Metal complex type non-fullerene electron acceptor material, preparation method and application

Abstract

The invention discloses a metal complex type non-fullerene electron acceptor material, a preparation method and application, and relates to the technical field of organic photovoltaic devices, the novel metal complex type non-fullerene electron acceptor material is designed and synthesized by introducing metal ions into non-fullerene acceptor molecules. By reasonably designing the structure of the metal complex, the extinction coefficient of the material is remarkably improved, so that the material has higher light absorption capacity under unit thickness, and the light capture efficiency is improved. Heavy metal elements in the metal complex have relatively long excited state life and relatively strong carrier migration characteristics, so that the life of a photon-generated carrier is effectively prolonged, the recombination loss is reduced, and the photoelectric conversion efficiency is further improved. By introducing the metal complex, the charge transmission performance of a non-fullerene receptor is enhanced, the problems of short exciton diffusion distance and high exciton recombination rate in a traditional organic semiconductor material are solved, and photon-generated carriers can be effectively separated and migrated in a thin active layer.

Description

Technical Field

[0001] The present invention relates to the technical field of organic photovoltaic devices, in particular to a metal complex type non-fullerene electron acceptor material, a preparation method and an application thereof. Background Art

[0002] With the growing demand for renewable energy, organic solar cells (OSCs) have become a research hotspot for future energy solutions due to their low cost, tunability, and flexibility. In recent years, non-fullerene acceptor materials, as a key component of organic solar cells, have gradually become a research focus. Compared with traditional fullerene acceptor materials, non-fullerene acceptor materials exhibit significant advantages in optoelectronic performance, stability, and synthetic tunability, and therefore are widely used in the research of high-efficiency organic solar cells.

[0003] Organic semiconductor materials exhibit weak intermolecular interactions and high exciton binding energies, resulting in a short diffusion length for excitons within the material. Excitons are prone to recombination before reaching the charge separation interface, reducing device efficiency and thus limiting their potential to improve photoelectric conversion efficiency. Furthermore, the short exciton diffusion length limits the thickness of the active layer. Thinner active layers require non-fullerene acceptors to improve their light-harvesting capacity per unit thickness. To address these deficiencies, existing technologies have introduced various structures and elements to enhance the material's light absorption capacity and carrier transport properties, particularly by adjusting the material's electronic structure to increase its light absorption area and improve the lifetime of photogenerated carriers. Metal complexes, as novel optoelectronic functional materials, offer unique advantages in enhancing photoelectric performance. For example, heavy metal complexes possess strong light absorption properties and long excited-state lifetimes, effectively increasing the transport distance of photogenerated carriers, thereby improving the photoelectric conversion efficiency of organic solar cells. However, research on metal complex-based non-fullerene acceptor materials is still in its infancy, and related synthesis methods and performance optimization remain technical challenges in this field. Therefore, how to design a new type of metal complex-type non-fullerene acceptor material that can simultaneously improve the material's extinction coefficient, extend the lifetime of photogenerated carriers, and improve the efficiency of organic solar cells has become a technical problem that needs to be urgently solved in this field. Summary of the Invention

[0004] In order to overcome the problems existing in the prior art and further improve the efficiency and stability of organic solar cells, the present invention proposes a metal complex type non-fullerene electron acceptor material, a preparation method and an application thereof.

[0005] The technical solution adopted by the present invention to solve the technical problem is: a metal complex type non-fullerene electron acceptor material, the structural formula of the acceptor material is one of the structural formulas NFA-MC1 to NFA-MC5: ; Wherein, M is one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, scandium, yttrium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, lanthanum, cerium, neodymium, tin, and lead; L1 and L2 are Cl-, amino, phenyl, or 2-thienyl; R1 and R1' are C1~C20 alkyl groups, and the alkyl groups include straight chain structures, branched chain structures, and any combination of straight chain structures and branched chain structures; R2 and R2' are C1~C20 alkyl groups, and the alkyl groups include straight chain structures, branched chain structures, and any combination of straight chain structures and branched chain structures; A1 and A2 are electron-withdrawing groups.

[0006] In the above-mentioned metal complex type non-fullerene electron acceptor material, the specific structural formulas of A1 and A2 are any one of the following structures: ; Among them, E is O, S, or Se atom; X is F, Cl, Br, or I atom; X1 and X2 are F, Cl, Br, or I atoms.

[0007] A method for preparing a metal complex type non-fullerene electron acceptor material is used to prepare the metal complex type non-fullerene electron acceptor material as described above. The specific synthesis route is: ; Compound A is subjected to a reduction reaction with LiAlH4 to obtain compound B; Compound B is reacted with a quinoxaline fragment and its derivative to obtain compound C; Compound C is reacted with a formylating agent via Vilsmeier-Haack reaction to obtain compound D; Compound D and EG ketone are reacted by Knoevenagel reaction to obtain non-fullerene acceptor material compound E; Compound E reacts with a metal complex to obtain NFA-MCx, where x = 1, 2, 3, 4, 5.

[0008] In the above-mentioned method for preparing a metal complex type non-fullerene electron acceptor material, the EG ketone is any one of the following structures: ; Among them, E is O, S, or Se atom; X is F, Cl, Br, or I atom; X1 and X2 are F, Cl, Br, or I atoms.

[0009] In the above-mentioned method for preparing a metal complex-type non-fullerene electron acceptor material, the quinoxaline fragment and its derivatives are any one of the following structures: .

[0010] A metal complex type non-fullerene electron acceptor material, the structural formula of which is NFA-MC6: ; Wherein, M is one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, scandium, yttrium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, lanthanum, cerium, neodymium, tin, and lead; R1 and R1' are C1~C20 alkyl groups, and the alkyl groups include straight chain structures, branched chain structures, and any combination of straight chain structures and branched chain structures; R2 and R2' are C1~C20 alkyl groups, and the alkyl groups include straight chain structures, branched chain structures, and any combination of straight chain structures and branched chain structures; A1 and A2 are electron-withdrawing groups.

[0011] In the above-mentioned metal complex type non-fullerene electron acceptor material, the specific structural formulas of A1 and A2 are any one of the following structures: ; Among them, E is O, S, or Se atom; X is F, Cl, Br, or I atom; X1 and X2 are F, Cl, Br, or I atoms.

[0012] A method for preparing a metal complex type non-fullerene electron acceptor material is used to prepare the metal complex type non-fullerene electron acceptor material as described above. The specific synthesis route is: ; Compound A is subjected to a reduction reaction with LiAlH4 to obtain compound B; Compound B is reacted with salicylaldehyde to obtain compound F; Compound F is reacted with a formylating agent via Vilsmeier-Haack reaction to obtain compound G; Compound G and EG ketone are reacted via Knoevenagel reaction to obtain non-fullerene acceptor material compound H; Compound H reacts with a metal complex to give NFA-MC6.

[0013] In the above-mentioned method for preparing a metal complex type non-fullerene electron acceptor material, the EG ketone is any one of the following structures: ; Among them, E is O, S, or Se atom; X is F, Cl, Br, or I atom; X1 and X2 are F, Cl, Br, or I atoms.

[0014] The use of any of the above-mentioned metal complex-type non-fullerene electron acceptor materials or the metal complex-type non-fullerene electron acceptor materials prepared by any of the above-mentioned preparation methods as electron acceptor materials in organic optoelectronic devices is characterized in that the organic optoelectronic devices include organic solar cell devices, sensors and electronic paper.

[0015] The present invention has the beneficial effect of providing a metal complex-based non-fullerene acceptor material. By rationally designing the metal complex structure, the material's extinction coefficient is significantly increased, resulting in a stronger light absorption capability per unit thickness, thereby improving light capture efficiency. The heavy metal elements (such as Pt) in the metal complex possess long excited state lifetimes and strong carrier mobility properties, effectively extending the lifetime of photogenerated carriers, reducing recombination losses, and thereby improving photoelectric conversion efficiency. This effectively enhances the efficiency of organic solar cells.

[0016] Furthermore, the present invention enhances the charge transport properties of non-fullerene acceptors by introducing metal complexes, overcoming the short exciton diffusion distance and high exciton recombination rate issues inherent in traditional organic semiconductor materials. This allows for the efficient separation and migration of photogenerated carriers within the thin active layer. This not only effectively addresses the limitations of existing technologies but also provides a new solution for the development of high-efficiency organic solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is the hydrogen spectrum of compound 3 in Example S1 of the present invention; Figure 2 This is the hydrogen spectrum of compound 4 in Example S1 of the present invention; Figure 3 This is the hydrogen spectrum of compound 5 in Example S1 of the present invention; Figure 4 This is the hydrogen spectrum of compound 6 in Example S1 of the present invention; Figure 5 is the normalized UV-visible absorption spectrum of compound 6 in Example S1 of the present invention; Figure 6 is the UV-visible absorption spectrum of compound 6 in Example S1 of the present invention; Figure 7 This is the JV curve of the solar device described in Example S1, Compound 6 of the present invention; Figure 8 This is the EQE spectrum of the solar device described in Example S1, Compound 6 of the present invention. DETAILED DESCRIPTION

[0018] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0019] Example 1 The structural formula of the receptor material in this embodiment is: ; The synthetic route is as follows: ; The synthesis method is as follows: a. Under an argon atmosphere, compound 1 TPB26 (0.2 g, 0.18 mmol) was dissolved in tetrahydrofuran (30 mL), lithium aluminum hydride (0.13 g, 3.6 mmol) was added at 0°C, and the reaction was continued at 80°C overnight. After the reaction was completed, water was added to quench the reaction, and the mixture was 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 compound 2 phen-5,6-dione in EtOH:CH3COOH (1:1, 20 mL) and reacted 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 an orange oil compound 3 Y6-FLL, the hydrogen spectrum of which is shown as follows: Figure 1 shown.

[0020] b. Under an argon atmosphere, compound 3 Y6-FLL (0.2 g, 0.16 mmol) was dissolved in 20 mL of 1,2-dichloroethane and the temperature was lowered to 0°C. DMF (0.3 mL) and phosphorus oxychloride (0.2 mL) were then added sequentially to the solution. The reaction was continued at 0°C for 1 h, then the temperature was raised to 80°C and the reaction was continued for 10 h. After the reaction, the mixture was poured into ice water and neutralized with sodium acetate. Extraction was performed with dichloromethane, drying was performed with anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to obtain an orange solid 4 Y6-FLL-CHO. The hydrogen spectrum was shown in FIG. Figure 2 shown.

[0021] c. Under an argon atmosphere, compound 4 Y6-FLL-CHO (0.1 g, 0.078 mmol) and IC-2F (0.054 g, 0.234 mmol) were dissolved in chloroform, 0.1 mL of pyridine was added, and the temperature was raised to 60°C. The reaction was allowed to proceed overnight. After the reaction, the solvent was removed under reduced pressure, and the crude product was purified by column chromatography to obtain compound 5 Y6-FLL-IC as a black solid. The H 2 O spectrum is shown in FIG. Figure 3 shown.

[0022] d. Under an argon atmosphere, compound 5 Y6-FLL-IC (0.05 g, 0.029 mmol) and Pt(DMSO)2Cl2 (0.013 g, 0.029 mmol) were dissolved in chloroform and allowed to react in the dark at room temperature for 10 hours. After the reaction, the product was precipitated in methanol and isolated by filtration. The product was separated and purified by gel chromatography to obtain compound 6 Y6-FLL-IC-Pt, a black solid. The H 2 O spectrum is shown in Figure 2. Figure 4 shown.

[0023] Figure 5 Normalized UV-visible absorption spectra of prepared compound 6 Y6-FLL-IC-pt in chloroform solution and on quartz plate. Figure 5 It can be seen that the maximum absorption value of the thin film of compound 6 is around 865 nm, the onset peak is around 320 nm, and the optical band gap is 1.61 eV. The optical band gap can be calculated according to the formula Eg=1240 / λonset, where Eg is the optical band gap and λonset is the maximum absorption sideband value of the thin film absorption.

[0024] Figure 6 UV-visible absorption spectra of L8BO and prepared compound 6 Y6-FLL-IC-pt in chloroform solution. Figure 6 It can be seen that the molar extinction coefficient of compound 6 is much higher than that of L8BO, indicating that the introduction of metal elements can significantly increase the extinction coefficient of the material, making this material have stronger light absorption ability per unit thickness, thereby improving the light capture efficiency.

[0025] Depend on Figure 7 It can be seen that the short-circuit current Jsc of the organic solar cell prepared by compound 6 is (24.6) mA cm-2, the open-circuit voltage Voc is (0.93) V, the fill factor FF is (69.77)%, and the energy conversion efficiency PCE is (15.46)%.

[0026] Figure 8 This is the external quantum efficiency curve of the device. The absorption of compound 6 synthesized in the embodiment of this patent is complementary to that of the polymer donor D18-Cl, thereby achieving effective utilization of visible-near-infrared light and obtaining a higher short-circuit current.

[0027] Example 2 The structural formula of the receptor material in this embodiment is: ; The synthetic route is: ; The specific synthesis method is as follows: a. Under an argon atmosphere, compound 1 TPB26 (0.2 g, 0.18 mmol) was dissolved in tetrahydrofuran (30 mL). Lithium aluminum hydride (0.13 g, 3.6 mmol) was added at 0°C and reacted overnight at 80°C. After completion of the reaction, the product 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 resulting oil was dissolved in compound Di-2-pyridylglyoxal in EtOH:CH3COOH (1:1, 20 mL) and reacted at 100°C for 8 h. After completion of the reaction, the product 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 compound 3 Y6-Pyr as an orange oil. MS (ESI) (M+, C76H106N6S4) Exact Mass: 1230.74.

[0028] b. Under an argon atmosphere, compound 3 Y6-Pyr (0.2 g, 0.16 mmol) was dissolved in 20 mL of 1,2-dichloroethane and the temperature was lowered to 0°C. DMF (0.3 mL) and phosphorus oxychloride (0.2 mL) were then added sequentially to the solution. The reaction was continued at 0°C for 1 h, then the temperature was raised to 80°C and the reaction continued for 10 h. After the reaction, the mixture was poured into ice water and neutralized with sodium acetate. 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 yield 4 Y6-Pyr-CHO as an orange solid. MS (ESI) (M+, C78H106N6O2S4) Exact Mass: 1286.73.

[0029] c. Under an argon atmosphere, compound 4 Y6-Pyr-CHO (0.1 g, 0.077 mmol) and IC-2F (0.054 g, 0.234 mmol) were dissolved in chloroform, 0.1 mL of pyridine was added, and the temperature was raised to 60°C for overnight reaction. After completion of the reaction, the solvent was removed under reduced pressure, and the crude product was purified by column chromatography to obtain compound 5 Y6-Pyr-IC as a black solid. MS (ESI) (M+, C102H110F4N10O2S4) Exact Mass: 1711.77.

[0030] d. Under argon, compound 5 Y6-Pyr-IC (0.05 g, 0.029 mmol) and Pt(DMSO)2Cl2 (0.013 g, 0.029 mmol) were dissolved in chloroform and allowed to react at room temperature in the dark for 10 hours. After the reaction, the product was precipitated in methanol and isolated by filtration. The product was separated and purified by gel chromatography to obtain compound 6 Y6-Pyr-IC-Pt as a black solid. MS (ESI) (M+, C102H110Cl2F4N10O2PtS4) Exact Mass: 1976.67.

[0031] Example 3 The structural formula of the receptor material in this embodiment is: ; The synthetic route is: ; The specific synthesis method is as follows: a. Under an argon atmosphere, compound 1 TPB26 (0.2 g, 0.18 mmol) was dissolved in tetrahydrofuran (30 mL). Lithium aluminum hydride (0.13 g, 3.6 mmol) was added at 0°C and reacted overnight at 80°C. After completion of the reaction, the product 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 resulting oil was dissolved in compound Ethanedione, bis(2-thiazolyl)-(9CI) in EtOH:CH3COOH (1:1, 20 mL) and reacted at 100°C for 8 h. After completion of the reaction, the product 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 compound 3 Y6-Thi as an orange oil. MS(ESI)(M+,C72H102N6S6)Exact Mass: 1242.65.

[0032] b. Under an argon atmosphere, compound 3 Y6-Thi (0.2 g, 0.16 mmol) was dissolved in 20 mL of 1,2-dichloroethane and the temperature was lowered to 0°C. DMF (0.3 mL) and phosphorus oxychloride (0.2 mL) were then added sequentially to the solution. The reaction was continued at 0°C for 1 h, then the temperature was raised to 80°C and the reaction continued for 10 h. After the reaction, the mixture was poured into ice water and neutralized with sodium acetate. 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 yield 4 Y6-Thi-CHO as an orange solid. MS (ESI) (M+, C74H102N6O2S6) Exact Mass: 1298.64.

[0033] c. Under argon, compound 4 Y6-Thi-CHO (0.1 g, 0.080 mmol) and IC-2F (0.054 g, 0.234 mmol) were dissolved in chloroform. 0.1 mL of pyridine was added, and the temperature was raised to 60°C for overnight reaction. After completion of the reaction, the solvent was removed under reduced pressure, and the crude product was purified by column chromatography to obtain compound 5 Y6-Thi-IC as a black solid. MS (ESI) (M+, C98H106F4N10O2S6) Exact Mass: 1723.68.

[0034] d. Under argon, compound 5 Y6-Thi-IC (0.05 g, 0.028 mmol) and Pt(DMSO)2Cl2 (0.013 g, 0.029 mmol) were dissolved in chloroform and allowed to react at room temperature in the dark for 10 hours. After the reaction, the product was precipitated in methanol and isolated by filtration. The product was separated and purified by gel chromatography to obtain compound 6 Y6-Thi-IC-Pt as a black solid. MS (ESI) (M+, C98H106Cl2F4N10O2PtS6) Exact Mass: 1989.58.

[0035] Example 4 The structural formula of the receptor material in this embodiment is: ; The synthetic route is: ; The specific synthesis method is as follows: a. Under an argon atmosphere, compound 1 TPB26 (0.2 g, 0.18 mmol) was dissolved in tetrahydrofuran (30 mL). Lithium aluminum hydride (0.13 g, 3.6 mmol) was added at 0°C and reacted overnight at 80°C. After completion of the reaction, the product 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 resulting oil was dissolved in benzo(h)quinoline-5,6-dione in EtOH:CH3COOH (1:1, 20 mL) and reacted at 100°C for 8 h. After completion of the reaction, the product 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 compound 3 Y6-Bqi as an orange oil. MS (ESI) (M+, C77H105N5S4) Exact Mass: 1227.73.

[0036] b. Under an argon atmosphere, compound 3 Y6-Bqi (0.2 g, 0.16 mmol) was dissolved in 20 mL of 1,2-dichloroethane and the temperature was lowered to 0°C. DMF (0.3 mL) and phosphorus oxychloride (0.2 mL) were then added sequentially to the solution. The reaction was continued at 0°C for 1 h, then the temperature was raised to 80°C and the reaction continued for 10 h. After the reaction, the mixture was poured into ice water and neutralized with sodium acetate. 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 yield 4 Y6-Bqi-CHO as an orange solid. MS (ESI) (M+, C79H105N5O2S6) Exact Mass: 1283.72.

[0037] c. Under argon, compound 4 Y6-Bqi-CHO (0.1 g, 0.077 mmol) and IC-2F (0.054 g, 0.234 mmol) were dissolved in chloroform. 0.1 mL of pyridine was added, and the temperature was raised to 60°C for overnight reaction. After completion of the reaction, the solvent was removed under reduced pressure, and the crude product was purified by column chromatography to obtain compound 5 Y6-Bqi-IC as a black solid. MS (ESI) (M+, C103H109F4N9O2S4) Exact Mass: 1708.76.

[0038] d. Under argon, compound 5 Y6-Bqi-IC (0.05 g, 0.028 mmol) and Pt(DMSO)2Cl2 (0.013 g, 0.029 mmol) were dissolved in chloroform and allowed to react at room temperature in the dark for 10 hours. After the reaction, the product was precipitated in methanol and isolated by filtration. The product was separated and purified by gel chromatography to obtain compound 6 Y6-Bqi-IC-Pt as a black solid. MS (ESI) (M+, C103H108Cl2F4N9O2PtS4) Exact Mass: 1972.65.

[0039] Example 5 The structural formula of the receptor material in this embodiment is: ; The synthetic route is: ; The specific synthesis method is as follows: a. Under an argon atmosphere, compound 1 TPB26 (0.2 g, 0.18 mmol) was dissolved in tetrahydrofuran (30 mL). Lithium aluminum hydride (0.13 g, 3.6 mmol) was added at 0°C and reacted overnight at 80°C. After completion of the reaction, the product 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 resulting oil was dissolved in compound 2 Ethyl glyoxalate in EtOH:THF (3:1, 20 mL) and stirred at room temperature for 8 h. After completion of the reaction, the product 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 compound 3 Y6-Egl as an orange oil. MS (ESI) (M+, C66H100N4OS4): 1092.65.

[0040] b. Under an argon atmosphere, compound 3 Y6-Egl (0.2 g, 0.18 mmol) was dissolved in 2 mL of phosphorus oxychloride and the temperature was lowered to 0°C. 0.5 mL of DMF was then added to the solution. The reaction was continued at 0°C for 1 h, then the temperature was raised to 90°C and the reaction continued for 10 h. After the reaction, the mixture was poured into ice water and neutralized with sodium acetate. 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 yield 4 Y6-Egl-CHO as an orange solid. MS (ESI) (M+, C68H99ClN4O2S4): 1166.62.

[0041] c. In a pre-dried Schlenk tube, compound 4 Y6-Egl-CHO (0.2 g, 0.17 mmol), 5 2-(Tributylstannyl)pyridine (0.1 g, 0.34 mmol), and Pd(PPh3)4 (0.02 g, 0.017 mmol) were dissolved in 20 mL of degassed toluene. The mixture was heated at 120°C for 24 h. After cooling to room temperature, the organic layer was washed with brine, extracted twice with dichloromethane, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to yield 6 Y6-Egl-CHO-N as an orange solid. MS (ESI) (M+, C73H103N5O2S4) Exact Mass: 1209.72.

[0042] d. Under an argon atmosphere, compound 6 Y6-Egl-CHO-N (0.1 g, 0.082 mmol) and IC-2F (0.056 g, 0.246 mmol) were dissolved in chloroform, 0.1 mL of pyridine was added, and the temperature was raised to 60°C for overnight reaction. After completion of the reaction, the solvent was removed under reduced pressure, and the crude product was purified by column chromatography to obtain compound 7 Y6-Egl-IC as a black solid. MS (ESI) (M+, C97H107F4N9O2S4) Exact Mass: 1633.75.

[0043] e. Under argon, compound 7 (0.05 g, 0.030 mmol) and Pt(DMSO)2Cl2 (0.014 g, 0.030 mmol) were dissolved in chloroform and allowed to react in the dark at room temperature for 10 h. After the reaction, the product was precipitated in methanol and filtered. Purification by gel chromatography afforded compound 8 Y6-Egl-IC-Pt as a black solid. MS (ESI) (M+, C97H107Cl2F4N9O2PtS4) Exact Mass: 1898.62.

[0044] Example 6 The structural formula of the receptor material in this embodiment is: ; The synthetic route is: ; The synthesis method is as follows: a. Under an argon atmosphere, compound 1 TPB26 (0.2 g, 0.18 mmol) was dissolved in tetrahydrofuran (30 mL). Lithium aluminum hydride (0.13 g, 3.6 mmol) was added at 0°C and reacted overnight at 80°C. After the reaction, water was added to quench the mixture, and the mixture was 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 resulting oil and compound 2 (salicylaldehyde) were dissolved in 20 mL of EtOH and reacted overnight at 80°C. After the reaction, the mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The resulting oil was dissolved in 15 mL of DMF, and potassium tetrachloroplatinate (0.15 g, 0.18 mmol) dissolved in 2 mL of DMF was added dropwise to the solution. The reaction was continued at 80°C for 10 h. After the reaction, the mixture was extracted with dichloromethane and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the crude product was purified by column chromatography to obtain the orange compound 3Y6-Sal-Pt. MS (ESI) (M+, C78H108N4O2PtS4): 1457.05.

[0045] b. Under an argon atmosphere, compound 3 Y6-Sal-Pt (0.2 g, 0.14 mmol) was dissolved in 20 mL of 1,2-dichloroethane and the temperature was lowered to 0°C. DMF (0.3 mL) and phosphorus oxychloride (0.2 mL) were then added sequentially to the solution. The reaction was continued at 0°C for 1 h, then the temperature was raised to 80°C and the reaction continued for 10 h. After the reaction, the mixture was poured into ice water and neutralized with sodium acetate. 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 yield 4 Y6-Sal-Pt-CHO as an orange solid. MS (ESI) (M+, C80H108N4O4PtS4): 1513.10.

[0046] c. Under an argon atmosphere, compound 4 (0.1 g, 0.066 mmol) and IC-2F (0.054 g, 0.198 mmol) were dissolved in chloroform, 0.1 mL of pyridine was added, and the temperature was raised to 60°C for overnight reaction. After completion of the reaction, the solvent was removed under reduced pressure, and the crude product was purified by column chromatography to obtain compound 5 Y6-Sal-Pt-IC as a black solid. MS (ESI) (M+, C104H112F4N8O4PtS4): 1937.41.

[0047] In the synthesis methods of all embodiments of the present invention, the reaction time is not particularly limited, and the reaction endpoint can be monitored by TLC plate.

[0048] In the synthesis methods of all embodiments of the present invention, there is no particular limitation on post-treatment, and those skilled in the art can separate the target product by conventional column chromatography separation methods based on the physical and physicochemical properties.

[0049] 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 may make various modifications or equivalent substitutions to the present invention within the spirit and scope of protection of the present invention, and such modifications or equivalent substitutions shall also be deemed to fall within the scope of protection of the present invention.

Claims

1. A metal complex type non-fullerene electron acceptor material, characterized in that: The general structural formula of the receptor material is one of the general structural formulas NFA-MC1 to NFA-MC5: ； Wherein, M is one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, scandium, yttrium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, lanthanum, cerium, neodymium, tin, and lead; L1 and L2 are Cl-, amino, phenyl, or 2-thienyl; R1 and R1' are C1-C20 alkyl groups, and the alkyl group includes a straight chain structure, a branched chain structure, and any combination of a straight chain structure and a branched chain structure; R2 and R2' are C1-C20 alkyl groups, and the alkyl group includes a straight chain structure, a branched chain structure, and any combination of a straight chain structure and a branched chain structure; A1 and A2 are electron withdrawing groups.

2. A metal complex type non-fullerene electron acceptor material according to claim 1, characterized in that: The specific structural formula of A1 and A2 is any one of the following structures: ; Among them, E is O, S, Se atom; X is F, Cl, Br, I atom; X1 and X2 are F, Cl, Br, I atoms.

3. A method for preparing a metal complex type non-fullerene electron acceptor material, characterized in that: For preparing the metal complex type non-fullerene electron acceptor material according to any one of claims 1 to 2, the specific synthesis route is: ; Compound A is subjected to a reduction reaction with LiAlH4 to obtain compound B; Compound B is reacted with a quinoxaline fragment and a derivative thereof to obtain compound C; Compound C is reacted with a formylating agent via a Vilsmeier-Haack reaction to obtain compound D; Compound D and EG ketone are reacted by Knoevenagel reaction to obtain non-fullerene acceptor material compound E; Compound E reacts with a metal complex to obtain NFA-MCx, where x=1,2,3,4,5.

4. The method for preparing a metal complex type non-fullerene electron acceptor material according to claim 3, characterized in that: The EG ketone is any one of the following structures: ; Among them, E is O, S, Se atom; X is F, Cl, Br, I atom; X1 and X2 are F, Cl, Br, I atoms.

5. The method for preparing a metal complex type non-fullerene electron acceptor material according to claim 3, characterized in that: The quinoxaline fragment and its derivatives are any one of the following structures: 。 6. A metal complex type non-fullerene electron acceptor material, characterized in that: The structural formula is NFA-MC6: ; Wherein, M is one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, scandium, yttrium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, lanthanum, cerium, neodymium, tin, and lead; R1 and R1' are C1-C20 alkyl groups, and the alkyl group includes a straight chain structure, a branched chain structure, and any combination of a straight chain structure and a branched chain structure; R2 and R2' are C1-C20 alkyl groups, and the alkyl group includes a straight chain structure, a branched chain structure, and any combination of a straight chain structure and a branched chain structure; A1 and A2 are electron withdrawing groups.

7. A metal complex type non-fullerene electron acceptor material according to claim 6, characterized in that: The specific structural formula of A1 and A2 is any one of the following structures: ; Among them, E is O, S, Se atom; X is F, Cl, Br, I atom; X1 and X2 are F, Cl, Br, I atoms.

8. A method for preparing a metal complex type non-fullerene electron acceptor material, characterized in that: For preparing the metal complex type non-fullerene electron acceptor material as claimed in claim 7, the specific synthesis route is: ; Compound A is subjected to a reduction reaction with LiAlH4 to obtain compound B; Compound B is reacted with salicylaldehyde to obtain compound F; Compound F is reacted with a formylating agent via Vilsmeier-Haack reaction to obtain compound G; Compound G and EG ketone are reacted by Knoevenagel reaction to obtain non-fullerene acceptor material compound H; Compound H reacts with a metal complex to obtain NFA-MC6.

9. The method for preparing a metal complex type non-fullerene electron acceptor material according to claim 3, characterized in that: The EG ketone is any one of the following structures: ; Among them, E is O, S, Se atom; X is F, Cl, Br, I atom; X1 and X2 are F, Cl, Br, I atoms.

10. Use of any one of the metal complex type non-fullerene electron acceptor materials according to claims 1-2, claims 6-7, or the metal complex type non-fullerene electron acceptor material prepared by any one of the preparation methods according to claims 3-5, claims 8-9 as an electron acceptor material in an organic optoelectronic device, characterized in that: The organic optoelectronic devices include organic solar cell devices, sensors and electronic paper.

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