY. Therefore, designing a novel non-fullerene acceptor material with a fluoroboron coordination structure, by introducing a strong luminescent fluoroboron dipyrrole group and combining it with coordination bond conformation locking technology, to improve the material's PLQY while simultaneously enhancing the rigidity of the molecular backbone and reducing non-radiative energy loss, has become a pressing technical challenge in this field. Summary of the Invention

[0004] To overcome the aforementioned problems in the prior art, this invention proposes a fluorine-boron coordinated non-fullerene electron acceptor material, its preparation method, and its application.

[0005] The technical solution adopted by this invention to solve its technical problem is: a fluorine-boron coordination type non-fullerene electron acceptor material, wherein the general structural formula of the acceptor material is one of the general structural formulas NFA-FB1 to NFA-FB5. ; Where R1 and R1' are C1~C 20 The alkyl group includes a straight-chain structure, a branched structure, and any combination of straight-chain and straight-chain structures; R2 and R2' are C1~C 20 The alkyl group includes a straight-chain structure, a branched structure, and any combination of straight-chain and straight-chain structures; A1 and A2 are electron-withdrawing groups.

[0006] The above-mentioned fluorine-boron coordination-type non-fullerene electron acceptor material, its preparation method, and its application, wherein the specific structural formulas of A1 and A2 are any one of the following structures: ; Where E represents O, S, and Se atoms; X represents F, Cl, Br, and I atoms; and X1 and X2 represent F, Cl, Br, and I atoms.

[0007] A method for preparing a fluorine-boron coordinated non-fullerene electron acceptor material, used to prepare NFA-FB1 acceptor material, is described below: ; Compound A was reduced with LiAlH4 to obtain compound B; Compound B was reacted with 2-pyridinecarboxaldehyde to give compound C; Compound C reacts with boron trifluoride diethyl ether under alkaline conditions to give compound D; Compound D reacts with a formylation reagent via a Vilsmeier-Haack reaction to yield compound E; Compound E and EG ketone were reacted via a Knoevenagel reaction to yield the non-fullerene acceptor material compound NFA-FB1.

[0008] A method for preparing a fluorine-boron coordinated non-fullerene electron acceptor material, used to prepare NFA-FB2 acceptor material, is described below: ; Compound A was reduced with LiAlH4 to obtain compound B; Compound B reacts with compound 1 to give compound F; Compound F reacts with boron trifluoride diethyl ether under alkaline conditions to give compound G; Compound G reacts with a formylation reagent via a Vilsmeier-Haack reaction to yield compound K; Compound K and EG ketone were reacted via a Knoevenagel reaction to yield the non-fullerene acceptor material compound NFA-FB2.

[0009] A method for preparing fluorine-boron coordinated non-fullerene electron acceptor materials, used to prepare NFA-FB3 acceptor materials, is described below: ; Compound A was reduced with LiAlH4 to obtain compound B; Compound B reacts with compound 2 to give compound L; Compound L reacts with boron trifluoride diethyl ether under alkaline conditions to give compound M; Compound M reacts with a formylation reagent via a Vilsmeier-Haack reaction to yield compound N; Compound N and EG ketone were reacted via a Knoevenagel reaction to yield the non-fullerene acceptor material compound NFA-FB3.

[0010] A method for preparing a fluorine-boron coordinated non-fullerene electron acceptor material, used to prepare NFA-FB4 acceptor material, is described below: ;

[0011] Compound A was reduced with LiAlH4 to obtain compound B; Compound B reacts with compound 2 to give compound L; Compound L reacts with boron trifluoride diethyl ether under alkaline conditions to give compound P; Compound P reacts with a formylation reagent via a Vilsmeier-Haack reaction to yield compound Q; Compound Q and EG ketone were reacted via a Knoevenagel reaction to yield the non-fullerene acceptor material compound NFA-FB4.

[0012] A method for preparing a fluorine-boron coordinated non-fullerene electron acceptor material, used to prepare NFA-FB5 acceptor material, is described below: ;

[0013] Compound A was reduced with LiAlH4 to obtain compound B; Compound B reacts with compound 3 to give compound R; Compound R reacts with boron trifluoride diethyl ether under alkaline conditions to give compound S; Compound S reacts with a formylation reagent via a Vilsmeier-Haack reaction to yield compound T; Compound T and EG ketone were reacted via a Knoevenagel reaction to yield the non-fullerene acceptor material compound NFA-FB5.

[0014] In the above preparation method, the EG ketone is any one of the following structures: ;

[0015] Where E represents O, S, and Se atoms; X represents F, Cl, Br, and I atoms; and X1 and X2 represent F, Cl, Br, and I atoms.

[0016] The application of a fluorine-boron coordinated non-fullerene electron acceptor material as an electron acceptor material in organic optoelectronic devices. The fluorine-boron coordinated non-fullerene electron acceptor material has the structural formula as described above, or is prepared by the above preparation method. The organic optoelectronic devices include organic solar cell devices, sensors, photodetectors, and electronic paper.

[0017] The beneficial effects of this invention are as follows: The objective of this invention is to provide a fluorine-boron coordinated non-fullerene acceptor material. By introducing the strongly luminescent fluorine-boron dipyrrole group into the molecular backbone and binding it with coordination bonds for conformational locking, the fluorescence quantum yield of the material is significantly improved, thereby greatly reducing the nonradiative energy loss of excitons. Through the rational design of the fluorine-boron coordination structure, the planarity and rigidity of the molecular backbone are enhanced, significantly improving the extinction coefficient of the material. Furthermore, by constructing a fluorine-boron coordination system based on the fluorine-boron dipyrrole core, this invention effectively suppresses intramolecular vibrations and significantly reduces nonradiative recombination.

[0018] This invention not only effectively solves the problem of severe voltage loss caused by large non-radiative energy loss and low fluorescence quantum yield in existing acceptor materials, but also provides a new solution for developing high-efficiency organic solar cells that combine high voltage and high current. Attached Figure Description

[0019] Figure 1 This is the proton NMR spectrum of compound 3 in Example S1 of the present invention; Figure 2 This is the proton NMR spectrum of compound 4 in Example S1 of the present invention; Figure 3 This is the proton NMR spectrum of compound 5 in Example S1 of the present invention; Figure 4 This is the proton NMR spectrum of compound L8-FB in Example S1 of the present invention; Figure 5 The JV curve of the solar energy device described by compound L8-FB in Example S1 of this invention; Figure 6 The EQE spectrum of the solar energy device described by compound L8-FB in Example S1 of this invention; Figure 7 The JV curve of the solar energy device described by compound L8-FB2 in Embodiment S2 of the present invention; Figure 8 The JV curve of the solar energy device described by compound L8-FB3 in Example S3 of this invention; Figure 9 The JV curve of the solar energy device described by compound L8-FB4 in Example S4 of this invention; Figure 10 The JV curve of the solar energy device described by compound L8-FB5 in Example S5 of this invention; Detailed Implementation

[0020] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0021] Example 1 The structural formula of the receptor material in this embodiment is:

[0022] The synthesis route is shown below:

[0023] The synthesis method was as follows: a. Under an argon atmosphere, compound 1 (0.2 g, 0.16 mmol) was dissolved in tetrahydrofuran (30 mL), and lithium aluminum hydride (0.13 g, 3.6 mmol) was added at 0 °C. The reaction was carried out overnight at 80 °C. After the reaction was completed, the mixture was quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to obtain a dark green oil. Under an argon atmosphere, the obtained oil was dissolved in toluene (20 mL) with compound 2 (2-Pyridinecarboxaldehyde) and P-toluenesulfonic acid, and the reaction was carried out at 110 °C for 8 h. After the reaction was completed, the mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to obtain a yellow oil compound 3. The proton NMR spectrum is shown below. Figure 1 As shown.

[0024] b. Under an argon atmosphere, compound 3 (0.2 g, 0.15 mmol), 1,8-diazabicycloundec-7-ene (DBU, 0.35 mmol), was dissolved in 20 mL of toluene. The mixture was heated under reflux for 10 minutes, followed by the addition of boron trifluoride diethyl ether (0.1 mL, 0.7 mmol), and refluxed for 4 hours. The mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to give an orange oil, compound 4. The 1H NMR spectrum is shown below. Figure 2 As shown.

[0025] c. Under an argon atmosphere, compound 4 (0.2 g, 0.15 mmol) was dissolved in 20 mL of tetrahydrofuran, and the temperature was lowered to -78 °C. Then, LDA (0.4 mL) was added to the solution, and the reaction was continued at -78 °C for 1 h. Then, DMF (1 mL) was added, and the reaction was continued for 3 h. After the reaction was complete, the mixture was poured into ice water and neutralized with sodium acetate. Extraction was performed with dichloromethane, drying over anhydrous magnesium sulfate, solvent removal under reduced pressure, and purification of the crude product by column chromatography to give orange oil 5. The 1H NMR spectrum is shown below. Figure 3 As shown.

[0026] d. Under an argon atmosphere, compound 5 (0.1 g, 0.072 mmol) and IC-2F (0.054 g, 0.234 mmol) were dissolved in chloroform, and 0.1 mL of pyridine was added. The mixture was heated to 60 °C and reacted overnight. After the reaction was complete, the solvent was removed under reduced pressure, and the crude product was purified by column chromatography to give a black solid compound L8-FB. The proton NMR spectrum is shown below. Figure 4 As shown.

[0027] Depend on Figure 5 It can be seen that the short-circuit current Jsc of the organic solar cell prepared by compound L8-FB is (20.1) mA·cm. 2 The open-circuit voltage Voc is (0.90)V, the fill factor FF is (65.67)%, and the power conversion efficiency PCE is (11.66)%.

[0028] Figure 6 The external quantum efficiency curve of the device is shown. In this embodiment, the synthesized compound L8-FB has complementary absorption with the polymer donor D18, which enables effective utilization of visible-near infrared light and obtains a high short-circuit current.

[0029] Example 2 The structural formula of the receptor material in this embodiment is:

[0030] The synthetic route is as follows:

[0031] The synthesis method was as follows: a. Under an argon atmosphere, compound 1 (0.2 g, 0.16 mmol) was dissolved in tetrahydrofuran (30 mL), and lithium aluminum hydride (0.13 g, 3.6 mmol) was added at 0 °C. The reaction was carried out overnight at 80 °C. After the reaction was completed, the mixture was quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to obtain a dark green oil. Under an argon atmosphere, the obtained oil and compound 2 were dissolved in EtOH:CH3COOH (1:1, 20 mL), and the reaction was carried out at 100 °C for 8 h. After the reaction was completed, the mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to obtain a yellow oil compound 3. MS (ESI) (M+, C 84 H 124 N5S4)Exact Mass: 1330.9.

[0032] b. Under an argon atmosphere, compound 3 (0.2 g, 0.15 mmol), 1,8-diazabicycloundec-7-ene (DBU, 0.35 mmol), was dissolved in 20 mL of toluene. The mixture was heated under reflux for 10 minutes, followed by the addition of boron trifluoride diethyl ether (0.1 mL, 0.7 mmol), and refluxed for 4 hours. The mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to give an orange oil, 4. MS (ESI) (M+, C 84 H 124 BF2N5S4)Exact Mass: 1381.0.

[0033] c. Under an argon atmosphere, compound 4 (0.2 g, 0.15 mmol) was dissolved in 20 mL of tetrahydrofuran, and the temperature was lowered to -78 °C. Then, LDA (0.4 mL) was added to the solution, and the reaction was continued at -78 °C for 1 h. DMF (1 mL) was then added, and the reaction was continued for 3 h. After the reaction was complete, the mixture was poured into ice water and neutralized with sodium acetate. Extraction was performed with dichloromethane, drying to anhydrous magnesium sulfate, solvent removal under reduced pressure, and purification of the crude product by column chromatography to give an orange oil, compound 5. MS (ESI) (M+, C 86 H 124 BF2N5O2S4)Exact Mass: 1437.0.

[0034] d. Under an argon atmosphere, compound 5 (0.1 g, 0.072 mmol) and IC-2F (0.054 g, 0.234 mmol) were dissolved in chloroform, and 0.1 mL of pyridine was added. The mixture was heated to 60 °C and reacted overnight. After the reaction was complete, the solvent was removed under reduced pressure, and the crude product was purified by column chromatography to give the black solid compound L8-FB2. MS (ESI) (M+, C110 H 128 BF6N9O2S4)ExactMass: 1861.3.

[0035] Depend on Figure 7 It can be seen that the short-circuit current Jsc of the organic solar cell prepared by compound L8-FB2 is (18.49) mA·cm. 2 The open-circuit voltage Voc is (0.92)V, the fill factor FF is (66.85)%, and the power conversion efficiency PCE is (11.37)%.

[0036] Example 3 The structural formula of the receptor material in this embodiment is:

[0037] The synthetic route is as follows:

[0038] The synthesis method was as follows: a. Under an argon atmosphere, compound 1 (0.2 g, 0.16 mmol) was dissolved in tetrahydrofuran (30 mL), and lithium aluminum hydride (0.13 g, 3.6 mmol) was added at 0 °C. The reaction was carried out overnight at 80 °C. After the reaction was completed, the mixture was quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to obtain a dark green oil. Under an argon atmosphere, the obtained oil and compound 2 were dissolved in EtOH:CH3COOH (1:1, 20 mL), and the reaction was carried out at 100 °C for 8 h. After the reaction was completed, the mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to obtain a yellow oil compound 3. MS (ESI) (M+, C 84 H 126 N6S4)Exact Mass: 1348.2.

[0039] b. Under an argon atmosphere, compound 3 (0.2 g, 0.15 mmol), 1,8-diazabicycloundec-7-ene (DBU, 0.35 mmol), was dissolved in 20 mL of toluene. The mixture was heated under reflux for 10 minutes, followed by the addition of boron trifluoride diethyl ether (0.1 mL, 0.7 mmol), and refluxed for 4 hours. The mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to give an orange oil, 4. MS (ESI) (M+, C 84 H 124 B2F2N6S4)Exact Mass: 1443.8.

[0040] c. Under an argon atmosphere, compound 4 (0.2 g, 0.15 mmol) was dissolved in 20 mL of tetrahydrofuran, and the temperature was lowered to -78 °C. Then, LDA (0.4 mL) was added to the solution, and the reaction was continued at -78 °C for 1 h. DMF (1 mL) was then added, and the reaction was continued for 3 h. After the reaction was complete, the mixture was poured into ice water and neutralized with sodium acetate. Extraction was performed with dichloromethane, drying to anhydrous magnesium sulfate, solvent removal under reduced pressure, and purification of the crude product by column chromatography to give an orange oil, compound 5. MS (ESI) (M+, C 86 H 124 B2F2N6O2S4)Exact Mass: 1499.8.

[0041] d. Under an argon atmosphere, compound 5 (0.1 g, 0.072 mmol) and IC-2F (0.054 g, 0.234 mmol) were dissolved in chloroform, and 0.1 mL of pyridine was added. The mixture was heated to 60 °C and reacted overnight. After the reaction was complete, the solvent was removed under reduced pressure, and the crude product was purified by column chromatography to give the black solid compound L8-FB3. MS (ESI) (M+, C 110 H 128 B2F8N 10 O2S4)ExactMass: 1924.1.

[0042] Depend on Figure 8 It can be seen that the short-circuit current Jsc of the organic solar cell prepared by compound L8-FB3 is (20.16) mA·cm. 2 The open-circuit voltage Voc is (0.86)V, the fill factor FF is (62.91)%, and the power conversion efficiency PCE is (10.91)%.

[0043] Example 4 The structural formula of the receptor material in this embodiment is:

[0044] The synthetic route is as follows:

[0045] The synthesis method was as follows: a. Under an argon atmosphere, compound 1 (0.2 g, 0.16 mmol) was dissolved in tetrahydrofuran (30 mL), and lithium aluminum hydride (0.13 g, 3.6 mmol) was added at 0 °C. The reaction was carried out overnight at 80 °C. After the reaction was completed, the mixture was quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to obtain a dark green oil. Under an argon atmosphere, the obtained oil and compound 2 were dissolved in EtOH:CH3COOH (1:1, 20 mL), and the reaction was carried out at 100 °C for 8 h. After the reaction was completed, the mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to obtain a yellow oil compound 3. MS (ESI) (M+, C 84 H 126 N6S4)Exact Mass: 1348.2.

[0046] b. Under an argon atmosphere, compound 3 (0.2 g, 0.15 mmol), 1,8-diazabicycloundec-7-ene (DBU, 0.17 mmol), was dissolved in 20 mL of toluene. The mixture was heated under reflux for 10 minutes, followed by the addition of boron trifluoride diethyl ether (0.05 mL, 0.35 mmol), and refluxed for 4 hours. The mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to give an orange oil, 4. MS (ESI) (M+, C 84 H 125 BF2N6S4)Exact Mass: 1396.0.

[0047] c. Under an argon atmosphere, compound 4 (0.2 g, 0.15 mmol) was dissolved in 20 mL of tetrahydrofuran, and the temperature was lowered to -78 °C. Then, LDA (0.4 mL) was added to the solution, and the reaction was continued at -78 °C for 1 h. DMF (1 mL) was then added, and the reaction was continued for 3 h. After the reaction was complete, the mixture was poured into ice water and neutralized with sodium acetate. Extraction was performed with dichloromethane, drying to anhydrous magnesium sulfate, solvent removal under reduced pressure, and purification of the crude product by column chromatography to give an orange oil, compound 5. MS (ESI) (M+, C 86 H 125 BF2N6O2S4)Exact Mass: 1450.9.

[0048] d. Under an argon atmosphere, compound 5 (0.1 g, 0.072 mmol) and IC-2F (0.054 g, 0.234 mmol) were dissolved in chloroform, and 0.1 mL of pyridine was added. The mixture was heated to 60 °C and reacted overnight. After the reaction was complete, the solvent was removed under reduced pressure, and the crude product was purified by column chromatography to give the black solid compound L8-FB4. MS (ESI) (M+, C110 H 129 BF6N 10 O2S4)ExactMass: 1876.4.

[0049] Depend on Figure 9 It can be seen that the short-circuit current Jsc of the organic solar cell prepared by compound L8-FB4 is (19.50) mA·cm. 2 The open-circuit voltage Voc is (0.92)V, the fill factor FF is (66.82)%, and the power conversion efficiency PCE is (11.98)%.

[0050] Example 5 The structural formula of the receptor material in this embodiment is:

[0051] The synthetic route is as follows:

[0052] The synthesis method was as follows: a. Under an argon atmosphere, compound 1 (0.2 g, 0.16 mmol) was dissolved in tetrahydrofuran (30 mL), and lithium aluminum hydride (0.13 g, 3.6 mmol) was added at 0 °C. The reaction was carried out overnight at 80 °C. After the reaction was completed, the mixture was quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to obtain a dark green oil. Under an argon atmosphere, the obtained oil and compound 2 were dissolved in EtOH:CH3COOH (1:1, 20 mL), and the reaction was carried out at 100 °C for 8 h. After the reaction was completed, the mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to obtain a yellow oil compound 3. MS (ESI) (M+, C 80 H 123 N5S4)Exact Mass: 1283.1.

[0053] b. Under an argon atmosphere, compound 3 (0.2 g, 0.15 mmol), 1,8-diazabicycloundec-7-ene (DBU, 0.17 mmol), was dissolved in 20 mL of toluene. The mixture was heated under reflux for 10 minutes, followed by the addition of boron trifluoride diethyl ether (0.05 mL, 0.35 mmol), and refluxed for 4 hours. The mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to give an orange oil, 4. MS (ESI) (M+, C 80 H 122 BF2N5S4)Exact Mass: 1330.9.

[0054] c. Under an argon atmosphere, compound 4 (0.2 g, 0.15 mmol) was dissolved in 20 mL of tetrahydrofuran, and the temperature was lowered to -78 °C. Then, LDA (0.4 mL) was added to the solution, and the reaction was continued at -78 °C for 1 h. DMF (1 mL) was then added, and the reaction was continued for 3 h. After the reaction was complete, the mixture was poured into ice water and neutralized with sodium acetate. Extraction was performed with dichloromethane, drying to anhydrous magnesium sulfate, solvent removal under reduced pressure, and purification of the crude product by column chromatography to give an orange oil, compound 5. MS (ESI) (M+, C 82 H 122 BF2N5O2S4)Exact Mass: 1387.0.

[0055] d. Under an argon atmosphere, compound 5 (0.1 g, 0.072 mmol) and IC-2F (0.054 g, 0.234 mmol) were dissolved in chloroform, and 0.1 mL of pyridine was added. The mixture was heated to 60 °C and reacted overnight. After the reaction was complete, the solvent was removed under reduced pressure, and the crude product was purified by column chromatography to give the black solid compound L8-FB5. MS (ESI) (M+, C 106 H 126 BF6N9O2S4)ExactMass: 1811.3.

[0056] Depend on Figure 10 It can be seen that the short-circuit current Jsc of the organic solar cell prepared by compound L8-FB5 is (19.46) mA·cm. 2 The open-circuit voltage Voc is (0.86)V, the fill factor FF is (62.92)%, and the power conversion efficiency PCE is (10.53)%.

[0057] In the synthesis methods of all embodiments of the present invention, there is no particular limitation on the reaction time, and the reaction endpoint can be monitored by TLC plate.

[0058] In the synthesis methods of all embodiments of the present invention, there are no particular limitations on the post-processing. Those skilled in the art can use conventional column chromatography separation methods based on the physical and chemical properties of the material to achieve the separation of the target product.

[0059] The above embodiments are merely exemplary embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art can make various modifications or equivalent substitutions to the present invention within its scope and spirit, and such modifications or equivalent substitutions should also be considered to fall within the scope of protection of the present invention.

Claims

1. A fluorine-boron coordination-type non-fullerene electron acceptor material, characterized in that, The receptor material has a general structural formula of one of the NFA-FB1 to NFA-FB5 structural formulas: ； Where R1 and R1' are C1~C 20 The alkyl group includes a straight-chain structure, a branched structure, and any combination of straight-chain and straight-chain structures; R2 and R2' are C1~C 20 The alkyl group includes a straight-chain structure, a branched structure, and any combination of straight-chain and straight-chain structures; A1 and A2 are electron-withdrawing groups.

2. The fluorine-boron coordination-type non-fullerene electron acceptor material, its preparation method, and its application according to claim 1, characterized in that, The specific structural formulas of A1 and A2 are any one of the following structures: ; Where E represents O, S, and Se atoms; X represents F, Cl, Br, and I atoms; and X1 and X2 represent F, Cl, Br, and I atoms.

3. A method for preparing a fluorine-boron coordinated non-fullerene electron acceptor material, characterized in that, The specific synthetic route for preparing the NFA-FB1 receptor material of claim 1 is as follows: ; Compound A was reduced with LiAlH4 to obtain compound B; Compound B was reacted with 2-pyridinecarboxaldehyde to give compound C; Compound C reacts with boron trifluoride diethyl ether under alkaline conditions to give compound D; Compound D reacts with a formylation reagent via a Vilsmeier-Haack reaction to yield compound E; Compound E and EG ketone were reacted via a Knoevenagel reaction to yield the non-fullerene acceptor material compound NFA-FB1.

4. A method for preparing a fluorine-boron coordinated non-fullerene electron acceptor material, characterized in that, The specific synthetic route for preparing the NFA-FB2 receptor material of claim 1 is as follows: ; Compound A was reduced with LiAlH4 to obtain compound B; Compound B reacts with compound 1 to give compound F; Compound F reacts with boron trifluoride diethyl ether under alkaline conditions to give compound G; Compound G reacts with a formylation reagent via a Vilsmeier-Haack reaction to yield compound K; Compound K and EG ketone were reacted via a Knoevenagel reaction to yield the non-fullerene acceptor material compound NFA-FB2.

5. A method for preparing a fluorine-boron coordinated non-fullerene electron acceptor material, characterized in that, The specific synthetic route for preparing the NFA-FB3 receptor material of claim 1 is as follows: ; Compound A was reduced with LiAlH4 to obtain compound B; Compound B reacts with compound 2 to give compound L; Compound L reacts with boron trifluoride diethyl ether under alkaline conditions to give compound M; Compound M reacts with a formylation reagent via a Vilsmeier-Haack reaction to yield compound N; Compound N and EG ketone were reacted via a Knoevenagel reaction to yield the non-fullerene acceptor material compound NFA-FB3.

6. A method for preparing a fluorine-boron coordinated non-fullerene electron acceptor material, characterized in that, The specific synthetic route for preparing the NFA-FB4 receptor material of claim 1 is as follows: ; Compound A was reduced with LiAlH4 to obtain compound B; Compound B reacts with compound 2 to give compound L; Compound L reacts with boron trifluoride diethyl ether under alkaline conditions to give compound P; Compound P reacts with a formylation reagent via a Vilsmeier-Haack reaction to yield compound Q; Compound Q and EG ketone were reacted via a Knoevenagel reaction to yield the non-fullerene acceptor material compound NFA-FB4.

7. A method for preparing a fluorine-boron coordinated non-fullerene electron acceptor material, characterized in that, The specific synthetic route for preparing the NFA-FB5 receptor material of claim 1 is as follows: ； Compound A was reduced with LiAlH4 to obtain compound B; Compound B reacts with compound 3 to give compound R; Compound R reacts with boron trifluoride diethyl ether under alkaline conditions to give compound S; Compound S reacts with a formylation reagent via a Vilsmeier-Haack reaction to yield compound T; Compound T and EG ketone were reacted via a Knoevenagel reaction to yield the non-fullerene acceptor material compound NFA-FB5.

8. The preparation method according to any one of claims 3-7, characterized in that, The EG ketone is any one of the following structures: ； Where E represents O, S, and Se atoms; X represents F, Cl, Br, and I atoms; and X1 and X2 represent F, Cl, Br, and I atoms.

9. The application of a fluorine-boron coordinated non-fullerene electron acceptor material as an electron acceptor material in organic optoelectronic devices, characterized in that, The fluorine-boron coordinated non-fullerene electron acceptor material is structurally as described in any one of claims 1-2, or prepared by the preparation method described in any one of claims 3-8. The organic optoelectronic device includes organic solar cell devices, sensors, photodetectors, and electronic paper.

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