Preparation method and application of [60] fullerene 3-hydroxyindan and derivative thereof

Abstract

The invention discloses a preparation method and application of [60] fullero-3-hydroxyindan and derivatives thereof, and the preparation method comprises the following steps: taking [60] fullerene and halogenated benzaldehyde as reaction substrates, and carrying out one-step thermal reaction under the action of a catalyst, an acid catalyst, a main solvent and a cosolvent to obtain a target product [60] fullero-3-hydroxyindan derivative. The obtained [60] fullerene 3-hydroxyindan is subjected to derivatization research, and an ester derivative of the [60] fullerene 3-hydroxyindan derivative is further synthesized. The obtained [60] fullerene indan derivatives are novel in structure, and most of the [60] fullerene indan derivatives have good solubility and selectivity. A compound redox potential map obtained through cyclic voltammetry testing shows that the compound has good redox activity and has certain application potential in the field of solar cells.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis and relates to a preparation method and application of

[60] fullerene 3-hydroxyindane and its derivatives. Background Art

[0002]

[60] Fullerene, as a crucial electron transport material (ETM), has attracted widespread attention in the field of inverted perovskite solar cells (IPSCs). Its advantages mainly come from the uniform and stable structure formed by thermal deposition technology. In recent years, researchers have successfully developed a variety of functionalized fullerene derivatives through chemical modification and applied them in IPSCs, showing excellent performance. In particular, the strategy of combining indane structure with fullerene has attracted widespread attention.

[0003] As shown in Formula 1, in 2011, Professor Wang Guanwu's research group reported a manganese acetate-promoted free radical reaction of

[60] fullerene with 2-arylmalonate, 2-benzylmalonate and 2-arylcyanoacetate to prepare

[60] fullerene-fused tetralin and indane derivatives (Organic Letters, 2011, 13: 6130-6133).

[0004]

[0005] As shown in Formula 2, Professor Wang Guanwu's research group reported in 2013 that FeCl 3 The promoted reaction of

[60] fullerene with N-benzylsulfonamide gave

[60] fullerene-fused indane derivatives (Organic letters, 2013, 15: 3408-3411.).

[0006]

[0007] As shown in Equation 3, Professor Wang Guanwu's research group reported in 2016 that palladium-catalyzed enolate-directed sp 2 CH bond activation and sp 3 The CH bond functionalization reaction achieved the coupling of

[60] fullerene with 2-arylcyclic 1,3-dicarbonyl compounds and prepared

[60] fullerene-fused spiroindene derivatives (Organic letters, 2016, 18: 2616-2619).

[0008]

[0009] In 2023, a research team led by Yutaka Matsuo successfully synthesized a fullerene derivative fullerene indanone (FIDO) with evaporation properties, which endowed IPSC with high power conversion efficiency (PCE) and long-lasting storage stability (as shown in Formula 4) (Journal of the American Chemical Society, 2023, 145: 27307-27315).

[0010]

[0011] In 2024, a research team led by Yutaka Matsuo successfully synthesized a hydrophobic, evaporable

[60] fullerene-5-trifluoromethylindanone (CF 3 -FIDO) (as shown in Formula 5), ​​which provides the lowest sublimation temperature reported so far for fullerene monoadduct derivatives. 3 -FIDO was used as an electron transport layer (ETL) in perovskite solar cells. After 500 hours in air, the device showed long-term stability and maintained 60% of its initial photoelectric conversion efficiency (Chemical Communications, 2024, 60:9420-9423).

[0012]

[0013] The research shows that these new

[60] fullerene and indane derivatives have great potential and broad application prospects in the field of solar cells. However, the structural types and synthetic routes of

[60] fullerene and indane derivatives are relatively limited, and the synthetic raw materials used are mostly complex. Therefore, it is urgent to expand the structural diversity of

[60] fullerene and indane derivatives and develop an efficient method for synthesizing such compounds. Summary of the invention

[0014] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a preparation method and application based on a

[60] fullerene and 3-hydroxyindane and its derivatives, mainly using

[60] fullerene, palladium acetate, halogenated benzaldehyde and p-toluenesulfonic acid monohydrate to react and prepare

[60] fullerene and 3-hydroxyindane and its derivatives, and then on the basis of

[60] fullerene and 3-hydroxyindane, derivatization research is carried out to increase the types and methods of synthesizing new

[60] fullerene and indane derivatives, and to improve the yield of these target derivatives and verify the universality of the products. The redox potential diagram of the compound is obtained by cyclic voltammetry test to show that it has good redox activity and has certain application potential in the field of solar cells.

[0015] The present invention adopts the following technical solutions:

[0016] A method for preparing a derivative of

[60] fullerene and 3-hydroxyindane based on palladium acetate catalysis comprises the following preparation steps:

[0017] In the first step,

[60] fullerene and o-halogenated benzaldehyde derivatives were used as raw materials, palladium acetate was used as a catalyst, and p-toluenesulfonic acid monohydrate (TsOH·H 2 O) as an acid catalyst, o-dichlorobenzene (ODCB) as the main solvent, acetonitrile as the co-solvent, heating reaction in air to synthesize the derivative of

[60] fullerene and 3-hydroxyindane:

[0018]

[0019] In the second step, the derivative of

[60] fullerene and 3-hydroxyindane and aromatic carboxylic acid are used as raw materials, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI) is used as a dehydrating agent for esterification reaction, 4-dimethylaminopyridine (DMAP) is used as an acyl transfer agent, and o-dichlorobenzene is used as a solvent. The reaction is heated in air to synthesize the ester derivative of

[60] fullerene and 3-hydroxyindane:

[0020]

[0021] Where R 1 is a hydrogen atom or a halogen atom, R 2 It is one of a hydrogen atom, a methyl group, a phenyl group, a halogen atom and a carboxyl group.

[0022] Preferably, in step 1, the molar ratio of

[60] fullerene, palladium acetate, o-halogenated benzaldehyde derivative and p-toluenesulfonic acid monohydrate is 1:0.4:2:2, and the heating reaction temperature is 80°C.

[0023] Preferably, the synthesis equation of step 1 is:

[0024]

[0025] I is a halogen atom.

[0026] Preferably, in step 2, the molar ratio of the

[60] fullerene 3-hydroxyindane derivative, aromatic carboxylic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI) and 4-dimethylaminopyridine (DMAP) is 1:5:2:3, and the heating reaction temperature is 150°C.

[0027] Preferably, the synthesis equation of step 2 is:

[0028]

[0029] Preferably, the specific steps of preparing the

[60] fullerene 3-hydroxyindane derivative in step 1 are:

[0030]

[60] fullerene, o-halogenated benzaldehyde derivative, p-toluenesulfonic acid monohydrate, and palladium acetate were added to a round-bottom flask, and o-dichlorobenzene was added as the main solvent and acetonitrile as the auxiliary solvent, and then completely dissolved under an ultrasonicator. The mixture was then heated and stirred in an oil bath under air conditions and tracked by thin layer chromatography (TLC) spot plate.

[0031] After the reaction is completed, the reaction solution is first cooled with room temperature water, and then directly added to a silica gel column for separation. Unreacted

[60] fullerene is first obtained using carbon disulfide as an eluent, and then carbon disulfide and dichloromethane are used as eluents for further separation to finally obtain a brown solid

[60] fullerene and 3-hydroxyindane derivative.

[0032] The o-halogenated benzaldehyde derivatives include one or more of 2-iodobenzaldehyde, 5-bromo-2-iodobenzaldehyde, 4-bromo-2-iodobenzaldehyde, and 5-fluoro-2-iodobenzaldehyde.

[0033] Preferably, the specific steps of preparing the ester derivative of

[60] fullerene-3-hydroxyindane in step 2 are:

[0034]

[60] fullerene and 3-hydroxyindane derivatives, aromatic carboxylic acids, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI) and 4-dimethylaminopyridine (DMAP) are added to a reaction bottle. The compound is then completely dissolved in o-dichlorobenzene by ultrasonic oscillation, the reaction solution is placed in a preset oil bath and heated and stirred under air conditions, and the reaction is tracked by thin layer chromatography (TLC). When the reaction stops, the untreated reaction solution is filtered using a short silica gel column, and the solvent is removed under reduced pressure to obtain a crude product. Finally, column chromatography technology is used for separation and purification. The crude product is first dissolved with a small amount of carbon disulfide, and the target product is first obtained using carbon disulfide as an eluent, and then carbon disulfide and dichloromethane are used as eluents to continue to obtain unreacted

[60] fullerene and 3-hydroxyindane derivatives.

[0035] The aromatic carboxylic acid includes one or more of benzoic acid, o-toluic acid, 4-phenylbenzoic acid, 5-chloro-2-iodobenzoic acid, and terephthalic acid.

[0036] The brown solid

[60] fullerene 3-hydroxyindane derivative comprises one of the following compounds:

[0037]

[0038] The step 2 of preparing the ester derivative of

[60] fullerene-3-hydroxyindane comprises one of the following compounds:

[0039]

[0040] Compared with the prior art, the present invention has the following outstanding advantages:

[0041] 1. The

[60] fullerene-3-hydroxyindane and its ester derivatives, namely

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate, prepared by the present invention have great application prospects in the field of inverted perovskite solar cells (IPSCs). Specifically: due to its unique electronic properties and structural stability, it can improve the photoelectric conversion efficiency and device stability of IPSCs; as an electron transport layer material, it effectively promotes the injection and transmission of electrons and reduces the recombination loss; as a light absorption layer material, it helps to improve the light absorption efficiency and photocurrent of solar cells.

[0042] 2. The

[60] fullerene derivative obtained by the method has a novel structure, enriching the preparation method of novel

[60] fullerene and indane derivatives. The product has excellent solubility and selectivity, and is convenient for separation and purification operations. If terephthalic acid is selected as the raw material in the preparation of

[60] fullerene 2,3-dihydro-1H-indene-1-ylbenzoate, a

[60] fullerene double ball structure can be prepared, which provides a new method for preparing

[60] fullerene double ball structure.

[0043] 3. The substrate used in the present invention has a wide range of applications and good universality, and the method for preparing

[60] fullerene-3-hydroxyindane and

[60] fullerene 2,3-dihydro-1H-indane-1-yl benzoate can be prepared by a one-step thermal reaction in the air. Compared with the prior art, the technology shows higher tolerance in preparation conditions and processes, and effectively reduces the difficulty of synthesizing

[60] fullerene-indane derivatives.

[0044] 4. In the process of preparing

[60] fullerene-3-hydroxyindane, compared with only changing the type of promoter under the condition of keeping other conditions unchanged, the use of p-toluenesulfonic acid monohydrate can greatly improve the selectivity of the system.

[0045] 5. The redox potential diagram of the compound obtained by cyclic voltammetry test can show that it has good redox activity and has certain application potential in the field of solar cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 The present invention is Example 1

[60] fullerene 3-hydroxyindane A 1 H NMR spectrum;

[0047] Figure 2 The present invention is Example 1

[60] fullerene 3-hydroxyindane A 13 C NMR spectrum;

[0048] Figure 3 Example 2 of the present invention

[60] fullerene 3-hydroxyindane B 1 H NMR spectrum;

[0049] Figure 4 Example 2 of the present invention

[60] fullerene 3-hydroxyindane B 13 C NMR spectrum;

[0050] Figure 5 Example 3 of the present invention

[60] fullerene 3-hydroxyindane C 1 H NMR spectrum;

[0051] Figure 6 Example 3 of the present invention

[60] fullerene 3-hydroxyindane C 13 C NMR spectrum;

[0052] Figure 7 Example 4

[60] Fullerene 3-hydroxyindane D of the present invention 1 H NMR spectrum;

[0053] Figure 8 Example 4

[60] Fullerene 3-hydroxyindane D of the present invention 13 C NMR spectrum;

[0054] Fig. 9 Example 5

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate E of the present invention 1 H NMR spectrum;

[0055] Fig.10 Example 5

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate E of the present invention 13 C NMR spectrum;

[0056] Fig.11 Example 6 of the present invention

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate F 1 H NMR spectrum;

[0057] Fig.12 Example 6 of the present invention

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate F 13 C NMR spectrum;

[0058] Fig.13Example 7 of the present invention

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate G 1 H NMR spectrum;

[0059] Fig.14 Example 7 of the present invention

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate G 13 C NMR spectrum;

[0060] Fig.15 Example 8 of the present invention

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate H 1 H NMR spectrum;

[0061] Fig.16 Example 8 of the present invention

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate H 13 C NMR spectrum;

[0062] Fig.17 Example 9 of the present invention

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate I 1 H NMR spectrum;

[0063] Fig.18 is the by-product

[60] fullerene indanone J synthesized in Comparative Example 1 1 H NMR spectrum;

[0064] Fig.19 It is for the published

[60] fullerenoindanone J 1 H NMR spectrum;

[0065] Fig. 20 This is a TLC plate comparison chart of the reaction endpoints of Example 1 and Comparative Example 1;

[0066] Fig.21 This is a TLC plate comparison chart of the reaction endpoints of Example 1 and Comparative Example 2;

[0067] Fig. 22 This is a TLC plate comparison chart of the reaction endpoints of Example 1 and Comparative Example 3;

[0068] Fig.23 This is the CV curve of

[60] fullerene 3-hydroxyindane A. Specific implementation plan

[0069] The above contents of the present invention are further described in detail below through examples, but the contents of the present invention are not limited by these examples.

[0070] Example 1

[0071] This example introduces

[60] fullereno-3-hydroxyindane A Preparation method:

[0072]

[60] fullerene (36.0 mg, 0.05 mmol), 2-iodobenzaldehyde (23.2 mg, 0.1 mmol), p-toluenesulfonic acid monohydrate (19.0 mg, 0.1 mmol), palladium acetate (4.5 mg, 0.02 mmol) were added to a flask and treated with ultrasound in an ultrasonic cleaner using a mixed solution of 6 mL of o-dichlorobenzene and 0.5 mL of acetonitrile to ensure that the mixture was completely dissolved. Subsequently, the solution was quickly transferred to an oil bath preset at 80 °C and heated with stirring at this temperature for 12 hours. The progress of the reaction was monitored by thin layer chromatography (TLC) until the reaction reached the end point and the heating was stopped.

[0073] After the reaction is terminated, the reaction mixture is preliminarily purified by a short silica gel column to remove insoluble impurities therein, and then the solvent is removed by vacuum distillation in a rotary evaporator, and the residue is further chromatographed by a chromatography column. Using carbon disulfide as an eluent, unreacted

[60] fullerene is first separated, and then a mixed solution of carbon disulfide and dichloromethane is used as an eluent to further separate brown solid

[60] fullerene and 3-hydroxyindane A. The yield of

[60] fullerene and 3-hydroxyindane A in this example is 32%.

[0074] The reaction synthesis equation is:

[0075]

[0076] like Figure 1 As shown, it is

[60] fullerene 3-hydroxyindane A 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / DMSO-d 6 )δ8.07–8.00(m,1H),7.96–7.89(m,1H),7.64–7.54(m,2H),7.05(d,J=7.3Hz,1H),6.84(d,J=7.3Hz,1H).

[0077] like Figure 2 As shown, it is

[60] fullerene 3-hydroxyindane A 13 C NMR spectrum 13 C NMR (150MHz, CS 2 / DMSO-d 6)(all 1C unless indicated)δ156.87,154.58,154.26,153.56,146.52,146.02,145.97,145.42,145.13,144.90(2C),144.75,14 4.67(3C),144.62(2C),144.54,144.43,144.07,143.99(2C),143.94,143.87(3C),143.81,143.44(2C),143.34 ,143.12,143.04,142.53,141.85,141.76,141.38,141.25,141.20(2C),141.07(3C),140.96,140.71(2C),140. 52(2C),140.47(2C),140.34,139.29,138.89,138.55,138.22,135.29,134.68,134.02,133.24,129.02(2C,aryl C),128.19(2C,aryl C),126.80(aryl C),124.31(arylC),83.55,75.88,73.00.

[0078] Example 2

[0079] This example introduces

[60] fullereno-3-hydroxyindan B Preparation method:

[0080]

[60] fullerene (36.0 mg, 0.05 mmol), 5-bromo-2-iodobenzaldehyde (31.1 mg, 0.1 mmol), p-toluenesulfonic acid monohydrate (19.0 mg, 0.1 mmol), palladium acetate (4.5 mg, 0.02 mmol) were added to a flask and treated with ultrasound in an ultrasonic cleaner using a mixed solution of 6 mL of o-dichlorobenzene and 0.5 mL of acetonitrile to ensure that the mixture was completely dissolved. Subsequently, the solution was quickly transferred to an oil bath preset at 80°C and heated with stirring at this temperature for 12 hours. The progress of the reaction was monitored by thin layer chromatography (TLC) until the reaction reached the end point and heating was stopped.

[0081] After the reaction is terminated, the reaction mixture is preliminarily purified by a short silica gel column to remove insoluble impurities therein, and then the solvent is removed by vacuum distillation in a rotary evaporator, and the residue is further chromatographed by a chromatography column. Using carbon disulfide as an eluent, unreacted

[60] fullerene is first separated, and then a mixed solution of carbon disulfide and dichloromethane is used as an eluent to further separate brown solid

[60] fullerene and 3-hydroxyindane B. The yield of

[60] fullerene and 3-hydroxyindane B in this example is 31%.

[0082] The reaction synthesis equation is:

[0083]

[0084] like Figure 3 As shown, it is

[60] fullerene 3-hydroxyindane B 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / DMSO-d 6 )δ8.07(d,J=1.9Hz,1H),7.96(d,J=8.2Hz,1H),7.71(dd,J=8.2,1.9Hz,1H),7.14(d,J=7.0Hz,1H),6.82(d,J=7.0Hz,1H).

[0085] like Figure 4 As shown, it is

[60] fullerene 3-hydroxyindane B 13 C NMR spectrum 13 C NMR (150MHz, CS 2 / CDCl 3)(all 1C unless indicated)δ155.89,153.59,152.82,152.47,146.56(2C),146.47(2C),146.09,145.74,145.40(3C),145.28(2 C),145.25(3C),145.21,144.73,144.69,144.60,144.50,144.47,144.39(3C),144.35,143.72,143.69,143.51 ,143.48,142.31,142.26,141.87,141.80,141.72(2C),141.45,141.37(3C),141.24,141.14,141.11,141.04,1 40.96,140.85,139.81,139.55,139.24,139.02,135.74(2C),134.74,134.42,133.86,133.14,126.47(2C,aryl C),123.45(aryl C),123.11(aryl C),122.89(aryl C),118.29(aryl C),77.02,73.05(2C).

[0086] Example 3

[0087] This example introduces

[60] fullereno-3-hydroxyindan C Preparation method:

[0088]

[60] fullerene (36.0 mg, 0.05 mmol), 4-bromo-2-iodobenzaldehyde (31.1 mg, 0.1 mmol), p-toluenesulfonic acid monohydrate (19.0 mg, 0.1 mmol), and palladium acetate (4.5 mg, 0.02 mmol) were added to a flask and treated with ultrasound in an ultrasonic cleaner using a mixed solution of 6 mL of o-dichlorobenzene and 0.5 mL of acetonitrile to ensure that the mixture was completely dissolved. Subsequently, the solution was quickly transferred to an oil bath set at a preset temperature of 80°C and heated with stirring at this temperature for 12 hours. The progress of the reaction was monitored by thin layer chromatography (TLC) until the reaction reached the endpoint and the heating was stopped.

[0089] After the reaction is terminated, the reaction mixture is preliminarily purified by a short silica gel column to remove insoluble impurities therein, and then the solvent is removed by vacuum distillation in a rotary evaporator, and the residue is further chromatographed by a chromatography column. Using carbon disulfide as an eluent, unreacted

[60] fullerene is first separated, and then a mixed solution of carbon disulfide and dichloromethane is used as an eluent to further separate brown solid

[60] fullerene and 3-hydroxyindane C. The yield of

[60] fullerene and 3-hydroxyindane C in this example is 28%.

[0090] The reaction synthesis equation is:

[0091]

[0092] like Figure 5 As shown, it is

[60] fullerene and 3-hydroxyindane C 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / DMSO-d 6 )δ8.17(d,J=1.8Hz,1H),7.85(d,J=8.1Hz,1H),7.70(dd,J=8.2,1.8Hz,1H),7.14(d,J=7.1Hz,1H),6.78(d,J=7.1Hz,1H).

[0093] like Figure 6 As shown, it is

[60] fullerene and 3-hydroxyindane C 13 C NMR spectrum 13 C NMR (150MHz, CS 2 / CDCl 3)(all 1C unless indicated)δ155.57,153.25,152.53,152.26,146.47,146.37,145.91,145.31(3C),145.18,145.11(2C),145. 08(3C),144.64(3C),144.48(2C),144.38(2C),144.30(3C),144.25,143.96,143.58(2C),143.42,143.39,142 .20,142.15,141.76,141.70,141.64,141.62,141.33,141.24(2C),141.12,141.08,141.03,140.94,140.90,1 40.84,140.79,139.76,139.50,139.17,138.97,135.61,134.68(2C),134.33,133.78,132.42,128.06(3C,aryl C),124.58(3C,aryl C),76.13,72.67(2C).

[0094] Example 4

[0095] This example introduces

[60] fullereno-3-hydroxyindane D Preparation method:

[0096]

[60] fullerene (36.0 mg, 0.05 mmol), 5-fluoro-2-iodobenzaldehyde (25.0 mg, 0.1 mmol), p-toluenesulfonic acid monohydrate (19.0 mg, 0.1 mmol), palladium acetate (4.5 mg, 0.02 mmol) were added to a flask and treated with ultrasound in an ultrasonic cleaner using a mixed solution of 6 mL of o-dichlorobenzene and 0.5 mL of acetonitrile to ensure that the mixture was completely dissolved. Subsequently, the solution was quickly transferred to an oil bath set at a preset temperature of 80°C and heated with stirring at this temperature for 12 hours. The progress of the reaction was monitored by thin layer chromatography (TLC) until the reaction reached the end point and the heating was stopped.

[0097] After the reaction is terminated, the reaction mixture is preliminarily purified by a short silica gel column to remove insoluble impurities therein, and then the solvent is removed by vacuum distillation in a rotary evaporator, and the residue is further chromatographed by a chromatography column. Using carbon disulfide as an eluent, unreacted

[60] fullerene is first separated, and then a mixed solution of carbon disulfide and dichloromethane is used as an eluent to further separate brown solid

[60] fullerene and 3-hydroxyindane D. The yield of

[60] fullerene and 3-hydroxyindane D in this example is 28%.

[0098] The reaction synthesis equation is:

[0099]

[0100] like Figure 7 As shown, it is

[60] fullerene 3-hydroxyindane D 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / DMSO-d 6 )δ8.03(dd,J=8.5,4.8Hz,1H),7.61(dd,J=8.3,2.5Hz,1H),7.35–7.27(m,1H),7.10(d,J=7.0Hz,1H),6.81(d,J=6.9Hz,1H).

[0101] like Figure 8 As shown, it is

[60] fullerene 3-hydroxyindane D 13 C NMR spectrum 13 C NMR (150MHz, CS 2 / CDCl 3 )(all 1C unless indicated)δ155.51,153.29,152.59,152.42,146.05,145.96,145.60,144.90,144.85(2C),144.77(2C),144.74 ,144.69,144.67(2C),144.64,144.25,144.20,144.07(2C),143.99,143.96(2C),143.88(2C),143.84(2C),143.2 2,143.19,143.02,142.99,141.82,141.76,141.36,141.28,141.22,141.20,140.94,140.91,140.85,140.81,14 0.76,140.63,140.59,140.52,140.46,140.34,139.30,139.02,138.73,138.52,136.69,135.24,134.16(2C,aryl C),133.80,133.43,126.01(3C,aryl C),117.23(3C,aryl C),76.15,72.02(2C).

[0102] Example 5

[0103] This example describes the synthesis of

[60] fullerene 2,3-dihydro-1H-inden-1-ylbenzoate E Preparation method:

[0104]

[60] fullerene 3-hydroxyindane A (18.2 mg, 0.022 mmol), benzoic acid (0.11 mmol), EDCI (8.4 mg, 0.044 mmol), and DMAP (8.1 mg, 0.066 mmol) were added to a flask and treated with ultrasound in an ultrasonic cleaner using 4 mL of o-dichlorobenzene to ensure that the mixture was completely dissolved. Subsequently, the solution was quickly transferred to an oil bath preset at 100 °C and heated with stirring at this temperature for 1.5 hours. The reaction progress was monitored by thin layer chromatography (TLC) until the reaction reached the endpoint and heating was stopped.

[0105] After the reaction is terminated, the reaction mixture is preliminarily purified by a short silica gel column to remove insoluble impurities therein, and then the solvent is removed by vacuum distillation in a rotary evaporator, and the resulting residue is further chromatographically separated by a chromatography column. Using carbon disulfide as an eluent, the brown solid

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate E is first separated, and then a mixed solution of carbon disulfide and dichloromethane is used as an eluent to further separate the unreacted

[60] fullerene and 3-hydroxyindane A. The yield of

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate E in this embodiment is 90%. The reaction synthesis equation is:

[0106]

[0107] like Fig. 9 As shown,

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate E 1 H NMR spectrum 1 HNMR (400MHz, CS 2 / DMSO-d 6 )δ8.20(s,1H),8.17(d,J=7.7Hz,1H),8.03(d,J=7.2Hz,2H),7.97(d,J=7.6Hz,1H),7.7 3(t,J=7.5Hz,1H), 7.65(t,J=7.4Hz,1H), 7.54(t,J=7.5Hz,1H), 7.40(t,J=7.7Hz,2H).

[0108] like Fig.10 As shown,

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate E 13 C NMR spectrum 13 CNMR(150MHz,CS 2 / DMSO-d 6)(all 1C unless indicated)δ163.89(C=O),154.24,153.13,152.89,151.47,146.11,145.99,145.12,144.99(3C),144.90(2C),144.74(2C ),144.71(2C),144.68,144.50,144.39,144.31,144.22,144.10,144.05,144.02,143.95(2C),143.93,143.90,143.27,14 3.24,143.13,143.10,142.22,141.81(2C),141.37(2C),141.28,141.04,140.98,140.83,140.75,140.71,140.66,140.54 ,140.50,140.42,140.34,139.37,139.17,138.44,138.25,137.53,135.04,134.36,134.05,133.65,132.48,130.29(aryl C),128.97(2C,aryl C),128.84(3C,aryl C),128.13(aryl C),127.61(3C,arylC),127.01(aryl C),124.75(aryl C),83.00,73.33,73.24.

[0109] Example 6

[0110] This example describes the synthesis of

[60] fullerene 2,3-dihydro-1H-inden-1-ylbenzoate F Preparation method:

[0111]

[60] fullerene 3-hydroxyindane A (18.2 mg, 0.022 mmol), o-toluic acid (14.9 mg, 0.11 mmol), EDCI (8.4 mg, 0.044 mmol), and DMAP (8.1 mg, 0.066 mmol) were added to a flask and ultrasonicated in an ultrasonic cleaner using 4 mL of o-dichlorobenzene to ensure that the mixture was completely dissolved. Subsequently, the solution was quickly transferred to an oil bath preset at 100°C and heated with stirring at this temperature for 1.5 hours. The reaction progress was monitored by thin layer chromatography (TLC) until the reaction reached the endpoint and heating was stopped.

[0112] After the reaction is terminated, the reaction mixture is preliminarily purified by a short silica gel column to remove insoluble impurities therein, and then the solvent is removed by vacuum distillation in a rotary evaporator, and the resulting residue is further chromatographed by a chromatography column. Using carbon disulfide as an eluent, brown solid

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate F is first separated, and then a mixed solution of carbon disulfide and dichloromethane is used as an eluent to further separate unreacted

[60] fullerene and 3-hydroxyindane A. The yield of

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate F in this example is 48%.

[0113] The reaction synthesis equation is:

[0114]

[0115] like Fig.11 As shown,

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate F 1 H NMR spectrum 1 HNMR (400MHz, CS 2 / DMSO-d 6 )δ8.18(s,1H),8.15(d,J=7.6Hz,1H),7.97(d,J=7.6Hz,1H),7.92(d,J=7 .9Hz,1H),7.75–7.69(m,1H),7.69–7.62(m,1H),7.39–7.32(m,1H),7.22–

[0116] 7.14(m,2H),2.59(s,3H).

[0117] like Fig.12 As shown,

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate F 13 C NMR spectrum 13 CNMR(150MHz,CS 2 / DMSO-d 6)(all 1C unless indicated)δ164.30(C=O),154.04,152.88,152.63,151.22,145.82,145.69,145.01,144.79,144.70(2C),144.62(2C), 144.44(3C),144.39(2C),144.21,144.11,144.03,143.92,143.79,143.75(2C),143.66(2C),143.62(2C),142.98,142.9 6,142.84,142.81,141.88,141.51,141.09,140.99(2C),140.74,140.71,140.69,140.55,140.45,140.42,140.36,140. 23,140.13,140.05,139.38,139.07,138.89,138.11,137.81,137.32,134.87,134.04,133.76,133.35(2C),131.40(aryl C),130.58(2C,aryl C),130.04(aryl C),129.53(aryl C),128.78(aryl C),126.87(arylC),126.70,(aryl C)124.73(2C,aryl C),124.53(2C,aryl C),82.53,73.12,72.99,20.78.

[0118] Example 7

[0119] This example describes the synthesis of

[60] fullerene 2,3-dihydro-1H-inden-1-ylbenzoate G Preparation method:

[0120]

[60] fullerene 3-hydroxyindane A (18.2 mg, 0.022 mmol), 4-phenylbenzoic acid (21.8 mg, 0.11 mmol), EDCI (8.4 mg, 0.044 mmol), and DMAP (8.1 mg, 0.066 mmol) were added to a flask and treated with ultrasound in an ultrasonic cleaner using 4 mL of o-dichlorobenzene to ensure that the mixture was completely dissolved. Subsequently, the solution was quickly transferred to an oil bath preset at 100 °C and heated with stirring at this temperature for 1.5 hours. The reaction progress was monitored by thin layer chromatography (TLC) until the reaction reached the endpoint and heating was stopped.

[0121] After the reaction is terminated, the reaction mixture is preliminarily purified by a short silica gel column to remove insoluble impurities therein, and then the solvent is removed by vacuum distillation in a rotary evaporator, and the resulting residue is further chromatographed by a chromatography column. Using carbon disulfide as an eluent, the brown solid

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate G is first separated, and then a mixed solution of carbon disulfide and dichloromethane is used as an eluent to further separate the unreacted

[60] fullerene and 3-hydroxyindane A. The yield of

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate G in this example is 89%.

[0122] The reaction synthesis equation is:

[0123]

[0124] like Fig.13 As shown,

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate G 1 H NMR spectrum 1 HNMR (400MHz, CS 2 / DMSO-d 6 )δ8.06(d,J=7.7Hz,1H),7.93(s,1H),7.67(t,J=7.5Hz,2H),7.58–7.52(m,1H), 7.52–7.45(m,2H),7.36–7.31(m,1H),7.30–7.27(m,1H),7.24(d,J=3.7Hz,5H).

[0125] like Fig.14 As shown,

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate G 13 C NMR spectrum 13 CNMR(150MHz,CS 2 / DMSO-d 6)(all 1C unless indicated)δ166.17(C=O),154.49,153.26(2C),151.45,146.44,146.29,145.56,145.33,145.30,145.28(2C),145.20 ,145.05(2C),145.02(2C),144.99(2C),144.83,144.68(2C),144.51,144.39,144.32(2C),144.25(3C),143.58,143.5 5,143.42(2C),142.37,142.13,142.09,141.72,141.58,141.37,141.33,141.24,141.11,141.05,140.95,140.83,140 .74,140.69,140.65,139.83,139.64,139.42,138.67,138.31,137.31,135.72,134.87,134.37,133.86,130.82(C,aryl C),130.27(2C,aryl C),130.18(C,aryl C),129.14(C,aryl C),129.10(2C,aryl C),128.84(C,aryl C),127.88(3C,aryl C),127.40(3C,aryl C),127.27(C,aryl C),126.49(2C,aryl C),124.80(C,aryl C),83.48,73.41,73.34.

[0126] Example 8

[0127] This example describes the synthesis of

[60] fullerene 2,3-dihydro-1H-inden-1-ylbenzoate H Preparation method:

[0128]

[60] fullerene 3-hydroxyindane A (18.2 mg, 0.022 mmol), 5-chloro-2-iodobenzoic acid (31.1 mg, 0.11 mmol), EDCI (8.4 mg, 0.044 mmol), and DMAP (8.1 mg, 0.066 mmol) were added to a flask and ultrasonically treated in an ultrasonic cleaner using 4 mL of o-dichlorobenzene to ensure that the mixture was completely dissolved. Subsequently, the solution was quickly transferred to an oil bath preset at 100°C and heated with stirring at this temperature for 1.5 hours. The reaction progress was monitored by thin layer chromatography (TLC) until the reaction reached the endpoint and heating was stopped.

[0129] After the reaction is terminated, the reaction mixture is preliminarily purified by a short silica gel column to remove insoluble impurities therein, and then the solvent is removed by vacuum distillation in a rotary evaporator, and the resulting residue is further chromatographically separated by a chromatography column. Using carbon disulfide as an eluent, the brown solid

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate H is first separated, and then a mixed solution of carbon disulfide and dichloromethane is used as an eluent to further separate the unreacted

[60] fullerene and 3-hydroxyindane A. The yield of

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate H in this embodiment is 82%. The reaction synthesis equation is:

[0130]

[0131] like Fig.15 As shown, it is

[60] fullerene 2,3-dihydro-1H-inden-1-ylbenzoate H 1 H NMR spectrum 1 HNMR (400MHz, CS 2 / DMSO-d 6 )(all 1C unless indicated)δ8.16(d,J=7.4Hz,2H),8.08(d,J=7.5Hz,1H),7.89(d,J=8.4Hz,1H),7.77–7.71(m,2H),7.68(t,J=6.9Hz,1H),7.17(dd,J=8.4,2.6Hz,1H).

[0132] like Fig.16 As shown, it is

[60] fullerene 2,3-dihydro-1H-inden-1-ylbenzoate H 13 C NMR spectrum 13 CNMR(150MHz,CS 2 / DMSO-d 6)δ162.92(C=O),154.06,153.08,152.97,151.06,146.26(2C),146.11(2C),145.41,145.11(3C),145.04(2C),1 44.86(2C),144.75,144.63,144.47(2C),144.40,144.29(2C),144.23,144.10(3C),143.38(2C),143.27,143.21 ,142.50,141.93,141.51,141.42,141.17,141.07,140.90,140.83,140.80,140.65,140.59,140.54,140.49,139 .50,139.34,138.57,138.39,136.95,135.57,134.51,134.43,134.34,133.66,133.52,132.28,130.56(2C,aryl C),130.06(2C,aryl C),129.12(2C,aryl C),127.33(3C,arylC),124.87(3C,aryl C),84.12,

[0133] 73.33(2C).

[0134] Example 9

[0135] This example describes the synthesis of

[60] fullerene 2,3-dihydro-1H-inden-1-ylbenzoate I

[0136] Preparation method:

[0137]

[60] fullerene 3-hydroxyindane A (18.2 mg, 0.022 mmol), terephthalic acid (18.3 mg, 0.11 mmol), EDCI (8.4 mg, 0.044 mmol), and DMAP (8.1 mg, 0.066 mmol) were added to a flask and treated with ultrasound in an ultrasonic cleaner using 4 mL of o-dichlorobenzene to ensure that the mixture was completely dissolved. Subsequently, the solution was quickly transferred to an oil bath preset at 100 °C and heated with stirring at this temperature for 1.5 hours. The reaction progress was monitored by thin layer chromatography (TLC) until the reaction reached the endpoint and heating was stopped.

[0138] After the reaction is terminated, the reaction mixture is preliminarily purified by a short silica gel column to remove insoluble impurities therein, and then the solvent is removed by vacuum distillation in a rotary evaporator, and the resulting residue is further chromatographed by a chromatography column. Using carbon disulfide as an eluent, the brown solid

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate I is first separated, and then a mixed solution of carbon disulfide and dichloromethane is used as an eluent to further separate the unreacted

[60] fullerene and 3-hydroxyindane A. The yield of

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate H in this example is 31%.

[0139] The reaction synthesis equation is:

[0140]

[0141] like Fig.17 As shown,

[60] fullerene 2,3-dihydro-1H-inden-1-yl benzoate I 1 H NMR spectrum 1 HNMR (400MHz, CS 2 / DMSO-d 6 ).

[0142]

[60] Due to its poor solubility, it was not possible to obtain a carbon NMR spectrum of fullerene 2,3-dihydro-1H-inden-1-ylbenzoate I. 13 CNMR).

[0143] Comparative Example 1

[0144] In the process of preparing

[60] fullerene-3-hydroxyindane, the acid catalyst p-toluenesulfonic acid monohydrate was not added, and other conditions remained unchanged.

[0145] The reaction equation is:

[0146]

[0147] Preparation method:

[60] fullerene (36.0 mg, 0.05 mmol), 2-iodobenzaldehyde (23.2 mg, 0.1 mmol), palladium acetate (4.5 mg, 0.02 mmol) were added to a flask, and a mixed solution of 6 mL of o-dichlorobenzene and 0.5 mL of acetonitrile was ultrasonically treated in an ultrasonic cleaner to ensure that the mixture was completely dissolved. Subsequently, the solution was quickly transferred to an oil bath preset at 80°C and heated with stirring at this temperature for 12 hours. The reaction progress was monitored by thin layer chromatography (TLC) until the reaction reached the end point and heating was stopped.

[0148] After the reaction is terminated, the reaction mixture is preliminarily purified by a short silica gel column to remove insoluble impurities therein, and then the solvent is removed by vacuum distillation in a rotary evaporator, and the resulting residue is further chromatographically separated by a chromatography column. Using carbon disulfide as an eluent, unreacted

[60] fullerene is first separated, and then the by-product brown solid

[60] fullerene indanone J is separated, and then a mixed solution of carbon disulfide and dichloromethane is used as an eluent to further separate the brown solid

[60] fullerene indanone A. In this example, the yield of

[60] fullerene indanone A is 27%, and the yield of the by-product brown solid

[60] fullerene indanone J is 22%.

[0149] like Fig.18 As shown, the by-product

[60] fullerene indanone J 1 H NMR spectrum 1 H NMR (400MHz, CS 2 / DMSO-d 6 )δ8.49(d,J=7.8Hz,1H),8.37(d,J=7.7Hz,1H),8.12–8.06(m,1H),7.90–7.83(m,1H).

[0150] The byproduct

[60] fullerenoindanone J is a known compound. We compared its hydrogen spectrum with the hydrogen spectrum attached in the published paper (Journal of the American Chemical Society, 2023, 145: 27307-27315) (see Fig.19 The results were compared and showed that they were basically consistent.

[0151] Comparison was made between Example 1 and Comparative Example 1, and the TLC plates (such as Fig. 20 As shown in the figure, and the experimental data results, an additional by-product

[60] fullerene indanone J is generated in the reaction system of Comparative Example 1, and the yield of the target main product also decreases to a certain extent.

[0152] Comparative Example 2

[0153] In the process of preparing

[60] fullerene 3-hydroxyindane, the acid catalyst p-toluenesulfonic acid monohydrate is replaced with an equivalent amount of less acidic acetic acid.

[0154] The reaction equation is:

[0155]

[0156] Preparation method:

[60] fullerene (36.0 mg, 0.05 mmol), 2-iodobenzaldehyde (23.2 mg, 0.1 mmol), acetic acid (6 μL, 0.1 mmol), palladium acetate (4.5 mg, 0.02 mmol) were added to a flask, and a mixed solution of 6 mL of o-dichlorobenzene and 0.5 mL of acetonitrile was ultrasonically treated in an ultrasonic cleaner to ensure that the mixture was completely dissolved. Subsequently, the solution was quickly transferred to an oil bath preset at 80 ° C and heated with stirring at this temperature for 12 hours. The reaction progress was monitored by thin layer chromatography (TLC) until the reaction reached the end point and heating was stopped.

[0157] After the reaction is terminated, the reaction mixture is preliminarily purified by a short silica gel column to remove insoluble impurities therein, and then the solvent is removed by vacuum distillation in a rotary evaporator, and the resulting residue is further chromatographed by a chromatography column. Using carbon disulfide as an eluent, unreacted

[60] fullerene is first separated, and then the by-product brown solid

[60] fullerene indanone J is separated, and then a mixed solution of carbon disulfide and dichloromethane is used as an eluent to further separate the brown solid

[60] fullerene indanone A. In this example, the yield of

[60] fullerene indanone A is 31%, and the yield of the by-product brown solid

[60] fullerene indanone J is 13%.

[0158] Compare Example 1 and Comparative Example 2: Combine the TLC plates (such as Fig.21 As shown in the figure, an additional by-product

[60] fullerene indanone J is generated in the reaction system of Comparative Example 2.

[0159] Comparative Example 3

[0160] In the process of preparing

[60] fullerene 3-hydroxyindane, the acid catalyst p-toluenesulfonic acid monohydrate is replaced with an equivalent amount of trifluoromethanesulfonic acid, which is more acidic.

[0161] The expected reaction equation is:

[0162]

[0163] Preparation method:

[60] fullerene (36.0 mg, 0.05 mmol), 2-iodobenzaldehyde (23.2 mg, 0.1 mmol), trifluoromethanesulfonic acid (10 μL, 0.1 mmol), and palladium acetate (4.5 mg, 0.02 mmol) were added to a flask, and a mixed solution of 6 mL of o-dichlorobenzene and 0.5 mL of acetonitrile was ultrasonically treated in an ultrasonic cleaner to ensure that the mixture was completely dissolved. Subsequently, the solution was quickly transferred to an oil bath preset at 80°C and heated with stirring at this temperature for 12 hours. The reaction progress was monitored by thin layer chromatography (TLC) and it was found that no

[60] fullerene product was generated. The TLC plate at the end of the reaction was as follows: Fig. 22 shown.

[0164] Compare Example 1 with Comparative Example 3: Combine the TLC plates (such as Fig. 22 As shown), the reaction system of Comparative Example 3 did not produce the target product

[60] fullerene and 3-hydroxyindane A.

[0165] Based on the results of Example 1 and Comparative Examples 1-3, it can be seen that when other conditions remain unchanged, only the type of acid catalyst is changed, and the use of p-toluenesulfonic acid monohydrate can greatly improve the selectivity of the system.

[0166] Application Example 1

[0167] Cyclic voltammetry (CV) is a commonly used test method in electrochemistry. Its measurement principle is to make the potential on the working electrode scan as a triangle wave, that is, the potential changes from the starting potential E to the current potential E at a given rate v. 0 Scan to the end potential E λ Then scan back to E at the same rate. 0 , and record the corresponding current-potential (IE) curve, also known as the voltammetric curve.

[0168] Since the redox potential peak of the fullerene derivative is approximately in the range of -2.0-1.5 V, the voltage range is controlled at -3-3 V, the scanning speed is 0.1 V / s, the detection sensitivity is 0.001 V, and the waiting time is 4 s.

[0169] like Fig.23 As shown, the redox potential diagram of

[60] fullerene-3-hydroxyindane A was tested by cyclic voltammetry, and it was found that the oxidation potential peak of the compound appeared at around 1.17V, and the reduction potential peak of the compound appeared at around -1.12V.

[0170]

[60] The redox potentials of fullerene and 3-hydroxyindane A suggest that they may have potential applications in solar cells:

[0171] (1) The compound exhibits an oxidation potential peak of 1.17 V and a reduction potential peak of -1.12 V, indicating that it has dual functions as an electron donor and an acceptor. Therefore, the compound may play a role in constructing PN junction or heterojunction solar cells, improving cell performance by promoting charge separation and transport.

[0172] (2) In solar cells, this redox property can be used to promote the separation and transfer of photogenerated charges, thereby improving the photoelectric conversion efficiency of the cell. Specifically, the oxidized state of the compound can act as an electron acceptor to help transfer photogenerated electrons from the photosensitive material to the conductive substrate, while the reduced state can act as an electron donor to promote the transfer of holes. For example, fullerene derivatives commonly used in organic solar cells, such as [6,6]-phenyl-C 61 -Butyric acid methyl ester (PCBM), which has good electron accepting ability and redox potential, can effectively separate and transport photogenerated electrons. In addition, perovskite materials in perovskite solar cells, such as methylamine lead iodide (CH 3 NH 3 PbI 3 ), and also exhibited excellent redox properties, which helped to improve the photoelectric conversion efficiency of the battery.

[0173] (3) With the help of the redox properties of these compounds, they may also be used as electrode materials or electrolyte additives to enhance the energy storage capacity and cycle stability of the device by improving the charge storage and transport properties, or combined with organic semiconductors, inorganic semiconductors or perovskites to form composite materials, thereby achieving a wider light absorption range, higher charge separation efficiency and longer charge life.

Claims

1. A method for preparing a [60]fullerene 3-hydroxyindane derivative, characterized in that: (1) Using [60]fullerene and an o-halogenated benzaldehyde derivative as raw materials and palladium acetate as a catalyst, in the presence of an acid catalyst and various organic solvents, the target product [60]fullerene and 3-hydroxyindane derivatives are separated after heating: (2) using the [60]fullerene-3-hydroxyindane derivative obtained in step (1) and an aromatic carboxylic acid as raw materials, heating in the presence of a dehydrating agent, an acyl transfer agent and a solvent, and separating to obtain the target product, an ester derivative of [60]fullerene-3-hydroxyindane, Among them, R 1 is a hydrogen atom or a halogen atom, R 2 It is one of a hydrogen atom, a methyl group, a phenyl group, a halogen atom and a carboxyl group.

2. The preparation method according to claim 1, characterized in that: The synthesis equation in step (1) is: The synthesis equation of step (2) is:

3. The preparation method according to any one of claims 1 to 2, characterized in that: The acid catalyst in step (1) is p-toluenesulfonic acid monohydrate, and the plurality of organic solvents include a main solvent of o-dichlorobenzene and a co-solvent of acetonitrile; The specific steps of step (1) include adding [60]fullerene, an o-halogenated benzaldehyde derivative, an acid catalyst, and palladium acetate into a container, and then adding a main solvent and a co-solvent. After the mixture is completely dissolved, the mixture is heated and stirred under air. After the reaction is completed, the mixture is cooled to room temperature, and then the reaction solution is added to a silica gel column, and an eluent is used to separate and obtain a [60]fullerene and 3-hydroxyindane derivative; In the step (2), the dehydrating agent is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, the acyl transfer agent is 4-dimethylaminopyridine, and the solvent includes o-dichlorobenzene; The specific steps of step (2) include adding [60]fullerene and 3-hydroxyindane, aromatic carboxylic acid, dehydrating agent and acyl transfer agent into a reaction bottle, heating and stirring the mixture in air until the mixture is completely dissolved in the solvent, and separating and purifying the mixture by column chromatography technology after the reaction stops to obtain the target product and unreacted [60]fullerene and 3-hydroxyindane derivative respectively.

4. The preparation method according to claim 3, characterized in that: The o-halogenated benzaldehyde derivative in step (1) includes one or more of 2-iodobenzaldehyde, 5-bromo-2-iodobenzaldehyde, 4-bromo-2-iodobenzaldehyde, and 5-fluoro-2-iodobenzaldehyde.

5. The preparation method according to claim 3, characterized in that: The aromatic carboxylic acid in step (2) includes one or more of benzoic acid, o-toluic acid, 4-phenylbenzoic acid, 5-chloro-2-iodobenzoic acid, and terephthalic acid.

6. The preparation method according to claim 3, characterized in that: In the step (1), the molar ratio of [60]fullerene, palladium acetate, o-halogenated benzaldehyde derivative and p-toluenesulfonic acid monohydrate is 1:0.4:2:2, and the heating reaction temperature is 80°C.

7. The preparation method according to claim 3, characterized in that: In the step (2), the molar ratio of the [60]fullerene-3-hydroxyindane derivative, aromatic carboxylic acid, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 4-dimethylaminopyridine is 1:5:2:3, and the heating reaction temperature is 100°C.

8. A [60]fullereno-3-hydroxyindane derivative obtained by the preparation method according to any one of claims 1, 2, 3, 4, and 6, characterized in that: The following compounds are included, 9. An ester derivative of [60]fullereno-3-hydroxyindane obtained by the preparation method according to any one of claims 1, 2, 3, 5, and 7, characterized in that: The following compounds are included, 10. Use of the [60]fullereno-3-hydroxyindane derivative according to claim 8 or the [60]fullereno-3-hydroxyindane ester derivative according to claim 9 in the field of solar cells.

Images