Fullerene derivative as well as preparation method and application thereof
Chiral Bis-PCBM single crystals were prepared by in-situ growth, which solved the problems of macroscopic anisotropy and interface defects in Bis-PCBM polycrystals, and achieved more uniform physical properties, making them suitable for optoelectronic devices.
Patent Information
- Application Number
- CN202510945424.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-09
- Publication Date
- 2025-11-11
AI Technical Summary
In the prior art, Bis-PCBM polycrystals have low macroscopic anisotropy and many interface defects, resulting in uneven local properties, internal stress, and poor mechanical properties.
Chiral Bis-PCBM single crystals were prepared by in-situ growth. By preparing crude Bis-PCBM, chiral compounds, and single crystals, high-performance liquid chromatography and normal-phase silica gel column chromatography were used for separation and purification. The preparation parameters were optimized to form a highly ordered crystal structure.
It achieves high crystallinity and crystal integrity in chiral Bis-PCBM single crystals, resulting in more uniform physical properties, stronger anisotropy, and fewer interface defects, making it suitable for high-purity, low-defect scenarios.
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Figure CN120923344A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of organic synthesis technology, and in particular to a fullerene derivative, its preparation method, and its application. Background Technology
[0002] Fullerene derivatives are compounds obtained by chemically modifying the structure of fullerene parent structures, exhibiting good properties in electrical, optical, thermal, and mechanical aspects. Among them, Bis-PCBM, derived from fullerene C60, is officially named bis(1-(3-(methoxycarbonyl)propyl)-1-phenyl)-(6,6)-C62 or (6,6)-diphenyl-C62 bis(methyl butyrate), with the molecular formula C84H28O4 and a molecular weight of 1,101.14. Due to its excellent optical, electrical, and crystallinity properties, Bis-PCBM is used in the fabrication of organic solar cells and organic field-effect transistors. However, most existing research focuses on forming polycrystalline Bis-PCBM. While this method has lower preparation costs, the polycrystalline structure exhibits lower macroscopic anisotropy and more interface defects, leading to uneven local performance, internal stress, and poor mechanical properties. Therefore, it is essential to provide a fullerene derivative exhibiting good electrical, optical, thermal, and mechanical properties, along with its preparation method and applications. Summary of the Invention
[0003] The purpose of this invention is to solve the above problems and provide a fullerene derivative, its preparation method and application. The fullerene derivative obtained by this invention is a chiral Bis-PCBM single crystal, which has high crystallinity and crystal integrity. Due to its highly ordered lattice structure, its physical properties are generally more uniform and consistent than those of polycrystalline materials, with stronger anisotropy and fewer interface defects. This makes the fullerene derivative more advantageous in high-purity, low-defect scenarios.
[0004] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:
[0005] In a first aspect, the present invention provides a method for preparing a fullerene derivative, wherein the fullerene derivative is Bis-PCBM, comprising the steps of:
[0006] S1. Preparation of Bis-PCBM crude product: Prepare a first precursor solution and a fullerene solution respectively. Add the fullerene solution to the first precursor solution to obtain a first mixed solution. Heat the first mixed solution to 70-90℃ and stir the reaction for a first time under irradiation with a 100-200W sodium lamp to obtain a first product. Dry the first product to obtain a dark red solid crude product, namely the crude product Bis-PCBM.
[0007] S2. Preparation of Bis-PCBM chiral compound: Dissolve 700-1400 mg of the crude product Bis-PCBM obtained in step S1 in 500-900 mL of toluene to obtain a second mixed solution. Filter the second mixed solution to obtain a filtrate. Perform separation and purification recycling on the filtrate to obtain a chiral compound. Perform separation and purification recycling on the chiral compound to obtain the Bis-PCBM chiral compound. The Bis-PCBM chiral compound includes trans3-A-34,35-bis
[60] PCBM and trans3-C-34,35-bis
[60] PCBM.
[0008] S3. Preparation of chiral Bis-PCBM single crystal: The chiral Bis-PCBM compound obtained in step S2 is dissolved in m-xylene to prepare a second precursor solution with a concentration of 1.5-3 mg / mL. The second precursor solution is dropped onto a silicon wafer and allowed to stand to obtain the chiral Bis-PCBM single crystal.
[0009] Optionally, in step S1, the preparation of the first precursor solution includes the following steps: under a nitrogen atmosphere, dissolving 20-45g of methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone in 500-800mL of pyridine, and then adding 1-5g of NaOMe and stirring for 10-40min to prepare the first precursor solution.
[0010] Optionally, the preparation method of the methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone includes the following steps: adding 10-20g of p-toluenesulfonylhydrazine and 30-60mL of methanol to methyl 4-benzoylbutyrate, reacting at 70-110℃ for a second time to obtain a second product; cooling the obtained second product to a first temperature to precipitate white crystals, and washing, filtering, and drying the white crystals at the first temperature to obtain the methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone; wherein, the first temperature is -15±5℃.
[0011] Optionally, the step of washing, filtering, and drying the white crystals at the first temperature specifically includes the following steps: washing and filtering the white crystals with methanol at the first temperature, and then drying the washed and filtered white crystals at a second temperature to obtain methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone.
[0012] Optionally, the preparation method of the methyl 4-benzoylbutyrate includes the following steps: mixing 10-30g of 4-benzoylbutyric acid, 2-5g of p-toluenesulfonic acid, 70-140mL of methanol and 200-300mL of benzene and reacting for a third time to obtain a third product; cooling the third product to room temperature, washing the third product, and separating the organic layer solution; removing the water and solvent from the organic layer solution to obtain the methyl 4-benzoylbutyrate.
[0013] Optionally, washing the third product includes the steps of: sequentially adding 150-350 mL of ethyl acetate, 500-1000 mL of 5-20 wt% Na2CO3 aqueous solution and 500-1000 mL of distilled water to the first mixed reactants.
[0014] Optionally, the method for preparing the fullerene solution includes the step of dissolving 10-30g of fullerene in 2-3L of 1,2-dichlorobenzene to obtain the fullerene solution.
[0015] Optionally, in step S2, the filtrate is subjected to separation and purification cycling to obtain a chiral compound; this includes the following steps: separating and purifying the filtrate using single-channel high-performance liquid chromatography and a normal-phase silica column to obtain product F2 component; separating and purifying product F2 component through the separation and purification cycle to obtain product F2.3 component; and then separating and purifying product F2.3 component through the separation and purification cycle to obtain the chiral compound; wherein, the separation and purification cycling of the chiral compound specifically includes the following steps: separating and purifying the chiral compound using single-channel high-performance liquid chromatography and chiral chromatographic column purification, separating the chiral compound during the cycle, and collecting the desired Bis-PCBM chiral compound.
[0016] Secondly, the present invention provides a fullerene derivative, which is prepared by the preparation method described above.
[0017] Thirdly, the present invention provides an application of a fullerene derivative in optoelectronic devices, characterized in that the fullerene derivative is prepared by the preparation method described above.
[0018] The beneficial effects of this invention include at least the following:
[0019] This invention provides a fullerene derivative, its preparation method, and its application. The method for preparing the fullerene derivative involves synthesizing a crude Bis-PCBM product containing multiple chiral molecules via a nucleophilic cyclopropanation Binger reaction. The crude Bis-PCBM product is then purified by high-performance liquid chromatography (HPLC) to obtain chiral molecules with 99.9% purity, achieving the initial preparation of chiral fullerene molecules. Through parameter optimization during the preparation process, single crystals of the fullerene derivative were obtained, and the growth, size, and morphology of the chiral fullerene single crystals were controlled. The fullerene derivative obtained by this invention is a chiral Bis-PCBM single crystal, which exhibits high crystallinity and crystal integrity. Due to its highly ordered lattice structure, its physical properties are generally more uniform and consistent than those of polycrystalline materials, exhibiting stronger anisotropy and fewer interface defects. This makes the fullerene derivative more advantageous in high-purity, low-defect scenarios. Attached Figure Description
[0020] Figure 1 These are the separation chromatograms of the first (a) and the last (b) high performance liquid chromatography in Example 1 of the present invention; wherein, the horizontal axis is the liquid chromatography separation time and the vertical axis is the intensity of the ultraviolet absorption peak.
[0021] Figure 2 The NMR spectra of the two Bis-PCBM chiral compounds isolated in Example 1 of this invention are shown below. (a) is the NMR spectra of trans3-A-34,35-bis
[60] PCBM, and (b) is the NMR spectra of trans3-C-34,35-bis
[60] PCBM. The horizontal axis represents the chemical shift, with values of 80-25 ppm representing the carbon peak of sp3, 150-125 ppm representing the carbon peak of sp2, and 172-171 ppm representing the carbon peak of sp2.
[0022] Figure 3 These are optical microscope images of the single crystals prepared in Example 1 and Comparative Examples 1 and 2 of the present invention; wherein, (a) is Example 1, (b) is Comparative Example 1, and (c) is Comparative Example 2.
[0023] Figure 4 The voltage-voltage characteristic curve of a single-crystal field-effect transistor fabricated based on the Bis-PCBM single crystal of the present invention under illumination. Detailed Implementation
[0024] To facilitate understanding of the present invention, preferred embodiments are provided below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention.
[0025] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
[0026] In this invention, the use of terms such as "first" and "second" is for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated.
[0027] It should be noted that, unless otherwise specified, all raw materials involved in this invention can be obtained from suppliers known in the art or prepared by known methods.
[0028] A method for preparing a fullerene derivative, comprising the following steps:
[0029] S1. Preparation of Bis-PCBM crude product: A first precursor solution and a fullerene solution are prepared separately. The fullerene solution is added to the first precursor solution to obtain a first mixed solution. The first mixed solution is heated to 70-90℃ and stirred under irradiation with a 100-200W sodium lamp for a first time to obtain a first product. The first product is dried to obtain a dark red solid crude product, namely the crude product Bis-PCBM. The first time is 8-12 hours.
[0030] S2. Preparation of Bis-PCBM chiral compound: Dissolve 700-1400 mg of the crude product Bis-PCBM obtained in step S1 in 500-900 mL of toluene to obtain a second mixed solution. Filter the second mixed solution through a 0.45 μm polytetrafluoroethylene filter membrane to obtain a filtrate. Perform separation and purification recycling on the filtrate to obtain a chiral compound. Perform separation and purification recycling on the chiral compound to obtain the Bis-PCBM chiral compound. The Bis-PCBM chiral compound includes trans3-A-34,35-bis
[60] PCBM and trans3-C-34,35-bis
[60] PCBM.
[0031] S3. Preparation of chiral Bis-PCBM single crystal: The chiral Bis-PCBM compound obtained in step S2 is dissolved in m-xylene to prepare a second precursor solution with a concentration of 1.5-3 mg / mL. 30-70 μL of the second precursor solution is dropped onto a silicon wafer and allowed to stand for one day to obtain the chiral Bis-PCBM single crystal.
[0032] In the preparation method described in this invention, a chiral Bis-PCBM single crystal was synthesized for the first time via in-situ growth. Compared to the reverse solution method, the in-situ growth method can effectively reduce the thickness of the formed chiral Bis-PCBM single crystal. This feature is beneficial for subsequent detection of various crystal properties and for the fabrication of related devices. Furthermore, by controlling the concentration of the second precursor solution in the in-situ growth method, the size of the chiral Bis-PCBM single crystal can be macroscopically controlled. If the concentration of the second precursor solution is too low, the system is unlikely to reach critical supersaturation, leading to hindered nucleation. According to the basic principles of crystal growth, nucleation requires overcoming the surface energy barrier. In a low-concentration environment, the collision frequency of solute molecules decreases, significantly reducing the probability of uniform nucleation. Compared to Bis-PCBM polycrystals prepared by spin coating in existing technologies, chiral Bis-PCBM single crystals possess a complete, continuous, and ordered lattice structure without grain boundaries or particle boundaries. In contrast, Bis-PCBM polycrystals are composed of numerous grains interconnected by grain boundaries, which are the interfaces between different grains within a crystal. The atoms or molecules on the grain boundaries are relatively disordered. Therefore, chiral Bis-PCBM single crystals have higher crystallinity and crystal integrity. Furthermore, due to their highly ordered lattice structure, chiral Bis-PCBM single crystals typically exhibit more uniform and consistent physical properties than polycrystals. Chiral Bis-PCBM single crystals demonstrate superior performance in electrical, optical, thermal, and mechanical aspects, while Bis-PCBM polycrystals exhibit heterogeneity and inhomogeneity in their physical properties due to the presence of grain boundaries.
[0033] Optionally, in step S1, the preparation of the first precursor solution includes the following steps: under a nitrogen atmosphere, dissolving 20-45g of methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone in 500-800mL of pyridine, and then adding 1-5g of NaOMe and stirring for 10-40min to prepare the first precursor solution.
[0034] Optionally, the preparation method of the methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone includes the following steps: adding 10-20g of p-toluenesulfonylhydrazine and 30-60mL of methanol to methyl 4-benzoylbutyrate, reacting at 70-110℃ for a second time to obtain a second product; cooling the obtained second product to a first temperature to precipitate white crystals, and washing, filtering, and drying the white crystals at the first temperature to obtain the methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone; wherein the second time is 3-8h, and the first temperature is -15±5℃.
[0035] Optionally, the step of washing, filtering, and drying the white crystals at the first temperature specifically includes the following steps: washing and filtering the white crystals with methanol at the first temperature, and then drying the washed and filtered white crystals at a second temperature to obtain methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone; the second temperature is 30-60°C, and in some embodiments, the drying is carried out in a vacuum drying oven.
[0036] Optionally, the preparation method of the methyl 4-benzoylbutyrate includes the following steps: mixing 10-30g of 4-benzoylbutyric acid, 2-5g of p-toluenesulfonic acid, 70-140mL of methanol and 200-300mL of benzene and reacting for a third time, wherein the third time is 13-21h, to obtain a third product; cooling the third product to room temperature, washing the third product, and separating the organic layer solution; removing water and solvent from the organic layer solution to obtain the methyl 4-benzoylbutyrate.
[0037] Optionally, washing the third product includes the following steps: sequentially adding 150-350 mL of ethyl acetate, 500-1000 mL of a 5-20 wt% Na₂CO₃ aqueous solution, and 500-1000 mL of distilled water to the first mixed reactants. Removing water and solvent from the organic layer solution includes the following steps: adding solid MgSO₄ to the organic layer solution to absorb water, then evaporating the solvent from the organic layer solution using a rotary evaporator, and collecting the resulting pale yellow liquid, which is the methyl 4-benzoylbutyrate.
[0038] Optionally, the method for preparing the fullerene solution includes the step of dissolving 10-30g of fullerene in 2-3L of 1,2-dichlorobenzene to obtain the fullerene solution. The fullerene is C60.
[0039] Optionally, in step S2, the filtrate is subjected to separation and purification cycling to obtain a chiral compound; this includes the following steps: separating and purifying the filtrate using single-channel high-performance liquid chromatography and a normal-phase silica column to obtain product F2 component; separating and purifying product F2 component through the separation and purification cycle to obtain product F2.3 component; and then separating and purifying product F2.3 component through the separation and purification cycle to obtain the chiral compound; wherein, the separation and purification cycling of the chiral compound specifically includes the following steps: separating and purifying the chiral compound using single-channel high-performance liquid chromatography and chiral chromatographic column purification, and collecting the desired Bis-PCBM chiral compound. In the preparation of the chiral compound, the separation and purification process consisting of single-channel high-performance liquid chromatography (HPLC) and normal silica gel column purification is performed as a cycle until the desired target product is collected. Similarly, in the preparation of the Bis-PCBM chiral compound, the separation and purification process consisting of single-channel HPLC and chiral column purification is performed as a cycle, and the chiral compound is subjected to this cycle until the desired Bis-PCBM chiral compound is collected. It should be noted that the product F2 component is described in the literature Structural Identification of 19 Purified Isomers of the OPV Acceptor Material bis PCBM by 13C NMR and UV–Vis Absorption Spectroscopy and High-Performance Liquid Chromatography; Tong Liu, Isaac Abrahams and T. John S. Dennis; The Journal of Physical Chemistry A 2018 122(16), 4138-4152.Among them, the F2 component contains a variety of Bis-PCBMs, such as (C2v)52,60-bis
[60] PCBM and (C1)49,59-bis
[60] PCBM in F2.1, (Cs)32,33-bis
[60] PCBM in F2.2, and (C2)34,35-bis
[60] PCBM in F2.3, wherein F2.3 contains a high content of chiral Bis-PCBM molecules; furthermore, in this invention, the product F2 component is separated and purified by multiple cycles and normal phase silica gel column to obtain product F2.3 component, and then the product F2.3 component is separated and purified by multiple cycles to obtain Bis-PCBM chiral compounds; wherein the Bis-PCBM chiral compounds include trans3-A-34,35-bis
[60] PCBM and trans3-C-34,35-bis
[60] PCBM;
[0040] Secondly, in this embodiment of the invention, a fullerene derivative is provided, which is prepared by the preparation method described above.
[0041] Thirdly, this invention provides an application of a fullerene derivative in optoelectronic devices, characterized in that the fullerene derivative is prepared using the preparation method described above.
[0042] The optoelectronic devices include optoelectronic sensors, solar cells, organic field-effect transistors, 3D optical displays, quantum computing, and medical imaging devices.
[0043] Example 1:
[0044] A method for preparing a fullerene derivative, wherein the fullerene derivative is a chiral Bis-PCBM single crystal, includes the following steps:
[0045] (1) Synthesis of crude product Bis-PCBM, the specific process is as follows:
[0046] 1) Mix 25g of 4-benzoylbutyric acid, 3.75g of p-toluenesulfonic acid, 105mL of methanol, and 250mL of benzene and react for 18h to obtain a mixed reaction product. After the mixed reaction product is cooled to room temperature, add 250mL of ethyl acetate to the mixed reaction product and add 20g of Na2CO3 to 200mL of distilled water to prepare a 10% Na2CO3 solution. Prepare three portions of the solution. Wash the mixed reaction product three times, and then wash it three times with 200mL of distilled water to separate the organic layer solution. Add solid MgSO4 to the organic layer solution to absorb the remaining water. Then evaporate the solvent in the organic layer solution using a rotary evaporator and collect the pale yellow liquid. Blow N2 on the pale yellow liquid for 30min to remove the remaining solvent to obtain methyl 4-benzoylbutyrate for later use.
[0047] 2) Add 15.5g of p-toluenesulfonylhydrazine and 45mL of methanol to methyl 4-benzoylbutyrate and react at 95℃ for 6h. During this period, the mixture boils and the white powder gradually dissolves to obtain the reaction product. After the reaction product is cooled to room temperature, place it in a refrigerator and let it stand to cool to -15℃. At this time, white crystals precipitate from the reaction product. Place 200mL of methanol in the refrigerator and filter out the white crystals. Wash the filtered white crystals with methanol and place the washed white crystals in a vacuum drying oven at 50℃ to dry, to obtain the product methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone, for later use.
[0048] 3) Under a dry nitrogen atmosphere, 40 g of methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone was dissolved in 600 mL of dry pyridine, and then 2.88 g of sodium methoxide was added and stirred for 20 min to obtain a precursor solution. Then, 17.5 g of fullerene C60 was dissolved in 2.4 L of 1,2-dichlorobenzene to obtain a fullerene solution. The fullerene solution was added to the above precursor solution to obtain a mixed solution. The mixed solution was heated to 85 °C and stirred overnight under a 150 W sodium lamp. Finally, the product after the reaction was evaporated to dryness using a rotary evaporator to obtain a dark red solid crude product, namely the crude product Bis-PCBM, for later use.
[0049] (2) The purification process of Bis-PCBM chiral substances is as follows:
[0050] First, 1000 mg of the crude Bis-PCBM obtained above was dissolved in 500 mL of toluene to prepare a solution, and the solution was filtered through a 0.45 μm polytetrafluoroethylene filter membrane. The resulting filtrate was reserved for later use. Second, the filtrate was separated using single-channel high-performance liquid chromatography and a normal-phase silica gel column. The chromatogram obtained from the ultraviolet detector showed that the prepared Bis-PCBM contained 7 components, such as... Figure 1 As shown in (a), the first component is an impurity. Figure 1(a) Not shown, F2 component is obtained by separation; the separation and purification operation consisting of the single-channel high performance liquid chromatography and the normal phase silica column purification is one cycle. After 6 to 11 cycles of separation and purification, F2.1 and F2.2 components in F2 component are removed to obtain the desired product F2.3 component; the above cycle is repeated for 4 to 8 cycles to remove impurities and obtain chiral compounds. The chiral compounds are separated by single-channel high performance liquid chromatography and chiral column purification for 3 to 7 cycles to collect the desired Bis-PCBM chiral compounds; wherein the Bis-PCBM chiral compounds include trans3-A-34,35-bis
[60] PCBM and trans3-C-34,35-bis
[60] PCBM.
[0051] The spectrum obtained by the ultraviolet detector during this process shows that no other peaks appeared besides the main peak, such as... Figure 1 As shown in (b), this result indicates that the purity of the isolated Bis-PCBM chiral compounds is higher than 99.9%. The carbon NMR spectra of the obtained Bis-PCBM chiral compounds trans3-A-34,35-bis
[60] PCBM and trans3-C-34,35-bis
[60] PCBM were characterized by comparison. Figure 2 In (a) and (b), it is clearer that the two separated substances are enantiomers and have high purity; it should be noted that... Figure 2 (a) refers to Figure 2 The left column in the view, Figure 2 (b) refers to Figure 2 The column on the right side of the view.
[0052] (3) The growth process of Bis-PCBM single crystal is as follows:
[0053] First, the obtained Bis-PCBM chiral compounds were dissolved in xylene and allowed to stand for 60 minutes to ensure complete dissolution, thus preparing precursor solutions with a concentration of 2 mg / mL. Then, 70 μL of each precursor solution was pipetted onto a 1.5 cm x 1.5 cm silicon wafer and allowed to stand at 25 °C for 24 hours to allow the solvent to evaporate, yielding Bis-PCBM single crystals. These crystals were then observed using an optical electron microscope. Figure 3 As shown in (a), by Figure 3 (a) It can be seen that the chiral Bis-PCBM single crystal generated by this method has a regular hexagonal shape, a crystal size of 50 μm, and uniform thickness, which is beneficial for subsequent detection of its photoelectric related properties.
[0054] The obtained Bis-PCBM single crystal was used to fabricate a single-crystal field-effect transistor, and the photoelectric performance of the obtained single-crystal field-effect transistor under illumination was tested. The measured voltage-voltage characteristic curve is shown in the figure below. Figure 4 As shown. See also Figure 4 As shown, the organic field-effect transistor fabricated based on the Bis-PCBM single crystal exhibits a leakage current of up to 100 nA and an on / off ratio exceeding 1000 under illumination, indicating its promising prospects and potential application value in the field of optoelectronic applications.
[0055] Comparative Example 1:
[0056] Compared with Example 1, the difference in Comparative Example 1 is that after obtaining the Bis-PCBM chiral compounds, the obtained Bis-PCBM chiral compounds trans3-A-34,35-bis
[60] PCBM and trans3-C-34,35-bis
[60] PCBM were dissolved in xylene and allowed to stand for 20 min to dissolve, and both were prepared into precursor solutions with a concentration of 1 mg / mL; then, 70 μL of the precursor solution was pipetted onto a 1.5 cm * 1.5 cm silicon wafer and allowed to stand at 25 °C for 24 h to allow the solvent to evaporate, and Bis-PCBM single crystals were obtained. They were observed by an optical electron microscope, such as Figure 3 As shown in (b). Figure 3 (b) It can be seen that the short settling time leads to insufficient dissolution of the Bis-PCBM chiral compound, thus preventing spontaneous nucleation and formation of single crystals. In addition, the low precursor solution concentration results in a slow crystal formation rate, and no effective single crystals are formed after the solution evaporates.
[0057] Comparative Example 2:
[0058] Compared with Example 1, the difference in Comparative Example 1 is that after obtaining the Bis-PCBM chiral compounds, the obtained Bis-PCBM chiral compounds trans3-A-34,35-bis
[60] PCBM and trans3-C-34,35-bis
[60] PCBM were dissolved in chlorobenzene and allowed to stand for 60 minutes to fully dissolve, and each was prepared into a 1 mL precursor solution with a concentration of 3 mg / mL; then, the precursor solutions were respectively put into two 2 mL glass sample bottles, and the two sample bottles were placed open into a 20 mL sample bottle containing 10 mL of isopropanol, and the 20 mL sample bottles were tightened with screw caps and wrapped with sealing film to prevent the solution in the sample bottles from evaporating; finally, the sample bottles were wrapped with tin foil and placed in a cool place for a week to wait for the crystal particles to precipitate, and Bis-PCBM single crystals were obtained. They were observed by an optical electron microscope, such as Figure 3 As shown in (c). Figure 3 (c) It can be seen that although the crystal grown by the reverse solution method in this comparative example has a large size, its thickness is not uniform, which is not conducive to the subsequent detection of its photoelectric performance. In contrast, Example 1 has a wafer thickness of about 400 nm and a relatively flat wafer thickness while ensuring its own crystal size, which is beneficial to the subsequent detection of relevant photoelectric performance data.
[0059] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0060] The above embodiments merely illustrate preferred implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention should be determined by the appended claims.
Claims
1. A method for preparing a fullerene derivative, characterized in that, Including the following steps: S1. Preparation of Bis-PCBM crude product: Prepare a first precursor solution and a fullerene solution respectively, and add the fullerene solution to the first precursor solution to obtain a first mixed solution; The first mixed solution was heated to 70-90℃ and stirred under a 100-200W sodium lamp for a first time to obtain the first product; the first product was dried to obtain a dark red solid crude product, namely the crude product Bis-PCBM. S2. Preparation of Bis-PCBM chiral compound: Dissolve 700-1400 mg of the crude product Bis-PCBM obtained in step S1 in 500-900 mL of toluene to obtain a second mixed solution, and filter the second mixed solution to obtain the filtrate; The filtrate was separated, purified, and recycled to obtain a chiral compound; The chiral compound was separated and purified by cyclic processing to obtain the Bis-PCBM chiral compound; wherein the Bis-PCBM chiral compound includes trans3-A-34,35-bis[60]PCBM and trans3-C-34,35-bis[60]PCBM; S3. Preparation of chiral bis-PCBM single crystal: The chiral Bis-PCBM compound obtained in step S2 is dissolved in m-xylene to prepare a second precursor solution with a concentration of 1.5-3 mg / mL. The second precursor solution is dropped onto a silicon wafer and allowed to stand to obtain the chiral bis-PCBM single crystal.
2. The method for preparing fullerene derivatives according to claim 1, characterized in that, In step S1, the preparation of the first precursor solution includes the following steps: under a nitrogen atmosphere, dissolving 20-45g of methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone in 500-800mL of pyridine, and then adding 1-5g of NaOMe and stirring for 10-40min to prepare the first precursor solution.
3. The method for preparing fullerene derivatives according to claim 2, characterized in that, The preparation method of the methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone includes the following steps: adding 10-20g of p-toluenesulfonylhydrazine and 30-60mL of methanol to methyl 4-benzoylbutyrate, reacting at 70-110℃ for a second time to obtain a second product; cooling the obtained second product to a first temperature to precipitate white crystals, washing, filtering, and drying the white crystals at the first temperature to obtain the methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone; wherein, the first temperature is -15±5℃.
4. The method for preparing fullerene derivatives according to claim 3, characterized in that, The process of cleaning, filtering, and drying the white crystals at the first temperature specifically includes the following steps: cleaning and filtering the white crystals with methanol at the first temperature, and then drying the cleaned and filtered white crystals at a second temperature to obtain methyl 4-benzoylbutyrate p-toluenesulfonylhydrazone.
5. The method for preparing fullerene derivatives according to claim 3, characterized in that, The preparation method of the methyl 4-benzoylbutyrate includes the following steps: mixing 10-30g of 4-benzoylbutyric acid, 2-5g of p-toluenesulfonic acid, 70-140mL of methanol and 200-300mL of benzene and reacting for a third time to obtain a third product; cooling the third product to room temperature, washing the third product, and separating the organic layer solution; removing the water and solvent from the organic layer solution to obtain the methyl 4-benzoylbutyrate.
6. The method for preparing fullerene derivatives according to claim 5, characterized in that, The washing of the third product includes the steps of: sequentially adding 150-350 mL of ethyl acetate, 500-1000 mL of 5-20 wt% Na2CO3 aqueous solution and 500-1000 mL of distilled water to the first mixed reactant.
7. The method for preparing fullerene derivatives according to claim 1, characterized in that, The method for preparing the fullerene solution includes the following steps: dissolving 10-30g of fullerene in 2-3L of 1,2-dichlorobenzene to obtain the fullerene solution.
8. The method for preparing fullerene derivatives according to claim 1, characterized in that, In step S2, the filtrate is separated, purified, and recycled to obtain a chiral compound; The process includes the following steps: separating and purifying the filtrate using single-channel high-performance liquid chromatography and a normal-phase silica column to obtain product F2 component; separating and purifying product F2 component through the separation and purification cycle to obtain product F2.3 component; and further separating and purifying product F2.3 component through the separation and purification cycle to obtain the chiral compound; wherein, the separation and purification cycle of the chiral compound specifically includes the following steps: separating and purifying the chiral compound using single-channel high-performance liquid chromatography and chiral chromatographic column purification cycle, and collecting the desired Bis-PCBM chiral compound.
9. A fullerene derivative, characterized in that, The fullerene derivative was prepared by the preparation method according to any one of claims 1-8.
10. The application of a fullerene derivative in optoelectronic devices, characterized in that, The fullerene derivative was prepared by the preparation method according to any one of claims 1-8.