A halogenated fullerene pyrrolidine derivative, its preparation method and application

Abstract

This application provides a halogenated fullerene pyrrolidine derivative, its preparation method, and its application. The halogenated fullerene pyrrolidine derivative has the general structural formula I, where the fullerene ring comprises a C28-C120 fullerene ring; each X is independently a halogen atom or any one of C1-C3 haloalkyl; n is an integer from 1 to 5; R comprises any one of substituted or unsubstituted C6-C20 aryl, 5-20-membered heteroaryl, or C1-C6 alkyl, and the substituents of R include halogen, -SH, C1-C6 alkyl or haloalkyl, 5-10-membered heteroaryl, -C(O)O(C1-C6) alkyl, -NR 1 R 2 、-P(O)(OR 3 )2、-Si-(OR 4 )3. Any one of 12-20 crown ethers and 12-20 heterocrown ethers, R 1 R 2 Each R 3 Each R 4 Each is independently selected from H, C1-C6 alkyl, or tert-butoxycarbonyl.

Description

Technical Field

[0001] This application relates to the field of photoelectric conversion materials technology, specifically to a halohydrated fullerene pyrrolidine derivative, its preparation method and application. Background Technology

[0002] Since their introduction in 2009, perovskite solar cells have experienced rapid growth in photoelectric conversion efficiency, closely catching up with the efficiency levels of silicon-based solar cells. The device structures of perovskite solar cells are mainly divided into nip and pin configurations. While nip configuration cells exhibit excellent photoelectric conversion efficiency, their limited stability hinders their application expansion. Conversely, although pin configuration cells have slightly lower photoelectric conversion efficiency, they have become the focus of attention in academia and industry due to their ease of low-temperature solution handling, excellent long-term stability, and high adaptability to tandem cell designs.

[0003] Traditional C 60 While vapor deposition can achieve excellent performance layer construction, its high cost and adverse effects on large-scale industrial manufacturing cannot be underestimated. In contrast, solution-based fabrication, although still having room for improvement in some performance parameters, offers a broader prospect for the practical application and commercialization of perovskite solar cell technology due to its simple preparation process, significant cost-effectiveness, and flexibility in material modification to meet specific needs. This method not only synergizes well with large-scale manufacturing systems but also provides a practical strategy for continuously optimizing material performance and enhancing the overall stability of devices.

[0004] Against this backdrop, fullerenes, as electron transport layer materials, have played a crucial role in advancing the performance optimization of pin-type perovskite solar cells. Currently, C 60 Derivative PCBM([6,6]-phenyl-C 61 methyl butyrate (PCBM) remains the mainstream choice for electron transport layers in perovskites, but its synthesis is complex and costly. Therefore, designing and synthesizing novel fullerene derivatives that can replace PCBM is a key technology for high-efficiency, low-cost perovskite solar cell materials. Summary of the Invention

[0005] To reduce the fabrication cost of electron transport layer materials for perovskite solar cells and achieve high electron transport efficiency, this application provides a halofullerene pyrrolidine derivative, its preparation method, and its application.

[0006] The first aspect of this application provides a halogenated fullerene pyrrolidine derivative and its chemically acceptable salt, the halogenated fullerene pyrrolidine derivative having the general structural formula I:

[0007]

[0008] Wherein, the fullerene ring includes a C28-C120 fullerene ring; each X is independently a halogen atom or any one of a C1-C3 haloalkyl group; n is any integer from 1 to 5; R includes any one of a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted 5-20 member heteroaryl group, or a substituted or unsubstituted C1-C6 alkyl group, and the substituents of R include halogens, -SH, C1-C6 alkyl groups, C1-C6 haloalkyl groups, 5-10 member heteroaryl groups, -C(O)O(C1-C6) alkyl groups, and -NR. 1 R 2 -P(O)(OR) 3 )2、-Si-(OR 4 )3, any one of 12-20 crown ethers and 12-20 heterocrown ethers, R 1 R 2 Each R 3 Each R 4 Each is independently selected from H, C1-C6 alkyl, or tert-butoxycarbonyl.

[0009] The fullerene-pyrrole ring coupling structure of the halofullerene-pyrrole derivatives provided in this application gives the halofullerene-pyrrole derivatives excellent structural stability; and the benzene ring connected to the para-position of the pyrrole ring is replaced by a halogen-containing substituent X. The presence of halogen can improve solubility by increasing the polarity between molecules. In addition, since the halogen has a strong electronegativity, it can reduce the electron affinity of the halofullerene-pyrrole derivatives, thereby further improving their ability to attract and transfer electrons, and can be used as a more efficient electron transport material.

[0010] When applied to perovskite solar cells, it can improve the photoelectric conversion efficiency (PCE) of perovskite cells, achieving excellent photoelectric performance comparable to PCBM. Furthermore, the raw materials used to generate the aforementioned halofullerene pyrrolidine derivatives are readily available, and the reaction also has cost advantages due to its simplicity and the absence of metal catalysts.

[0011] In any embodiment of the first aspect, the fullerene ring is a C60 fullerene ring or a C70 fullerene ring.

[0012] In any embodiment of the first aspect, each X is independently any one of F, Cl, Br or C1-C3 haloalkyl, optionally F, Cl, Br or trifluoromethyl, further optionally F or Br; n is 1 or 2, optionally 1.

[0013] In any embodiment of the first aspect, R comprises any one of a substituted or unsubstituted C6-C10 aryl group, a substituted or unsubstituted 5-10-membered heteroaryl group, or a 5-10-membered heteroaryl-substituted C1-C3 alkyl group, wherein the substituents of the substituted C6-C10 aryl group or the substituted 5-10-membered heteroaryl group in R include halogens, -SH, C1-C3 alkyl groups, C1-C3 haloalkyl groups, -C(O)O(C1-C3) alkyl groups, and -NR. 1 R 2 -P(O)(OR) 3 )2、-Si-(OR 4 )3. Any one of 15-18 crown ethers and 15-18 heterocrown ethers, R 1 R 2 Each R 3 Each R 4 Each is independently selected from H, C1-C3 alkyl, or tert-butoxycarbonyl.

[0014] In any embodiment of the first aspect, the aryl group in the substituted or unsubstituted C6-C10 aryl group is phenyl.

[0015] In any embodiment of the first aspect, the heteroaryl group in the substituted or unsubstituted 5-10 member is any one of thienyl, furanyl, thiazolyl, pyridyl, pyrimidinyl, oxazolyl or imidazoleyl, and may be selected as thiazolyl or pyridyl.

[0016] In any embodiment of the first aspect, the alkyl group in the 5-10 member heteroaryl-substituted C1-C3 alkyl group is selected from methyl or ethyl, and the 5-10 member heteroaryl group is selected from pyridinyl or pyrimidinyl.

[0017] In any embodiment of the first aspect, R is selected from phenyl, thiazolyl or pyridyl, and the pyridyl group is optionally 2-pyridyl, 3-pyridyl or 4-pyridyl, and the pyridyl group is optionally 3-pyridyl or 4-pyridyl.

[0018] In any embodiment of the first aspect, the substituents of the C6-C10 aryl group or the substituted 5-10 heteroaryl group in R include any one of halogen, -SH, methyl, ethyl, propyl, trifluoromethyl, -C(O)OCH3, -C(O)OCH2CH3, -NH2, -NHBoc, -P(O)(OH)2, -P(O)(OCH2CH3)2, -Si-(OCH3)3, 15-18 crown ether, 15-18 aza crown ether, and 15-18 aza-sulfur co-crown ether.

[0019] In any embodiment of the first aspect, the substituents of the C6-C10 aryl group or the substituted 5-10 heteroaryl group in R are selected from ethyl or -C(O)OCH2CH3.

[0020] In any embodiment of the first aspect, the number of substituents in R is 0, 1, 2, 3, 4 or 5, optionally 0 or 1.

[0021] In any embodiment of the first aspect, the halofullerene pyrrolidine derivative has the following general structural formula II:

[0022]

[0023] In any embodiment of the first aspect, the haloalloben pyrrolidine derivative has the following general structural formula III:

[0024]

[0025] In any embodiment of the first aspect, the halogenated fullerene pyrrolidine derivative and its chemically acceptable salt are selected from any one or more of the following compounds:

[0026]

[0027]

[0028]

[0029]

[0030] The second aspect of this application provides a method for preparing a halogenated fullerene pyrrolidine derivative, which can prepare the halogenated fullerene pyrrolidine derivative in any embodiment of the first aspect. The preparation method includes: reacting a fullerene, a halogen-substituted N-phenylglycine, and an aromatic aldehyde derivative in a solvent to obtain the halogenated fullerene pyrrolidine derivative.

[0031] Halogen-substituted N-phenylglycine has structural formula IV:

[0032]

[0033] Aromatic aldehyde derivatives have the structural formula V:

[0034]

[0035] The definitions of X and n in structural form IV and R in structural form V are the same as those in the first aspect of this application.

[0036] In any embodiment of the second aspect, the above reaction satisfies one or more of the following conditions: 1) the molar ratio of fullerene, halogenated N-phenylglycine, and aromatic aldehyde derivative is 1:(4-15):(2-15), optionally 1:(2-10):(2-10); 2) the reaction temperature is 60℃-150℃; 3) the solvent includes o-dichlorobenzene or chlorobenzene; 4) the reaction is carried out under the protection of nitrogen or an inert gas.

[0037] In any embodiment of the second aspect, the preparation method further includes a process of purifying the halogenated fullerene pyrrolidine derivative, wherein the eluent used for purification includes one or a mixture of CS2, petroleum ether and toluene, and optionally the eluent includes a mixture of petroleum ether and toluene in a volume ratio of 1:1 to 10:1.

[0038] The third aspect of this application provides the use of a halogenated fullerene pyrrolidine derivative and its chemically acceptable salt in a battery, according to any embodiment of the first aspect.

[0039] The fourth aspect of this application provides a perovskite solar cell including an electron transport layer comprising a fullerene derivative, wherein the fullerene derivative includes the halofullerene pyrrolidine derivative and its chemically acceptable salts as described in any embodiment of the first aspect.

[0040] The fifth aspect of this application provides a fuel cell including an electrode assembly comprising a fullerene derivative, wherein the fullerene derivative includes the halogenated fullerene pyrrolidine derivative and its chemically acceptable salts as described in any embodiment of the first aspect. Attached Figure Description

[0041] To more clearly illustrate the specific embodiments of the present invention, the accompanying drawings used in the specific embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0042] Figure 1 The fullerene-pyrrolidine derivative L-6 synthesized in Example 1 is shown. 1 HNMR spectrum;

[0043] Figure 2 The fullerene-pyrrolidine derivative L-17 synthesized in Example 2 is shown. 1 HNMR spectrum;

[0044] Figure 3 The fullerene-pyrrolidine derivative L-56 synthesized in Example 3 is shown. 1 HNMR spectrum;

[0045] Figure 4 The fullerene-pyrrolidine derivative L-53 synthesized in Example 4 is shown. 1 HNMR spectrum;

[0046] Figure 5 The fullerene-pyrrolidine derivative L-51 synthesized in Synthesis Example 5 is shown. 1 HNMR spectrum;

[0047] Figure 6 The fullerene-pyrrolidine derivative L-52 synthesized in Synthesis Example 6 is shown. 1 HNMR spectrum;

[0048] Figure 7 The fullerene-pyrrolidine derivative L-40 synthesized in Synthesis Example 7 is shown. 1 HNMR spectrum;

[0049] Figure 8 The fullerene-pyrrolidine derivative L-50 synthesized in Synthesis Example 8 is shown. 1 HNMR spectrum;

[0050] Figure 9 The fullerene-pyrrolidine derivative L-66 synthesized in Synthesis Example 9 is shown. 1 HNMR spectrum;

[0051] Figure 10 The fullerene-pyrrolidine derivative L-69 synthesized in Synthesis Example 10 is shown. 1 H NMR spectrum;

[0052] Figure 11 The fullerene-pyrrolidine derivative L-74 synthesized in Synthesis Example 11 is shown. 1 H NMR spectrum;

[0053] Figure 12 The mass spectrum of the fullerene pyrrolidine derivative L-74 synthesized in Synthesis Example 11 is shown.

[0054] Figure 13 The fullerene-pyrrolidine derivative L-75 synthesized in Synthesis Example 12 is shown. 1 H NMR spectrum;

[0055] Figure 14 The mass spectrum of the fullerene pyrrolidine derivative L-75 synthesized in Synthesis Example 12 is shown;

[0056] Figure 15 The fullerene-pyrrolidine derivative L-76 synthesized in Synthesis Example 13 is shown. 1 H NMR spectrum;

[0057] Figure 16 The mass spectrum of the fullerene pyrrolidine derivative L-76 synthesized in Synthesis Example 13 is shown.

[0058] Figure 17 The fullerene-pyrrolidine derivative L-22 synthesized in Synthesis Example 14 is shown. 1 H NMR spectrum;

[0059] Figure 18 The fullerene-pyrrolidine derivative L-67 synthesized in Synthesis Example 15 is shown. 1 H NMR spectrum;

[0060] Figure 19 The fullerene-pyrrolidine derivative L-11 synthesized in Synthesis Example 16 is shown. 1 H NMR spectrum;

[0061] Figure 20 The fullerene-pyrrolidine derivative L-15 synthesized in Synthesis Example 17 is shown. 1 H NMR spectrum;

[0062] Figure 21 The fullerene-pyrrolidine derivative L-16 synthesized in Synthesis Example 18 is shown. 1 H NMR spectrum;

[0063] Figure 22 The fullerene-pyrrolidine derivative L-78 synthesized in Synthesis Example 19 is shown. 1 H NMR spectrum;

[0064] Figure 23 The fullerene-pyrrolidine derivative L-79 synthesized in Synthesis Example 20 is shown. 1 H NMR spectrum;

[0065] Figure 24 The JV curves of photovoltaic devices based on fullerene pyrrolidine derivative L-22 in application example A1 and on non-halogenated fullerene pyrrolidine derivative F1 in application comparative example 1 are shown.

[0066] Figure 25 The JV curve of the photovoltaic device based on fullerene pyrrolidine derivative L-17 in application example A2 is shown;

[0067] Figure 26 The JV curve of the photovoltaic device based on the fullerene pyrrolidine derivative L-11 in application example A3 is shown;

[0068] Figure 27 The JV curve of the photovoltaic device based on the fullerene pyrrolidine derivative L-15 in application example A4 is shown;

[0069] Figure 28 The JV curve of the photovoltaic device based on the fullerene pyrrolidine derivative L-16 in application example A5 is shown;

[0070] Figure 29 The JV curve of the photovoltaic device based on the fullerene pyrrolidine derivative L-78 in application example A6 is shown;

[0071] Figure 30 The JV curve of the photovoltaic device based on fullerene pyrrolidine derivative L-79 in application example A7 is shown;

[0072] Figure 31 The JV curves of the photovoltaic device based on the fullerene derivative PCBM in Comparative Example 2 are shown.

[0073] Figure 32 The polarization and power density curves of the H2-O2 fuel cell based on the fullerene pyrrolidine derivative L-15 in application example B1 are shown.

[0074] Figure 33 The polarization and power density curves of the H2-Air fuel cell based on the fullerene pyrrolidine derivative L-15 in Application Example B1 are shown. Detailed Implementation

[0075] The embodiments of this application will be described in further detail below with reference to the examples. The detailed description of the following embodiments is used to illustrate the principles of this application, but should not be used to limit the scope of this application, that is, this application is not limited to the described embodiments.

[0076] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0077] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0078] Among numerous fullerene derivatives, fullerene pyrrolidine derivatives have become the focus of current fullerene derivative research due to their ease of synthesis and high flexibility in structural modification. However, the synthesis of current fullerene pyrrolidine derivatives is complex and the preparation cost is high. To improve the electron transport efficiency of fullerene pyrrolidine derivatives while reducing costs, the first embodiment of this application provides a haloalized fullerene pyrrolidine derivative and its chemically acceptable salt, wherein the haloalized fullerene pyrrolidine derivative has the general structural formula I:

[0079]

[0080] Wherein, the fullerene ring includes a C28-C120 fullerene ring; each X is independently a halogen atom or any one of a C1-C3 haloalkyl group; n is any integer from 1 to 5; and R includes any one of a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted 5-20 member heteroaryl group, or a substituted or unsubstituted C1-C6 alkyl group, and the substituents of R include halogen, -SH, C1-C6 alkyl group, C1-C6 haloalkyl group, 5-10 member heteroaryl group, -C(O)O(C1-C6) alkyl group, -NR group, etc. 1 R 2 -P(O)(OR) 3 )2、-Si-(OR 4 )3, any one of 12-20 crown ethers and 12-20 heterocrown ethers, R 1 R 2 Each R 3 Each R 4 Each is independently selected from H, C1-C6 alkyl, or tert-butoxycarbonyl.

[0081] The fullerene-pyrrole ring coupling structure of the halofullerene-pyrrole derivatives provided in this application gives the halofullerene-pyrrole derivatives excellent structural stability; and the benzene ring connected to the para-position of the pyrrole ring is replaced by a halogen-containing substituent X. The presence of halogen can improve solubility by increasing the polarity between molecules. In addition, since the halogen has a strong electronegativity, it can reduce the electron affinity of the halofullerene-pyrrole derivatives, thereby further improving their ability to attract and transfer electrons, and can be used as a more efficient electron transport material.

[0082] When applied to perovskite solar cells, it can improve the photoelectric conversion efficiency (PCE) of perovskite cells, achieving excellent photoelectric performance comparable to PCBM. Furthermore, the raw materials used to generate the aforementioned halofullerene pyrrolidine derivatives are readily available, and the reaction also has cost advantages due to its simplicity and the absence of metal catalysts.

[0083] In the aforementioned halogenated fullerene pyrrolidine derivatives, the fullerene ring can be a C28-C120 fullerene ring, such as C28, C34, C60, C70, C84, C90, C104, or C120. Fullerenes themselves are typical electron-deficient conjugated systems with properties similar to aromatic hydrocarbons, capable of undergoing various chemical reactions with certain substances, including cycloaddition, nucleophilic, electrophilic addition, free radical addition, photochemical reactions, and redox reactions. Based on the 1,3-dipolar cycloaddition mechanism of the imine ylide intermediate, a series of fullerene pyrrolidines with high stereoselectivity can be prepared by cycloaddition of Schiff base intermediates synthesized from aldehydes, amines, or amino acids with fullerenes.

[0084] The difference in the number of carbon atoms in fullerene molecules is accompanied by the diversity of their geometric structures, resulting in differences in stability among fullerene molecules with different geometries. In some embodiments, the fullerene ring in the above-mentioned halogenated fullerene pyrrolidine derivatives is C10-C20. 60 Fullerene ring or C 70 Fullerene ring.

[0085] With C 60 For example, it is generally composed of 12 five-membered rings and 20 six-membered rings, with each carbon atom adopting an approximate sp ring structure. 2 Hybridization, with overlapping p orbitals between adjacent carbon atoms, forms a total of 30 C=C bonds. All double bonds alternately conjugate to form a highly delocalized large conjugated Π system, which has good electron-accepting properties and high electron mobility.

[0086] C 70 Fullerenes and C 60 Fullerenes have similar physicochemical properties, both being composed of compounds similar to sp. 2 Zero-dimensional conjugated spherical molecules composed of hybridized carbon atoms, consisting of five-membered and six-membered rings, and conforming to the isolated pentagon rule, exhibit high electrical conductivity. Compared to fullerene molecules with other numbers of carbon atoms, C... 60 and C 70 It is more readily available and has more stable properties.

[0087] Through extensive experimental preparation and testing, the inventors discovered that halogenated fullerene pyrrolidine derivatives with the following side chain R have relatively high yields.

[0088] In some embodiments, R comprises any one of substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted 5-10-membered heteroaryl, or 5-10-membered heteroaryl-substituted C1-C3 alkyl. The substituents of the substituted C6-C10 aryl or substituted 5-10-membered heteroaryl in R include halogens, -SH, C1-C3 alkyl, C1-C3 haloalkyl, -C(O)O(C1-C3) alkyl, and -NR. 1 R 2 -P(O)(OR) 3 )2、-Si-(OR 4 )3. Any one of 15-18 crown ethers and 15-18 heterocrown ethers, R 1 R 2 Each R 3 Each R 4 Each is independently selected from H, C1-C3 alkyl, or tert-butoxycarbonyl.

[0089] In some embodiments, R includes substituted or unsubstituted C6-C10 aryl groups, wherein the aryl group is phenyl;

[0090] In some embodiments, R includes substituted or unsubstituted 5-10-membered heteroaryl groups, wherein the heteroaryl group is any one of thienyl, furanyl, thiazolyl, pyridyl, pyrimidinyl, oxazolyl or imidazole, preferably thiazolyl or pyridyl.

[0091] In some embodiments, R includes substituted or unsubstituted C1-C3 alkyl groups, wherein the alkyl group is selected from methyl or ethyl;

[0092] In some embodiments, R is selected from phenyl, thiazolyl, or pyridyl, and the pyridyl group is optionally 2-pyridyl, 3-pyridyl, or 4-pyridyl;

[0093] In some embodiments, the substituents of the C6-C10 aryl group and the substituted 5-10 heteroaryl group in R include any one of halogen, -SH, methyl, ethyl, propyl, trifluoromethyl, -C(O)OCH3, -C(O)OCH2CH3, -NH2, -NHBoc, -P(O)(OH)2, -P(O)(OCH2CH3)2, -Si-(OCH3)3, 15-18 crown ether, 15-18 aza crown ether, and 15-18 aza-sulfur co-crown ether;

[0094] In some embodiments, the substituents of the C6-C10 aryl group substituted in R, and the substituents of the substituted 5-10 heteroaryl group are selected from ethyl or -C(O)OCH2CH3.

[0095] In some embodiments, the number of substituents in R is 0, 1, 2, 3, 4 or 5, and can be selected as 0 or 1.

[0096] In some embodiments, each X in general formula I is independently any one of F, Cl, Br, or a C1-C3 haloalkyl group, optionally F, Cl, Br, or trifluoromethyl, and further optionally F or Br; n is 1 or 2, optionally 1. This allows the role of the halogen to be fully utilized.

[0097] In some embodiments, the halogenated fullerene pyrrolidine derivatives have the following general structural formula II:

[0098]

[0099] Although the mechanism is not yet clear, the inventors have discovered through a large number of experiments and tests that the electron transport performance is better when X in the halogenated fullerene pyrrolidine derivative is in the N para position.

[0100] In some embodiments, the halogenated fullerene pyrrolidine derivatives have the following general structural formula III:

[0101]

[0102] In some embodiments, the halogenated fullerene pyrrolidine derivative and its chemically acceptable salt are selected from any one or more of the following compounds:

[0103]

[0104]

[0105]

[0106] The second embodiment of this application provides a method for preparing a halogenated fullerene pyrrolidine derivative, which can be used to prepare any one of the halogenated fullerene pyrrolidine derivatives in the first embodiment. The method includes: reacting a fullerene, a halogen-substituted N-phenylglycine, and an aromatic aldehyde derivative in a solvent to obtain the halogenated fullerene pyrrolidine derivative; the halogen-substituted N-phenylglycine has structural formula IV:

[0107]

[0108] Aromatic aldehyde derivatives have the structural formula V:

[0109]

[0110] The definitions of X and n in structural formula IV and R in structural formula V are consistent with those in the first embodiment, and will not be repeated here.

[0111] This application utilizes the Prato reaction to synthesize halogenated fullerene pyrrolidine derivatives in one step, yielding a single [6,6] closed-ring product. Most of the precursors required for the reaction are commercially available or easily prepared, thus reducing the preparation cost. Two substituents can be introduced into the pyrrole ring simultaneously to achieve product diversification.

[0112] Fullerenes are reacted with halogenated amino acids and corresponding aldehydes under heating conditions to prepare halogenated fullerene pyrrolidine derivatives. This preparation method involves inexpensive and readily available raw materials, requires no metal catalysts, has broad applicability, and yields excellent products. Furthermore, the resulting halogenated fullerene pyrrolidine derivatives exhibit superior performance as electron transport materials in perovskite solar cells.

[0113] In some implementations... Choose one of the following structural formulas:

[0114]

[0115] In some implementations... Choose one of the following structural formulas:

[0116]

[0117] In some embodiments, the above reaction satisfies one or more of the following conditions: 1) the molar ratio of fullerene, halogenated N-phenylglycine, and aromatic aldehyde derivative is 1:(4-15):(2-15), optionally 1:(2-10):(2-10); 2) the reaction temperature is 60℃~150℃; 3) the solvent includes o-dichlorobenzene or chlorobenzene; 4) the reaction is carried out under nitrogen or inert gas protection. Under the above reaction conditions, the synthesis efficiency is high, and high reaction yield and product purity can be obtained. The specific raw materials, reaction conditions, etc., can be flexibly adjusted by those skilled in the art based on the above description, and this application does not impose any special limitations. Exemplarily, the preparation method of halogenated fullerene pyrrolidine derivatives can be achieved by: under N2 or inert gas protection, adding fullerene (e.g., C24) sequentially to a dry double-necked round-bottom beaker. 60 Or C 70 The reaction mixture is prepared by halogen-substituted N-phenylglycine and derivatives of the corresponding aromatic aldehydes, followed by the addition of o-dichlorobenzene (or chlorobenzene). The reaction mixture is sonicated to completely dissolve the derivatives, and then heated in an oil bath at 60℃~150℃ until the reaction is complete.

[0118] In some embodiments, the above preparation method further includes a process of purifying the halogenated fullerene pyrrolidine derivative, wherein the eluent used for purification includes one or a mixture of CS2, petroleum ether and toluene, and optionally the eluent includes a mixture of petroleum ether and toluene in a volume ratio of 1:1 to 10:1.

[0119] In some embodiments, the purification process includes cooling the reaction solution to room temperature and then performing multiple separation and purification steps. First, the reaction product is filtered through a short silica gel column to remove insoluble matter, and the solvent is removed by rotary evaporation to obtain a crude product. The crude product is dissolved in CS2, and further separation and purification are performed using a long thin-layer chromatography silica gel column. First, CS2 is used as the eluent to recover unreacted fullerenes. Then, based on the polarity differences of the fullerene derivatives, the volume ratio of petroleum ether to toluene in the eluent is adjusted before elution to obtain the target product, the halogenated fullerene pyrrolidine derivative. The above purification process can be referenced from the conventional purification process for fullerene pyrrolidine derivatives and will not be elaborated further here.

[0120] The third embodiment of this application provides the application of any of the halofullerene pyrrolidine derivatives and their chemically acceptable salts from the first embodiment in a battery. The aforementioned battery includes, but is not limited to, organic solar cells, perovskite solar cells, and fuel cells.

[0121] The aforementioned halogenated fullerene pyrrolidine derivatives, as highly efficient electron transport materials, can improve photoelectric conversion efficiency or chemical energy to electrical energy conversion efficiency when applied in the aforementioned batteries.

[0122] The fourth embodiment of this application provides a perovskite solar cell including an electron transport layer comprising a fullerene derivative, wherein "fullerene derivative" includes any of the halofullerene pyrrolidine derivatives of the first embodiment and their chemically acceptable salts.

[0123] In perovskite solar cells where organometal halides (BMs) serve as the light-absorbing layer, considering the destructive effect of solvents used to dissolve PbI₂ on the structure of the organic electron transport layer, halogenated fullerene pyrrolidine derivatives and their chemically acceptable salts are mostly used in inverted (pin-type) devices, i.e., deposited on top of the perovskite photoactive layer. The halogenated fullerene pyrrolidine derivatives of this application achieve photoelectric performance comparable to PCBMs, and their synthesis and separation processes are extremely simple and easy to perform. They can serve as an alternative electron transport material to PCBMs for the fabrication of perovskite solar cells and other photovoltaic devices.

[0124] A fifth embodiment of this application provides a fuel cell including an electrode assembly comprising a fullerene derivative, wherein "fullerene derivative" includes any of the halogenated fullerene pyrrolidine derivatives and their chemically acceptable salts as described in the first embodiment. Compared to the electrode assembly of a conventional fuel cell, when the electrode assembly comprises halogenated fullerene pyrrolidine derivatives and their chemically acceptable salts, the power density of the fuel cell can be significantly improved, thereby enhancing the power output capability of the fuel cell.

[0125] The beneficial effects of this application will be further illustrated below with reference to embodiments and comparative examples, but the scope of the present invention is not limited to these embodiments.

[0126] Unless otherwise specified, the raw materials and reagents used in the following examples and comparative examples are commercially available.

[0127] Synthesis Example 1

[0128] Synthesis and characterization of fullerene-pyrrolidine derivative L-6:

[0129]

[0130] The specific synthesis steps are as follows:

[0131] Weigh C 60144.0 mg (0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (135.3 mg, 0.8 mmol), and 4-thiazolyl carboxaldehyde (90.5 mg, 0.8 mmol) were dissolved in 20 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 2 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C2. 60 Then, using petroleum ether and toluene in a volume ratio of 5:1 as eluent, a brown solid L-6 (84.5 mg, yield 45%) was obtained.

[0132] like Figure 1 As shown, L-6's 1 1H NMR spectrum (500MHz, CS2 / DMSO): δ 8.87 (s, 1H), 8.24 (s, 1H), 7.51–7.50 (m, 2H), 7.11 (t, J = 7.5Hz, 2H), 6.92 (s, 1H), 5.50 (d, J = 10.0Hz, 1H), 5.14 (d, J = 10.0Hz, 1H).

[0133] APCI-MS: [M] - m / z = 939.3 (measured value), 940.05 (calculated value).

[0134] Synthesis Example 2

[0135] Synthesis and characterization of fullerene-pyrrolidine derivative L-17:

[0136]

[0137] Weigh C 60 144.0 mg (0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (135.3 mg, 0.8 mmol), and 4-propylthiazolyl carboxaldehyde (31.1 mg, 0.8 mmol) were dissolved in 30 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 1.5 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C2. 60 Then, petroleum ether and toluene in a volume ratio of 8:1 were used as eluents to obtain brown solid L-17 (81.0 mg, yield 41%).

[0138] like Figure 2 As shown, L-17's 1H NMR spectrum (500MHz, CS2 / DMSO): δ7.95(s,1H),7.49-7.47(m,2H),7.10(t,J=10.0Hz,2H),6.77(s,1H),5.46(d ,J=10.0Hz,1H),5.12(d,J=10.0Hz,1H),2.92(t,J=5.0Hz,2H),1.84-1.77(m,2H),0.99(t,J=7.5Hz,3H).

[0139] APCI-MS: [M] - m / z = 981.4 (measured value), 982.09 (calculated value).

[0140] Synthesis Example 3

[0141] Synthesis and characterization of fullerene-pyrrolidine derivative L-56:

[0142]

[0143] Weigh C 60 144.0 mg (0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (135.3 mg, 0.8 mmol), and oxazolaldehyde (0.06 mL, 0.8 mmol) were dissolved in 30 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 2.5 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C2. 60 Then, petroleum ether and toluene in a volume ratio of 4:1 were used as eluents to obtain brown solid L-17 (81.0 mg, yield 41%).

[0144] like Figure 3 As shown, L-56's 1 1H NMR spectrum (500MHz, CS2 / DMSO): δ 8.14 (s, 1H), 7.46 (s, 1H), 7.36–7.35 (m, 2H), 7.14–7.09 (m, 3H), 5.56 (d, J = 5.0Hz, 1H), 5.42 (d, J = 5.0Hz, 1H).

[0145] APCI-MS: [M] - m / z = 925.8 (measured value), 924.07 (calculated value).

[0146] Synthesis Example 4

[0147] Synthesis and characterization of fullerene-pyrrolidine derivative L-53:

[0148]

[0149] Weigh C 60 144.0 mg (0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (135.3 mg, 0.8 mmol), and ethyl 4-aldehyde phenyl phosphate (134.5 mg, 0.8 mmol) were dissolved in 30 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 7 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C. 60 Then, using petroleum ether and toluene in a volume ratio of 6:1 as eluent, a brown solid L-53 (70.6 mg, 33%) was obtained.

[0150] like Figure 4 As shown, L-53's 1 1H NMR spectrum (500MHz, CS2 / DMSO): δ 7.94-7.93 (m, 2H), 7.74-7.69 (m, 2H), 7.46-7.43 (m, 2H), 7.10 (t, J = 10Hz, 2H), 6.24 (s, 1H), 5.68 (d, J = 10.0Hz, 1H), 5.02 (d, J = 10.0Hz, 1H), 4.02-3.93 (m, 4H), 1.29-1.26 (m, 6H).

[0151] APCI-MS: [M] - m / z = 1068.4 (measured value), 1069.12 (calculated value).

[0152] Synthesis Example 5

[0153] Synthesis and characterization of fullerene-pyrrolidine derivative L-51:

[0154]

[0155] Weigh C 60 144.0 mg (0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (135.3 mg, 0.8 mmol), and thiophenecarboxaldehyde (0.072 mL, 0.8 mmol) were dissolved in 30 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 2.5 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C. 60 Then, using petroleum ether and toluene in a volume ratio of 8:1 as eluent, a brown solid L-51 (81.6 mg, 44%) was obtained.

[0156] like Figure 5 As shown, L-51's 1 1H NMR spectrum (500MHz, CDCl3): δ 7.41 (d, J = 5.0Hz, 1H), 7.37 (s, 1H), 7.34 (d, J = 5.0Hz, 3H), 7.30–7.29 (m, 1H), 7.00–6.99 (m, 1H), 6.56 (s, 1H), 5.57 (d, J = 10Hz, 1H), 5.09 (d, J = 10.0Hz, 1H).

[0157] APCI-MS: [M] - m / z = 954.8 (measured value), 955.02 (calculated value).

[0158] Synthesis Example 6

[0159] Synthesis and characterization of fullerene-pyrrolidine derivative L-52:

[0160]

[0161] Weigh C 60 144.0 mg (0.2 mmol), 2-((4-chlorophenyl)amino)acetic acid (150.0 mg, 0.8 mmol), and 4-trifluoromethyl-2-pyridinecarboxaldehyde (140.1 mg, 0.8 mmol) were dissolved in 20 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 3.5 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and then concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C2O3. 60 Then, using petroleum ether and toluene in a volume ratio of 4:1 as eluent, a brown solid L-52 (71.3 mg, 35%) was obtained.

[0162] like Figure 6 As shown, L-52's 1 H NMR spectrum (500MHz, CDCl3): δ8.95 (s, 1H), 7.93 (s, 2H), 7.34 (d, J = 10.0Hz, 2H), 7.2 0(d,J=10.0Hz,2H),6.55(s,1H),5.82(d,J=10Hz,2H),5.18(d,J=10.0Hz,1H).

[0163] APCI-MS: [M] - m / z = 1017.6 (measured value), 1018.05 (calculated value).

[0164] Synthesis Example 7

[0165] Synthesis and characterization of fullerene-pyrrolidine derivative L-40:

[0166]

[0167] Weigh C 60 144.0 mg (0.2 mmol), 2-((4-bromophenyl)amino)acetic acid (184.2 mg, 0.8 mmol), and 4-bromo-3-pyridinebenzaldehyde (149.1 mg, 0.8 mmol) were dissolved in 20 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 4 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C2. 60 Then, using petroleum ether and toluene in a volume ratio of 5:1 as eluent, a brown solid L-40 (73.1 mg, 34%) was obtained.

[0168] like Figure 7 As shown, L-40's 1 1H NMR spectrum (500MHz, CDCl3): δ 8.80 (s, 1H), 7.98 (d, J = 10.0Hz, 1H), 7.46 (d, J = 10.0Hz, 1H), 7.38–7.35 (m, 2H), 7.11 (t, J = 7.5Hz, 2H), 5.99 (s, 1H), 5.50 (d, J = 10.0Hz, 1H), 4.89 (d, J = 10.0Hz, 1H).

[0169] APCI-MS: [M] - m / z = 1071.4 (measured value), 1071.92 (calculated value).

[0170] Synthesis Example 8

[0171] Synthesis and characterization of fullerene-pyrrolidine derivative L-50:

[0172]

[0173] Weigh C 60 144.0 mg (0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (135.1 mg, 0.8 mmol), and 4-trifluoromethylpyridinecarboxaldehyde (140.1 mg, 0.8 mmol) were dissolved in 30 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 8 hours under N2 protection. After the reaction, the reaction solution was cooled to room temperature and concentrated under vacuum, followed by column chromatography. Unreacted C2 was first eluted with CS2 to remove C2. 60Then, using petroleum ether and toluene in a volume ratio of 4:1 as eluent, a brown solid L-50 (70.1 mg, 29%) was obtained.

[0174] like Figure 8 As shown, L-50's 1 1H NMR spectrum (500MHz, CDCl3): δ 8.98 (s, 1H), 8.11 (d, J = 10.0Hz, 1H), 8.04 (d, J = 10.0Hz, 1H), 7.33-7.31 (m, 2H), 7.06 (t, J = 7.5Hz, 1H), 6.86 (s, 1H), 5.98 (d, J = 10.0Hz, 1H), 5.28 (d, J = 10.0Hz, 1H).

[0175] APCI-MS: [M] - m / z = 1001.3 (measured value), 1002.08 (calculated value).

[0176] Synthesis Example 9

[0177] Synthesis and characterization of fullerene-pyrrolidine derivative L-66:

[0178]

[0179] Weigh C 60 144.0 mg (0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (175.3 mg, 0.8 mmol), and pentafluorobenzaldehyde (272.1 mL, 0.8 mmol) were dissolved in 30 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 10 hours under N2 protection. After the reaction, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C2. 60 Then, using petroleum ether and toluene in a volume ratio of 10:1 as eluents, a brown solid L-66 (70.1 mg, 31%) was obtained.

[0180] like Figure 9 As shown, L-66's 1 1H NMR spectrum (500MHz, CDCl3): δ 7.31-7.29 (m, 2H), 7.15 (t, J = 7.5Hz, 2H), 7.04 (s, 1H), 5.58 (d, J = 10.0Hz, 1H), 5.30 (dd, J = 5.0, 10.0Hz, 1H).

[0181] APCI-MS: [M] - m / z = 1022.7 (measured value), 1023.05 (calculated value).

[0182] Synthesis Example 10

[0183] Synthesis and characterization of fullerene-pyrrolidine derivative L-69:

[0184]

[0185] Weigh C 60 144.0 mg (0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (175.3 mg, 0.8 mmol), and 4'-aldehyde benzo-18-crown-6 (272 mg, 0.8 mmol) were dissolved in 30 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 10 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C64. 60 Then, using petroleum ether and toluene in a volume ratio of 5:1 as eluent, a brown solid L-69 (77.1 mg, 33%) was obtained.

[0186] like Figure 10 As shown, L-66's 1 H NMR spectrum (500MHz, CDCl3): δ7.45-7.42(m,2H),7.32-7.31(m,2H),7.11(t,J=7.5Hz,2H),6.85(d,J=10.0Hz,1H),6.03(s,1H),5.66(d,J=10.0Hz,1H), 4.96(d,J=10.0Hz,1H),4.08-4.04(m,3H),3.99-3.95(m,1H),3.81(t,J= 5.0Hz, 2H), 3.73 (t, J = 5.0Hz, 2H), 3.68-3.65 (m, 2H), 3.63-3.55 (m, 12H).

[0187] APCI-MS: [M] - m / z = 1167.1 (measured value), 1167.21 (calculated value).

[0188] Synthesis Example 11

[0189] Synthesis and characterization of fullerene-pyrrolidine derivative L-74:

[0190]

[0191] Weigh C 70188.0 mg (0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (175.32 mg, 0.8 mmol), and 4-pyridinecarboxaldehyde (0.075 mL, 0.8 mmol) were dissolved in 30 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 10 hours under N2 protection. After the reaction, the reaction solution was cooled to room temperature and concentrated under vacuum, followed by column chromatography. Unreacted C2 was first eluted with CS2 to remove C2. 70 Then, using petroleum ether and toluene in a volume ratio of 6:1 as eluent, a brown solid L-74 (78.0 mg, 37%) was obtained.

[0192] like Figure 11 As shown, L-74's 1 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ15.57 (s, 1H), 4.89 (d, J = 10.0Hz, 1H), 4.73 (d, J = 10.0Hz, 1H); δ2 5.47(s,1H),4.28(d,J=10.0Hz,1H),4.19(d,J=10.0Hz,1H); δ3 5.37(s,1H),5.33(d,J=10.0Hz,1H),4.43(d,J=10.0Hz,1H); δ4 5.13(s,1H),4.95(d,J=10.0Hz,1H),3.99(d,J=10.0Hz,1H). L-74 consists of four isomers, the ratio of which is obtained by integrating the signal peaks in the pyrrolidine region, and the ratio is 0.23:0.22:0.42:0.13.

[0193] like Figure 12 As shown, APCI-MS: [M] - m / z = 1053.35 (measured value), 1054.09 (calculated value).

[0194] Synthesis Example 12

[0195] Synthesis and characterization of fullerene-pyrrolidine derivative L-75:

[0196]

[0197] Weigh C 70188.0 mg (0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (175.32 mg, 0.8 mmol), and 2-aminopyrimidine formaldehyde (197 mg, 0.8 mmol) were dissolved in 30 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 10 hours under N2 protection. After the reaction, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C. 70 Then, using petroleum ether and toluene in a volume ratio of 4:1 as eluent, a brown solid L-75 (72.8 mg, 34%) was obtained.

[0198] like Figure 13 As shown, L-75's 1 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ15.42(s,1H),4.76(d,J=10.0Hz,1H),4.12(d,J =10.0Hz,1H); δ25.30(s,1H),4.81(d,J=10.0Hz,1H),4.19(d,J=10.0Hz,1H); δ3 5.20(d,J=10.0Hz,1H),5.18(s,1H),4.33(d,J=10.0Hz,1H); δ4 4.96(s,1H),4.59(d,J=10.0Hz,1H),3.90(d,J=10.0Hz,1H). L-75 consists of four isomers, the ratio of which is obtained by integrating the signal peaks in the pyrrolidine region, and the ratio is 0.26:0.21:0.36:0.17.

[0199] like Figure 14 As shown, APCI-MS: [M] - m / z = 1069.30 (measured value), 1070.10 (calculated value).

[0200] Synthesis Example 13

[0201] Synthesis and characterization of fullerene-pyrrolidine derivative L-76:

[0202]

[0203] Weigh C 70188.0 mg (0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (175.32 mg, 0.8 mmol), and 4'-aldehyde benzo-18-crown-6 (272 mg, 0.8 mmol) were dissolved in 30 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 10 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C64. 70 Then, using petroleum ether and toluene in a volume ratio of 4:1 as eluent, a brown solid L-76 (92.8 mg, 36%) was obtained.

[0204] like Figure 15 As shown, L-76's 1 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ1 5.38(s,1H),4.88(d,J=10.0Hz,1H),4.72(d,J=10.0Hz,1H); δ25.34(d,J=10.0Hz,1H),5.18(s,1H),4.36(d,J=10.0Hz,1H); δ3 5.29 (s, 1H), 4.88 (d, J = 10.0Hz, 1H), 4.72 (d, J = 10.0Hz, 1H); δ 44.96 (s, 1H), 4.94 (d, J = 10.0Hz, 1H), 4.21-4.19 (m, 1H). L-76 consists of four isomers, the ratio of which is obtained by integrating the signal peaks in the pyrrolidine region, and the ratio is 0.25:0.24:0.34:0.17.

[0205] like Figure 16 As shown, APCI-MS: [M] - m / z = 1287.20 (measured value), 1287.21 (calculated value).

[0206] Synthesis Example 14

[0207] Synthesis and characterization of fullerene-pyrrolidine derivative L-22:

[0208]

[0209] Weigh C 60144 mg (0.2 mmol), 2-((4-fluorophenyl)amino)acetic acid (175.32 mg, 0.8 mmol), and ethyl 4-aldehyde benzoate (62.5 μL, 0.8 mmol) were dissolved in 20 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 6 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C. 60 Then, petroleum ether and toluene in a volume ratio of 5:1 were used as eluents to obtain brown solid L-22 (83 mg, yield 41%).

[0210] like Figure 17 As shown, L-22's 1 H NMR spectrum (500MHz, CDCl3): δ8.03(d,J=5.0Hz,2H),7.89(d,J=10.0Hz,2H),7.38~7.30(m,2H),7.08(t,J=5.0Hz, 2H), 6.13 (s, 1H), 5.68 (d, J = 10.0Hz, 1H), 5.0 (d, J = 10.0Hz, 1H), 4.33 (q, J = 8.3Hz, 2H), 1.35 (t, J = 7.5Hz, 3H).

[0211] APCI-MS: [M] - m / z = 1004.6 (measured value), 1005.12 (calculated value).

[0212] Synthesis Example 15

[0213] Synthesis and characterization of fullerene-pyrrolidine derivative L-67:

[0214]

[0215] Weigh C 60 144 mg (0.2 mmol), 2-((4-trifluoromethylphenyl)amino)acetic acid (175.33 mg, 0.8 mmol), and 4-pyridinecarboxaldehyde (0.075 mL, 0.8 mmol) were dissolved in 20 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 6 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C2. 60 Then, using petroleum ether and toluene in a volume ratio of 5:1 as eluent, a brown solid L-67 (68.9 mg, yield 35%) was obtained.

[0216] like Figure 18 As shown, L-67's1 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ8.62(d,J=5.0Hz,2H),7.77(d,J=10.0Hz,2H),7.62(d,J=10. 0Hz, 2H), 7.42 (d, J = 5.0Hz, 2H), 6.62 (s, 1H), 5.93 (d, J = 10.0Hz, 1H), 5.41 (d, J = 15.0Hz, 1H).

[0217] APCI-MS: [M] - m / z = 983.8 (measured value), 984.09 (calculated value).

[0218] Synthesis Example 16

[0219] Synthesis and characterization of fullerene-pyrrolidine derivative L-11:

[0220]

[0221] Weigh C 60 288 mg (0.4 mmol), 2-((4-fluorophenyl)amino)acetic acid (270.6 mg, 1.6 mmol), and 2-pyridinecarboxaldehyde (0.15 mL, 1.6 mmol) were dissolved in 20 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 6 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C2. 60 Then, petroleum ether and toluene in a volume ratio of 5:1 were used as eluents to obtain brown solid L-11 (138.2 mg, yield 37%).

[0222] like Figure 19 As shown, L-11's 1 1H NMR spectrum (500MHz, CS2 / DMSO-d6): δ 8.71 (d, J = 5.0Hz, 1H), 7.84 (d, J = 10.0Hz, 1H), 7.74-7.71 (m, 1H), 7.32-7.25 (m, 3H), 7.05 (t, J = 10.0Hz, 2H), 6.64 (s, 1H), 5.98 (d, J = 5.0Hz, 1H), 5.24 (d, J = 5.0Hz, 1H).

[0223] APCI-MS: [M] - m / z = 933.3 (measured value), 934.09 (calculated value).

[0224] Synthesis Example 17

[0225] Synthesis and characterization of fullerene-pyrrolidine derivative L-15:

[0226]

[0227] Weigh C 60 288 mg (0.4 mmol), 2-((4-fluorophenyl)amino)acetic acid (270.6 mg, 1.6 mmol), and 3-pyridinecarboxaldehyde (0.15 mL, 1.6 mmol) were dissolved in 20 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 6 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C. 60 Then, petroleum ether and toluene in a volume ratio of 5:1 were used as eluents to obtain brown solid L-15 (153.2 mg, yield 41%).

[0228] like Figure 20 As shown, L-15's 1 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ9.03(d,J=5.0Hz,1H),8.50(d,J=5.0Hz,1H),8.12(d,J=10.0Hz,1H),7.49-7.46 (m,2H),7.31-7.28(m,1H),7.11(t,J=10.0Hz,2H),6.26(s,1H),5.64(d,J=10.0Hz,1H),5.02(d,J=10.0Hz,1H).

[0229] APCI-MS: [M] - m / z = 933.3 (measured value), 934.09 (calculated value).

[0230] Synthesis Example 18

[0231] Synthesis and characterization of fullerene-pyrrolidine derivative L-16:

[0232]

[0233] Weigh C 60 288 mg (0.4 mmol), 2-((4-fluorophenyl)amino)acetic acid (270.6 mg, 1.6 mmol), and 4-pyridinecarboxaldehyde (0.15 mL, 1.6 mmol) were dissolved in 20 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 5 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C2. 60Then, using petroleum ether and toluene in a volume ratio of 5:1 as eluent, a brown solid L-16 (160.7 mg, yield 43%) was obtained.

[0234] like Figure 21 As shown, L-16's 1 1H NMR spectrum (500MHz, CS2 / DMSO-d6): δ 8.56 (t, J = 5.0Hz, 2H), 7.74 (d, J = 5.0Hz, 2H), 7.45-7.42 (m, 2H), 7.11 (t, J = 10.0Hz, 3H), 6.21 (s, 1H), 5.67 (d, J = 10.0Hz, 1H), 5.02 (d, J = 10.0Hz, 1H).

[0235] APCI-MS: [M] - m / z = 933.3 (measured value), 934.09 (calculated value).

[0236] Synthesis Example 19

[0237] Synthesis and characterization of fullerene-pyrrolidine derivative L-78:

[0238]

[0239] Weigh C 60 288 mg (0.4 mmol), 2-((4-chlorophenyl)amino)acetic acid (297 mg, 1.6 mmol), and 4-pyridinecarboxaldehyde (0.15 mL, 1.6 mmol) were dissolved in 20 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 6 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C. 60 Then, using petroleum ether and toluene in a volume ratio of 6:1 as eluent, a brown solid L-78 (148.2 mg, yield 39%) was obtained.

[0240] like Figure 22 As shown, L-78's 1 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ8.59 (d, J = 5.0 Hz, 2H), 7.73 (d, J = 5.0 Hz, 1H), 7.34 (s, 4H), 6.29 (s, 1H), 5.76 (d, J = 10.0 Hz, 1H), 5.11 (d, J = 10.0 Hz, 1H).

[0241] APCI-MS: [M] - m / z = 949.6 (measured value), 950.06 (calculated value).

[0242] Synthesis Example 20

[0243] Synthesis and characterization of fullerene-pyrrolidine derivative L-79:

[0244]

[0245] Weigh C 60 288 mg (0.4 mmol), 2-((4-bromophenyl)amino)acetic acid (360 mg, 1.6 mmol), and 4-pyridinecarboxaldehyde (0.15 mL, 1.6 mmol) were dissolved in 20 mL of chlorobenzene and sonicated until completely dissolved. The mixture was then stirred at 120 °C for 5 hours under N2 protection. After the reaction was complete, the reaction solution was cooled to room temperature and concentrated under vacuum. The solution was then separated by column chromatography, first eluting with CS2 to remove unreacted C. 60 Then, petroleum ether and toluene in a volume ratio of 6:1 were used as eluents to obtain brown solid L-79 (147.1 mg, yield 37%).

[0246] like Figure 23 As shown, L-79's 1 H NMR spectrum (500MHz, CS2 / DMSO-d6): δ8.59(d,J=5.0Hz,2H),7.73(d,J=5.0Hz,2H),7.48(d,J=5.0 Hz, 2H), 7.29 (d, J = 5.0 Hz, 2H), 6.30 (s, 1H), 5.77 (d, J = 10.0 Hz, 1H), 5.13 (d, J = 10.0 Hz, 1H).

[0247] APCI-MS: [M] - m / z = 993.5 (measured value), 994.01 (calculated value).

[0248] Application Example A1: Application of L-22, a halofullerene pyrrolidine derivative, in perovskite solar cells

[0249]

[0250] The fabrication method of perovskite solar cells is as follows:

[0251] (1) Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) was dissolved in chlorobenzene at a concentration of 2 mg / mL, and the resulting solution was spin-coated onto a pre-cleaned indium tin oxide (ITO) conductive glass and annealed at 100 °C for 10 min. Iodine formamidine (FAI), methyl iodide (MAI), cesium iodide (CsI), lead iodide (PbI2), and lead bromide (PbBr2) powders were prepared according to (FA...0.95 MA 0.05 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05 The components of 3 were mixed and dissolved in a mixed solvent of N,N-dimethylacetamide / dimethyl sulfoxide at a volume ratio of 4:1 to prepare a perovskite precursor solution with a concentration of 1.4 mol / L. The pre-prepared perovskite precursor solution was then spin-coated onto a PTAA substrate and annealed at 110°C for 30 min to obtain a perovskite photoactive layer.

[0252] (2) The halo-fullerene pyrrolidine derivative L-22 was fully dissolved in o-dichlorobenzene at a concentration of 20 mg / mL, and the solution was spin-coated onto the perovskite photoactive layer as a fullerene electron transport layer.

[0253] (3) Dissolve 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) in isopropanol at 0.5 mg / mL, and spin-coat the resulting solution onto the fullerene electron transport layer as a hole blocking layer.

[0254] (4) A silver electrode was prepared by depositing 100 nm Ag onto the hole blocking layer to obtain a photovoltaic device (perovskite solar cell) based on L-22.

[0255] The photovoltaic performance of the above-mentioned perovskite solar cells was measured:

[0256] At a light intensity of 100mW / cm 2 Under AM 1.5G simulated sunlight irradiation, the open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency of an L-22-based perovskite solar cell were measured. The current density-voltage (JV) characteristic curve of this photovoltaic device is shown below. Figure 24 As shown.

[0257] Application Example A2:

[0258] The fullerene pyrrolidine derivative L-17 in Application Example A1 was replaced with the fullerene pyrrolidine derivative L-22, and the rest was the same as in Application Example A1.

[0259]

[0260] At a light intensity of 100mW / cm 2 Under AM 1.5G simulated sunlight irradiation, the open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency of an L-17-based perovskite solar cell were measured. The current density-voltage (JV) characteristic curve of this photovoltaic device is shown below. Figure 25 As shown.

[0261] Application Example A3

[0262] The fullerene pyrrolidine derivative L-11 in Application Example A1 was replaced with the fullerene pyrrolidine derivative L-22, and the rest was the same as in Application Example A1.

[0263]

[0264] The photovoltaic performance of the above-mentioned perovskite solar cells was measured:

[0265] At a light intensity of 100mW / cm 2 Under AM 1.5G simulated sunlight irradiation, the open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency of an L-11-based perovskite solar cell were measured. The current density-voltage (JV) characteristic curve of this photovoltaic device is shown below. Figure 26 As shown.

[0266] Application Example A4:

[0267] The fullerene pyrrolidine derivative L-15 in Application Example A1 was replaced with the fullerene pyrrolidine derivative L-22, and the rest was the same as in Application Example A1.

[0268]

[0269] The photovoltaic performance of the above-mentioned perovskite solar cells was measured:

[0270] At a light intensity of 100mW / cm 2 Under AM 1.5G simulated sunlight irradiation, the open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency of an L-15 based perovskite solar cell were measured. The current density-voltage (JV) characteristic curve of this photovoltaic device is shown below. Figure 27 As shown.

[0271] Application Example A5:

[0272] The fullerene pyrrolidine derivative L-16 in Application Example A1 was replaced with the fullerene pyrrolidine derivative L-22, and the rest was the same as in Application Example A1.

[0273]

[0274] The photovoltaic performance of the above-mentioned perovskite solar cells was measured:

[0275] At a light intensity of 100mW / cm 2Under AM 1.5G simulated sunlight irradiation, the open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency of an L-16-based perovskite solar cell were measured. The current density-voltage (JV) characteristic curve of this photovoltaic device is shown below. Figure 28 As shown.

[0276] Application Example A6:

[0277] The fullerene pyrrolidine derivative L-78 in Application Example A1 was replaced with the fullerene pyrrolidine derivative L-22, and the rest was the same as in Application Example A1.

[0278]

[0279] The photovoltaic performance of the above-mentioned perovskite solar cells was measured:

[0280] At a light intensity of 100mW / cm 2 Under AM 1.5G simulated sunlight irradiation, the open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency of an L-78-based perovskite solar cell were measured. The current density-voltage (JV) characteristic curve of this photovoltaic device is shown below. Figure 29 As shown.

[0281] Application Example A7:

[0282] The fullerene pyrrolidine derivative L-79 in Application Example A1 was replaced with the fullerene pyrrolidine derivative L-22, and the rest was the same as in Application Example A1.

[0283]

[0284] The photovoltaic performance of the above-mentioned perovskite solar cells was measured:

[0285] At a light intensity of 100mW / cm 2 Under AM 1.5G simulated sunlight irradiation, the open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency of the L-79-based perovskite solar cell were measured. The current density-voltage (JV) characteristic curve of this photovoltaic device is shown below. Figure 30 As shown.

[0286] Application Comparative Example 1:

[0287] The halogenated fullerene pyrrolidine derivative L-22 in Application Example A1 was replaced with a non-halogenated fullerene pyrrolidine derivative F1, and the rest was the same as in Application Example A1.

[0288] The molecular structure of the non-halogenated fullerene pyrrolidine derivative F1 is as follows:

[0289]

[0290] The photovoltaic performance of the above-mentioned perovskite solar cells was measured:

[0291] At a light intensity of 100mW / cm 2 Under AM 1.5G simulated sunlight irradiation, the open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency of an F1-based perovskite solar cell were measured. The current density-voltage (JV) characteristic curve of this photovoltaic device is shown below. Figure 24 As shown.

[0292] Application Comparative Example 2:

[0293] The fullerene derivative PCBM was used to replace the halofullerene pyrrolidine derivative L-22 in Application Example A1, and the rest was the same as in Application Example A1.

[0294] The molecular structure of the fullerene derivative PCBM is as follows:

[0295]

[0296] The fabrication method of perovskite solar cells is as follows:

[0297] The photovoltaic performance of the above-mentioned perovskite solar cells was measured:

[0298] At a light intensity of 100mW / cm 2 Under AM 1.5G simulated sunlight irradiation, the open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency of a PCBM-based perovskite solar cell were measured. The current density-voltage (JV) characteristic curve of this photovoltaic device is shown below. Figure 31 As shown.

[0299] The values ​​of open-circuit voltage, short-circuit current density, and fill factor can be obtained from the current density-voltage (JV) characteristic curve. The value corresponding to the intersection of the JV curve and the horizontal axis is the open-circuit voltage (V). oc The unit is V; the value corresponding to the intersection of the JV curve and the vertical axis of the coordinate system is the short-circuit current density (J). sc (Unit: mA / cm) 2 The point on the JV curve corresponding to the perovskite solar cell having the maximum power is P. max (V max J max The fill factor (FF) can be calculated as follows: FF = (V max ·J max ) / (V oc ·J scPhotovoltaic conversion efficiency (PCE) refers to the efficiency with which a perovskite solar cell converts solar energy into electrical energy, and can be calculated as follows: PCE = (V0 / V0)2 oc ·J sc ·FF) / P in , where P in The irradiance under simulated sunlight of AM 1.5G is 100mW / cm². 2 .

[0300] The open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency of the above application examples A1 to A7 and application comparison examples 1 and 2 are recorded in Table 1.

[0301] Table 1

[0302]

[0303] It is evident that the photoelectric conversion performance of the aforementioned halofullerene pyrrolidine derivatives L-22, L-17, L-11, L-15, L-16, L-78, and L-79 is comparable to that of PCBM, and their synthesis and separation processes are extremely simple and easy to perform. The halofullerene pyrrolidine derivatives of this invention can be used as electron transport materials to replace PCBM in the fabrication of photovoltaic devices such as perovskite solar cells. Furthermore, compared to the non-halogenated fullerene pyrrolidine derivative F1, the perovskite solar cells fabricated using the halofullerene pyrrolidine derivative L-22 of this invention exhibit significantly higher photoelectric conversion efficiency.

[0304] Application Example B1: Application of Halogenated Fullerene Pyrrolidine Derivative L-15 in Fuel Cells

[0305] The preparation method of fuel cells using L-15 as an electrode additive is as follows:

[0306] Commercial Pt / C, Nafion, and homemade fullerene were dissolved in isopropanol to prepare ink.

[0307] The prepared ink was sprayed onto both sides of a proton exchange membrane (Gore, 12 μm thick) to form an electrode area of ​​5 cm². 2 Catalyst coating film (CCM);

[0308] The obtained CCM is placed between two pieces of carbon paper to form a membrane electrode assembly (MEA);

[0309] The above membrane electrode assembly was assembled into an H2-O2 fuel cell and an H2-Air fuel cell, respectively. The flow rates of both H2 and O2 / Air gases were 1000 sccm / 1000 sccm (2000 sccm), the back pressure was 100 kPa, and the noble metal loadings at both the anode and cathode were 0.1 mg·cm³. -2 .

[0310] The H2-O2 fuel cell was tested using an 850E Multi Range fuel cell test station at a battery temperature of 80°C. After introducing the halotype fullerene pyrrolidine derivative L-15, the power density increased from 1.87 W·cm³ before its introduction. -2 Increased to 2.83 W·cm -2 The polarization and power density curves of fuel cells using L-15 as an electrode additive are shown below. Figure 32 As shown.

[0311] The H2-Air fuel cell was tested using an 850E Multi Range fuel cell test station at a battery temperature of 80°C. After introducing the halogenated fullerene pyrrolidine derivative L-15, the power density increased from 0.84 W·cm³ before its introduction. -2 Increased to 1.6W·cm -2 The polarization and power density curves of fuel cells using L-15 as an electrode additive are shown below. Figure 33 As shown.

[0312] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A halogenated fullerene pyrrolidine derivative or a chemically acceptable salt thereof, said halogenated fullerene pyrrolidine derivative having the general structural formula II: Structural Formula II in, The fullerene ring is a C60 fullerene ring or a C70 fullerene ring; X is any one of F, Cl, Br or C1-C3 haloalkyl; n is 1; R is selected from any one of substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted pyridyl, thiazolyl, pyrimidinyl, the substituents of the substituted C6-C10 aryl, substituted pyridyl or thiazolyl or pyrimidinyl in said R are selected from halogen, -SH, C1-C3 alkyl, C1-C3 haloalkyl, -C(O)O(C1-C3)alkyl, -NR 1 R 2 , -P(O)(OR 3 )2, -Si-(OR 4 )3, any one of 15-18 crown ether, R 1 , R 2 , R 3 , R 4 are each independently selected from any one of H, C1-C3 alkyl, tert-butyloxycarbonyl.

2. The halogenated fullerene pyrrolidine derivative according to claim 1, or a chemically acceptable salt thereof, wherein, X is F, Cl, Br or trifluoromethyl.

3. The halogenated fullerene pyrrolidine derivative or a chemically acceptable salt thereof according to claim 2, wherein, X is either F or Br.

4. The halogenated fullerene pyrrolidine derivative or a chemically acceptable salt thereof according to any one of claims 1 to 3, wherein, The aryl group in the substituted or unsubstituted C6-C10 aryl group is phenyl.

5. The halogenated fullerene pyrrolidine derivative or a chemically acceptable salt thereof according to any one of claims 1 to 3, wherein, The R is selected from phenyl, thiazolyl, or pyridinyl.

6. The halogenated fullerene pyrrolidine derivative according to claim 5, or a chemically acceptable salt thereof, wherein, The pyridyl group is 2-pyridyl, 3-pyridyl, or 4-pyridyl.

7. The halogenated fullerene pyrrolidine derivative according to claim 6, or a chemically acceptable salt thereof, wherein, The pyridyl group is 3-pyridyl or 4-pyridyl.

8. The halogenated fullerene pyrrolidine derivative or a chemically acceptable salt thereof according to any one of claims 1 to 3, wherein, The aryl, pyridyl, thiazolyl, or pyrimidinyl substituents of C6-C10 in R are selected from any one of halogens, -SH, methyl, ethyl, propyl, trifluoromethyl, -C(O)OCH3, -C(O)OCH2CH3, -NH2, -NHBoc, -P(O)(OH)2, -P(O)(OCH2CH3)2, -Si-(OCH3)3, and 15-18 crown ethers.

9. The halogenated fullerene pyrrolidine derivative according to claim 8, or a chemically acceptable salt thereof, wherein, The substituted C6-C10 aryl, pyridyl, thiazolyl, or pyrimidinyl substituents in R are selected from ethyl or -C(O)OCH2CH3; and / or, The number of substituents in R is 1, 2, 3, 4 or 5.

10. The halogenated fullerene pyrrolidine derivative of claim 9 or a chemically acceptable salt thereof, wherein, The number of substituents in R is 1.

11. The halogenated fullerene pyrrolidine derivative or a chemically acceptable salt thereof according to any one of claims 1 to 3, wherein, The haloform fullerene pyrrolidine derivative has the following general structural formula III: Structural Formula III.

12. A halohydrin pyrrolidine derivative or a chemically acceptable salt thereof, wherein, The haloform fullerene pyrrolidine derivative or its chemically acceptable salt is selected from any one of the following compounds: 。 13. A method for preparing a halofullerene pyrrolidine derivative according to any one of claims 1 to 12, wherein, The preparation method includes: The fullerene, halogenated N-phenylglycine, and aromatic aldehyde derivatives are reacted in a solvent to obtain the halogenated fullerene pyrrolidine derivative. The halogen-substituted N-phenylglycine has structural formula IV: Structural IV; The aromatic aldehyde derivative has the structural formula V: Structural form V; The definitions of X in structural formula IV and R in structural formula V are the same as those defined in any one of claims 1 to 12.

14. The preparation method according to claim 13, wherein, The reaction satisfies one or more of the following conditions: 1) The molar ratio of the fullerene, the halogen-substituted N-phenylglycine, and the aromatic aldehyde derivative is 1:(4-15):(2-15); 2) The reaction temperature is 60℃-150℃; 3) The solvent is selected from o-dichlorobenzene or chlorobenzene; 4) The reaction is carried out under the protection of nitrogen or an inert gas.

15. The preparation method according to claim 14, wherein, The molar ratio of the fullerene, the halogen-substituted N-phenylglycine, and the aromatic aldehyde derivative is 1:(2-10):(2-10).

16. The preparation method according to any one of claims 13 to 15, wherein, The preparation method further includes a process of purifying the halogenated fullerene pyrrolidine derivative, wherein the eluent used for purification is selected from one or more of CS2, petroleum ether and toluene, or a mixture thereof.

17. The preparation method according to claim 16, wherein, The eluent is a mixture of petroleum ether and toluene in a volume ratio of 1:1 to 10:

1.

18. The use of a halofullerene pyrrolidine derivative or a chemically acceptable salt thereof, as described in any one of claims 1 to 12, in a perovskite solar cell or fuel cell.

19. A perovskite solar cell comprising an electron transport layer comprising a fullerene derivative, wherein the fullerene derivative is a halogenated fullerene pyrrolidine derivative of any one of claims 1 to 12 or a chemically acceptable salt thereof.

20. A fuel cell comprising an electrode assembly comprising a fullerene derivative, wherein the fullerene derivative is a halogenated fullerene pyrrolidine derivative of any one of claims 1 to 12 or a chemically acceptable salt thereof.

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