CN102173404A - Non-independent five-membered ring fullerene C50H10 and its synthesis method and application - Google Patents

Abstract

The non-independent five-membered ring fullerene C ₅₀ H ₁₀ and its synthesis method and application relate to a fullerene. Provide non-independent five-membered ring fullerene C ₅₀ H ₁₀ , derivatives C ₅₀ Cl ₁₀ O and their synthesis methods and applications in the preparation of organic solar cells; non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ Synthesis method: Synthesis of C ₅₀ H ₁₀ , synthesis of C ₅₀ H ₁₀ , separation of the product. The synthesis method of derivative C ₅₀ C1 ₁₀ O: put C ₅₀ H ₁₀ solid and iodine monochloride in a glass tube, vacuum seal the tube, react, cool, and remove iodine monochloride to obtain a yellow solid substance, which is dissolved in Toluene forms a yellow solution, which is passed through oxygen and oxidized for 2 hours under natural light conditions, and then the solvent is volatilized to obtain an orange-yellow solid substance, which is separated and purified by high-performance liquid chromatography, then dissolved in toluene, and the solution is slowly evaporated to dryness to obtain C ₅₀ Cl ₁₀ O crystal particles.

Description

Non-independent five-membered ring fullerene C50H10 and its synthesis method and application

technical field

The invention relates to a fullerene, in particular to a non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ and its synthesis method and application.

Background technique

In 1985, Smally, Curl and Kroto et al. (HWKroto, JRHealth, SCO'Brien, RFCurl, RESmalley, Nature, 1985, 318, 162-163) discovered C ₆₀ in the experimental process of laser evaporation of graphite, and since then revealed Prelude to the study of fullerenes. Fullerenes such as C ₆₀ have a cage-like structure and unique properties, making them useful in superconducting materials, nonlinear optical materials, solar cells, catalysts, solid lubricants, gas storage, sensors, rocket engine fuels, semiconductors and micromachines. and biomedicine have shown potential application prospects.

Kroto (H.W.Kroto, Nature, 1987, 329, 529-531) proposed in 1987 that in the common fullerene molecular structure composed of five-membered rings and six-membered rings, the five-membered rings are not adjacent to each other. They are separated from each other by a six-membered ring, which is called the "Isolated Pentagon Rule" (Isolated Pentagon Rule) rule, referred to as the IPR rule. According to this rule, fullerenes can be divided into IPR fullerenes (conventional fullerenes) and non-IPR fullerenes (non-independent five-membered ring fullerenes). IPR fullerenes are very stable, but their types and quantities are much smaller than non-IPR fullerenes. Although non-IPR fullerenes are structurally unstable, they are very important in the study of fullerenes. Because on the one hand, many non-IPR fullerenes are precursors and intermediate products for the synthesis of IPR fullerenes, the study of their structures and properties is very important for understanding the formation mechanism of fullerenes; The number of isomers is much more than that of IPR fullerene. If fullerene can be modified in a certain way to stabilize it, it will open the door to a treasure house of new materials; more importantly, Non -IPR fullerenes also have unusual optical, electrical, and magnetic properties, so methods for the synthesis and isolation of non-IPR fullerenes are of great importance.

Due to the high chemical activity of Non-IPR fullerene, it needs to be modified to stabilize it and obtain stable derivatives. According to different stabilization methods, non-IPR fullerene derivatives can be divided into external group non-IPR fullerene and internal metal non-IPR fullerene.

和Hoffman石墨电弧放电法，即在He气氛中引入Cl₂或CCl₄，合成了大量的具有新奇结构的non-IPR富勒烯。2004年，本申请的发明人谢素原等(S.Y.Xie，F.Gao，X.Lu，R.B.Huang，C.R.Wang，X.Zhang，M.L.Liu，S.L.Deng，L.S.Zheng，Science，2004，304，699-699)分离表征了C₅₀Cl₁₀，这是第一个明确表征的non-IPR富勒烯。此后，分离表征的其它non-IPR富勒烯氯化物包括：^#1809C₆₀Cl₈、^#1804C₆₀Cl₁₂、^#540C₅₄Cl₈、^#913C₅₆Cl₁₀、^#864C₅₆Cl₁₂、^#1911C₆₄Cl₄、^#4169C₆₆Cl₆、^#4169C₆₆Cl₁₀、^#11188C₇₂Cl₄。其它研究组表征的外接基团的non-IPR富勒烯衍生物有：C₂₀H₂₀(H.Prinzbach，A.Weiler，P.Landenderger，F.Wahl，J.Worth，L.T.Scott，M.Gelmont，D.Olevano，B.V.Issendorff，Nature，2000，407，60-63)，^#1911C₆₄H₄(C.R.Wang，Z.Q.Shi，L.J.Wan，X.Lu，L.Dunsch，C.Y.Shu，Y.L.Tang，H.Shinohara，J.Am.Chem.Soc.，2006，128，6605-6610)，^#18917C₇₆Cl₂₄(I.N.Ioffe，A.A.Goryunkov，N.B.Tamm，L.N.Sidorov，E.Kemnitz，S.I.Troyanov，Angew.Chem.Int.Ed.，2009，48，5904-5907)。In the external group non-IPR fullerene, the atoms and groups commonly used to capture active non-IPR fullerene include Cl, H, CF ₃ and so on. Gao Fei et al. (F.Gao, SYXie, RBHuang, LSZheng, Chem.Commun., 2003, 21, 2676-2677) adopted the improved

And Hoffman graphite arc discharge method, that is, introducing Cl ₂ or CCl ₄ in He atmosphere, synthesized a large number of non-IPR fullerenes with novel structures. In 2004, the inventors of the present application, Xie Suyuan et al. (SYXie, F.Gao, X.Lu, RBHuang, CRWang, X.Zhang, MLLiu, SLDeng, LSZheng, Science, 2004, 304, 699-699) isolated and characterized the C ₅₀ Cl ₁₀ , which is the first well-characterized non-IPR fullerene. Since then, other non-IPR fullerene chlorides isolated and characterized include: ^#1809 C ₆₀ Cl ₈ , ^#1804 C ₆₀ Cl ₁₂ , ^#540 C ₅₄ Cl ₈ , ^#913 C ₅₆ Cl ₁₀ , ^#864 C ₅₆ Cl ₁₂ , ^#1911 C ₆₄ Cl ₄ , ^#4169 C ₆₆ Cl ₆ , ^#4169 C ₆₆ Cl ₁₀ , ^#11188 C ₇₂ Cl ₄ . The non-IPR fullerene derivatives of external groups characterized by other research groups are: C ₂₀ H ₂₀ (H.Prinzbach, A.Weiler, P.Landenderger, F.Wahl, J.Worth, LT Scott, M.Gelmont, D. Olevano, BVIssendorff, Nature, 2000, 407, 60-63), ^#1911 C ₆₄ H ₄ (CRWang, ZQShi, LJWan, X.Lu, L.Dunsch, CYShu, YLTang, H.Shinohara, J.Am. Chem.Soc., 2006, 128, 6605-6610), ^#18917 C ₇₆ Cl ₂₄ (INIoffe, AAGoryunkov, NBTamm, LNSidorov, E.Kemnitz, SITroyanov, Angew.Chem.Int.Ed., 2009, 48, 5904- 5907).

Metal-intercalated non-IPR fullerenes stabilize non-IPR fullerenes by electron transfer from intercalated metals. In 2000, Wang Chunru et al. (CRWang, T.Kai, T.Tomiyama, T.Yoshida, Y.Kobayashi, E.Nishibori, M.Takata, M.Sakata, H.Shinohara, Nature, 2000, 408, 426-427) The first endometallofullerene Sc ₂ @C _2v - ^#4348 C ₆₆ containing adjacent five-membered rings was isolated. Stevenson et al. (S.Stevenson, PW Fowler, T.Heine, JCDuchamp, G.Rice, T.Glass, K.Harich, E.Hajdu, R.Bible, HCDorn, Nature, 2000,408,427-428) isolated and characterized The first endometallic compound fullerene Sc ₃ N@D ₃ - ^#6140 C ₆₈ containing adjacent five-membered rings. Since then, eight other metal-intercalated non-IPR fullerenes have been isolated and characterized, including: Sc ₂ C ₂ @C _2v - ^#6073 C ₆₈ , Sc ₃ N@C _2v - ^#7854 C ₇₀ , La@C ₂ - ^#10612 C ₇₂ , La ₂ @D ₂ - ^#10611 C ₇₂ , DySc ₂ N@C _s - ^#17490 C ₇₆ , Dy ₃ N@C ₂ - ^#22010 C ₇₈ , Gd ₃ N@C _s - ^{# 39663} C ₈₂ , Tb ₃ N@C _s - ^#51365 C ₈₄ .

With the depletion of coal, oil, natural gas and other fossil energy sources and the increasing environmental pollution, people urgently need to find new energy sources. Solar energy is considered to be one of the most promising, clean, and renewable energy sources.

In the past few decades, inorganic solar cells have achieved rapid development, and the Fraunhofer Institute for Solar Energy Systems (ISE) in Germany has achieved the highest efficiency of 41.1% so far. However, it has problems such as complex manufacturing process, high cost, high energy consumption in the preparation and purification of materials, and serious pollution. The research on organic solar cells began in the 1970s. Compared with inorganic semiconductor solar cells, organic solar cells not only have the advantages of large manufacturing area, simple fabrication, low cost, and light weight, but also can be prepared on curled and folded substrates. Flexible solar cells.

Organic solar cells are composed of an active layer mixed with a conjugated polymer or organic small molecule donor material and a soluble fullerene acceptor material sandwiched between a conductive glass anode and a low work function metal cathode. Fullerene acceptor materials are one of the key materials for high-performance organic solar cells. In 1992, Sariciftci et al. (NS Sariciftci, L.Smilowitz, AJHeeger, F.Wudl, Science, 1992, 258, 1474-1476) discovered the light-induced electron transfer phenomenon between the conjugated polymer MEHPPV and C ₆₀ , causing worldwide People began to explore the road of C ₆₀ /Polymer battery. In 1995, Yu Gang et al. (G.Yu, J.Gao, JCHummelen, F.Wudl, AJHeeger, Science, 1995, 270, 1789-1791) used C ₆₀ derivative PC ₆₀ BM as acceptor material and conjugated Polymers make up solar cells with a photoelectric conversion efficiency of 2.9%. Since then, PC ₆₀ BM and its corresponding C ₇₀ derivative PC ₇₀ BM have been widely used in organic solar cells. Hummelen et al. (FBKooistra, VDMihailetchi, LMPopescu, D.Kronholm, PWMBlom, JCHummelen, Chem.Mater., 2006, 18, 3068-3073) synthesized PC ₈₄ BM, a derivative of C ₈₄ , and combined it with MDMO-PPV Mix it into a battery. However, due to the poor solubility of high-carbon fullerenes and poor compatibility with polymers, the device efficiency is very low. Currently, Konarka has achieved the highest efficiency of 8.3% for organic solar cells. The open-circuit voltage of organic solar cells is related to the LUMO orbital of fullerene, and a high LUMO orbital can increase the open-circuit voltage of the device; while the short-circuit current is closely related to the solubility of fullerene. In order to further improve the efficiency of organic solar cells, a series of fullerene derivatives with high LUMO orbitals and good solubility have been synthesized, including disubstituted PC ₆₀ BM, disubstituted PC ₇₀ BM, disubstituted indene-C ₆₀ , disubstituted indene-C ₇₀ , embedded metal fullerene Lu ₃ N@C ₈₀ -PCBH, etc. At present, the fullerene materials used in organic solar cells are IPR fullerenes and their derivatives, and their types and quantities are limited; due to the large number of non-IPR fullerenes, their properties are different from those of IPR fullerenes. , using it in organic solar cells can greatly enrich the types and quantities of fullerene acceptor materials, and facilitate the screening of acceptor materials with better performance. However, so far, the application of non-IPR fullerenes in organic solar cells is almost blank.

Although C ₅₀ Cl ₁₀ was synthesized as early as 2004, it is difficult to realize industrial production because C ₅₀ Cl ₁₀ is synthesized by graphite arc discharge method; on the other hand, compared with the synthesis method of C ₅₀ Cl ₁₀ , The synthesis yield of C ₅₀ H ₁₀ in graphite arc discharge method is very low.

Contents of the invention

The purpose of the present invention is to provide non-independent five-membered ring fullerene C ₅₀ H ₁₀ .

The second object of the present invention is to provide a synthesis method of non-independent five-membered ring fullerene C ₅₀ H ₁₀ .

The third object of the present invention is to provide the application of non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ in the preparation of organic solar cells.

The fourth object of the present invention is to provide a derivative C ₅₀ Cl ₁₀ O of the non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ .

The fifth object of the present invention is to provide a method for synthesizing the _derivative C ₅₀ Cl ₁₀ O of the non-independent five-membered ring fullerene hydride C ₅₀ H 10 .

The sixth object of the present invention is to provide the application of C ₅₀ Cl ₁₀ O, a derivative of non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ , in the preparation of organic solar cells.

The structural formula of the non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ is:

Its physical and chemical properties are as follows: molecular symmetry is D _5h , soluble in medium polar solvents such as toluene, benzene and chloroform, slightly soluble in weak polar solvents such as n-pentane and n-hexane; oxidation reaction can occur under atmospheric conditions, Generate C ₅₀ H ₁₀ derivatives.

The synthesis method of the non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ adopts a low-pressure phenoxy diffusion combustion method. The combustion device can be a glass device (referring to the applicant's prior Chinese patent: the publication number is CN101012056A), and a stainless steel device (referring to the applicant's prior Chinese patent: the publication number is CN101503188A).

The synthesis method of the non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ comprises the following steps:

(1) Synthesis of C ₅₀ H ₁₀ using a glass device

1) Place the container holding the liquid benzene at a constant temperature in an oven;

2) Start the mechanical pump, turn on the cooling water, and check whether the device is leaking;

3) Take out the combustion head, inject acetylene gas, and ignite; then open the valve of the oxygen cylinder, open the ventilation valve, insert the combustion head into the grinding port at the lower end of the cavity, then close the ventilation valve, and make the flame burn stably;

4) Turn off the benzene vapor and oxygen until the flame is completely extinguished, then open the vent valve to put in the air, then turn off the mechanical pump and cooling water, and collect the carbon ash on the wall of the cavity and the filter;

5) Put the collected carbon ash in a brown jar with a stopper, add toluene, put it into an ultrasonic cleaner for ultrasonic extraction, let it settle, and transfer the supernatant until the extract is colorless or light yellow. Yes, concentrate the extract under reduced pressure;

In part 1) of step (1), the temperature of the oven may be 40-70° C., and the time for constant temperature may be 10-20 minutes.

In 3) of the step (1) part, the acetylene gas is introduced and ignited, preferably after the acetylene gas is introduced, the gas flow rate is adjusted to be 30-80mL/min (preferably 50mL/min); the flame The conditions for stable combustion are to control the flow rate of benzene vapor at 500-1200mL/min (preferably 800mL/min), the oxygen flow rate at 700-750mL/min (preferably 720mL/min), and the vacuum degree of the system at 10-20Torr (preferably 15 Torr).

In step (1) part 5), the supernatant is transferred until the extract is colorless or light yellow, the supernatant can be transferred by siphon, and the solvent toluene is constantly replaced until the extract is colorless or light yellow yellow.

(2) Synthesis of C ₅₀ H ₁₀ using a stainless steel device

1) Turn on the power supply of the incubator, and start heating the container containing benzene and the gas supply pipeline. Check the airtightness of the unit. Adjust the distance between the combustion nozzle and the tip of the copper electrode, so that the discharge can be sustained after ignition. Open the ventilation valve on the furnace body, close the vacuum ball valve, and start to pass cooling water.

2) Turn on the ignition switch to discharge between the copper electrode and the combustion nozzle. Pass acetylene (acetylene is ignited by electric spark when passing through the combustion nozzle), and then pass oxygen.

3) Turn on the mechanical pump, slowly open the vacuum ball valve, and start pumping the system. Then turn on the switch of the benzene steam rotameter to adjust the benzene steam flow. Fine-tune the vacuum ball valve and vent valve to maintain a certain degree of vacuum in the system. After stabilization, the lower part of the flame is bright yellow, the upper part is brownish yellow, and soot is produced. Combustion synthesis begins.

4) At the end of the experiment, first turn off the benzene vapor, then turn off the acetylene and oxygen, and the flame goes out. Open the ventilation valve to put in air, turn off the mechanical pump, and wait until the system pressure is equal to the external atmospheric pressure before closing the vacuum ball valve and cooling water. After the temperature of the furnace body drops, clean and collect the soot in the filter tank and combustion furnace for extraction and separation detection.

In part 1) of step (2), the temperature of the thermostat was set to 35°C.

In part 2) of step (2), acetylene gas is fed to adjust the flow rate to 0.5-0.6 L/min, and oxygen gas is fed to adjust the flow rate to 1.0-1.1 L/min.

In part 3) of step (2), the better synthesis conditions are to control the flow rate of benzene vapor to 1.0-1.2 L/min, and the vacuum degree of the system to be about 15 Torr.

(3) Separation of products

1) Separation of the concentrated solution by high performance liquid chromatography. The first round of separation is prepared by pyrenylbutyric acid-silica gel column, with toluene as the mobile phase, the flow rate is 10mL/min, the injection volume is 8mL, and the components are collected for 10-12.5min Carry out the next round of separation;

2) The second round of separation uses a semi-preparative Cosmosil 5PBB column with toluene as the mobile phase at a flow rate of 4mL/min, and collects components for 9.8 to 12.3 minutes for the next round of separation;

3) The third round of separation uses a semi-preparative Cosmosil Buckyprep column, with toluene as the solvent, and a flow rate of 4mL/min. The components are collected for 3.7 to 8.8 minutes for the next round of separation;

4) The fourth round of separation uses a semi-preparative Cosmosil 5PBB column (5μm, 10×250mm), toluene is used as the solvent, and the flow rate is 4mL/min. The component with a molecular weight of 610.1 is collected for the next round of separation;

5) Use a semi-preparative Cosmosil Buckyprep column (5μm, 10×250mm) for the fifth round of separation cycle separation, toluene as solvent, flow rate 4mL/min, collect components with a molecular weight of 610.1 for the next round of separation;

6) Use semi-preparative Cosmosil 5PBB column (5μm, 10×250mm) for the sixth round of circular separation and purification, toluene as solvent, flow rate 4mL/min, cut off the first and last impurity components, and finally collect the target product.

The purity of the finally collected target product is about 99%.

The electrochemical properties of the obtained non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ can be tested by cyclic voltammetry under anhydrous and oxygen-free conditions. The platinum disk electrode is used as the working electrode, and the platinum wire is used as the counter electrode and reference electrode respectively. Specific electrode, ferrocene as internal standard, electrolyte is tetra-n-butylammonium hexafluorophosphate (TBAPF ₆ ), solvent is anhydrous o-dichlorobenzene, sample concentration is about 8×10 ^-4 M, scan rate is 50mv/ s.

The obtained non-independent five-membered ring fullerene hydride C ₅₀ H ¹⁰ can be used to prepare organic solar cells, and the specific method is as follows:

1) Prepare o-dichlorobenzene solutions of P ₃ HT and C ₅₀ H ₁₀ with a concentration of 20 mg/ml, and mix the two with a mass ratio of 1:1 after dissolving;

2) Sonicate the ITO glass in detergent, deionized water, acetone, and isopropanol in sequence, and then dry it overnight;

3) Clean the cleaned ITO glass with ultraviolet ozone;

4) Spin-coat a layer of PEDOT:PSS (Baytron P VP AI 4083) on the UV-ozone-treated ITO and then anneal;

In step 4), the thickness of the spin-coated layer of PEDOT:PSS (Baytron PVP AI 4083) can be 40nm, and the annealing can be performed at 140°C for 10min.

5) Put the battery into a glove box, spin-coat the active layer P ₃ HT/C ₅₀ H ₁₀ , and then anneal;

In step 5), the thickness of the spin-coated active layer P ₃ HT/C ₅₀ H ₁₀ may be 100 nm, and the annealing temperature may be 150° C.

6) Put the battery into a vacuum coating apparatus to first evaporate the LiF layer, and then evaporate the aluminum layer;

In step 6), the thickness of the LiF layer may be 0.8nm, and the thickness of the aluminum layer may be 100nm.

7) Encapsulating the whole battery with epoxy resin to obtain an organic solar battery.

Organic solar cells based on C ₅₀ H ₁₀ use C ₅₀ H ₁₀ as the electron acceptor material.

The structural formula of the derivative C ₅₀ Cl ₁₀ O of the non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ is:

Its physical and chemical properties are as follows: the symmetry is C _2v , it is an orange-yellow solid at room temperature, soluble in common solvents such as toluene, benzene, carbon disulfide and chloroform, the solution is yellow, and it can exist stably in the air.

The synthesis method of the derivative C ₅₀ Cl ₁₀ O of the non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ is as follows:

Put 10mg of C ₅₀ H ₁₀ solid and 220mg of iodine monochloride into a glass tube, vacuum seal the tube, then react at 180°C for 24h, then cool to room temperature, remove iodine monochloride by rotary evaporator, and obtain a yellow Solid matter, dissolved in toluene to form a yellow solution, passed through oxygen and oxidized for 2h under natural light conditions, then the solvent was volatilized to obtain an orange-yellow solid matter, separated and purified by high performance liquid chromatography, then dissolved in toluene, and the solution was After slowly evaporating to dryness, C ₅₀ Cl ₁₀ O crystal particles were obtained.

The prepared non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ derivative C ₅₀ Cl ₁₀ O can be used to prepare organic solar cells, and the specific method is the same as that of the non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ similar.

In the present invention, C ₅₀ H ₁₀ is synthesized by a flame combustion method, which has low cost, simple operation, continuous production and potential for industrial production. On the other hand, their electrochemical properties were studied by cyclic voltammetry, and it was found that the electrochemical properties of C ₅₀ Cl ₁₀ were unstable and difficult to be used as acceptor materials for organic solar cells, while the electrochemical properties of C ₅₀ H ₁₀ were stable , the application of C ₅₀ H ₁₀ as a photoelectric conversion material is superior. Moreover, the solubility of C ₅₀ H ₁₀ in organic solvents is much greater than that of C ₅₀ Cl ₁₀ . More importantly, the first reduction potential of C ₅₀ H ₁₀ is about 0.5 V lower than that of C ₅₀ Cl ₁₀ as well as C ₆₀ and C ₇₀ , indicating that the LUMO orbital of C ₅₀ H ₁₀ is higher than that of C ₅₀ Cl ₁₀ and C ₆₀ and C ₇₀ The energy of the LUMO orbital is higher. Therefore, factors such as combustion synthesis, electrochemical properties, and solubility of C ₅₀ H ₁₀ determine that it is expected to be used as an acceptor material for organic solar cells, which can effectively increase the open circuit voltage of organic solar cells.

Description of drawings

Figures 1 to 6 are the multistage high performance liquid chromatography separation chromatograms of C ₅₀ H ₁₀ described in the present invention. In Figures 1-6, the abscissa is the time (min), the ordinate is the UV-Vis detection absorbance, the chromatographic detection wavelength is 330nm, and the shaded part represents the components containing C ₅₀ H ₁₀ .

Fig. 7 is an atmospheric pressure chemical ionization (APCI) mass spectrum of C ₅₀ H ₁₀ according to the present invention. In FIG. 7, the abscissa is the mass-to-charge ratio (m/z), and the ordinate is the response intensity. 1 represents the isotope distribution map of the experiment, and 2 is the isotope distribution map of the theoretical simulation.

Fig. 8 is the ¹ H NMR (600M, CDCl ₃ ) of C ₅₀ H ₁₀ described in the present invention. In Fig. 8, the abscissa is the chemical shift (ppm), and the ordinate is the response intensity.

Fig. 9 is a ¹³ C NMR chart of C ₅₀ H ₁₀ according to the present invention (CDCl ₃ is the solvent). In Fig. 9, the abscissa is the chemical shift (ppm), and the ordinate is the response intensity.

Fig. 10 is an infrared spectrogram of C ₅₀ H ₁₀ described in the invention. In FIG. 10 , the abscissa is the wave number (cm ⁻¹ ), and the ordinate is the absorption intensity.

Fig. 11 is a Raman spectrum of C ₅₀ H ₁₀ in the present invention. In FIG. 11 , the abscissa is the wave number (cm ⁻¹ ), and the ordinate is the response intensity.

Fig. 12 is an ultraviolet-visible spectrum diagram of C ₅₀ H ₁₀ in n-hexane solution according to the present invention. In FIG. 12, the abscissa is the wavelength (nm), and the ordinate is the absorption intensity.

Fig. 13 is the atmospheric pressure chemical ionization mass spectrum of the oxide of C ₅₀ H ₁₀ according to the present invention. In Fig. 13, the abscissa is the mass-to-charge ratio, and the ordinate is the response intensity.

Fig. 14 is a cyclic voltammogram of C ₅₀ H ₁₀ . In FIG. 14, the abscissa is the voltage (V), and the ordinate is the current intensity (mA).

Fig. 15 is a cyclic voltammogram of C ₅₀ H ₁₀ after adding ferrocene. In FIG. 15, the abscissa is the voltage (V), and the ordinate is the current intensity (mA).

Figure 16 is a cyclic voltammogram of C ₅₀ Cl ₁₀ . In FIG. 16, the abscissa is the voltage (V), and the ordinate is the current intensity (mA).

Fig. 17 is a cyclic voltammogram of C ₅₀ Cl ₁₀ after adding ferrocene. In FIG. 17, the abscissa is voltage (V), and the ordinate is current intensity (mA).

Fig. 18 is a schematic diagram of the structure of a P ₃ HT/C ₅₀ H ₁₀ solar cell. In FIG. 18 , ITO is indium tin oxide transparent conductive glass, PEDOT:PSS is poly 3,4-ethylenedioxythiophene/polystyrene sulfonic acid, and P ₃ HT is a polymer of 3-hexylthiophene.

Fig. 19 is a crystal structure diagram of C ₅₀ Cl ₁₀ O, a derivative of C ₅₀ H ₁₀ . In FIG. 19, each atom is represented by thermal vibration ellipsoids, which are drawn according to the Oak Ridge Thermal Ellipsoid Plot and represent 50% thermal vibration probability.

Detailed ways

The synthesis method of the non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ of the present invention adopts a low-pressure phenoxy diffusion combustion method. The combustion device can be either a glass device or a stainless steel device. The specific steps for using the two devices are as follows.

Example 1 Synthesis of non-IPR fullerene C ₅₀ H ₁₀ by low pressure phenoxy diffusion method

(1) Synthesis of C ₅₀ H ₁₀ using a glass device

Place the container holding the liquid benzene in an oven with a constant temperature of 50°C and keep the temperature constant. Start the mechanical pump, turn on the cooling water, and check the device for air leaks. Take out the combustion head, feed acetylene gas, adjust the mass flow meter to control the gas flow rate to 50mL/min, and ignite; then open the valve of the oxygen cylinder, adjust another mass flow meter to control the oxygen flow rate to 50mL/min, the flame becomes shorter and brighter , Open the vent valve, insert the combustion head into the grinding port at the lower end of the cavity, and then slowly close the vent valve, you can see that the flame gradually becomes longer, then slowly shortens, and shrinks into the outer tube of the combustion head. Increase the flow rate of acetylene and oxygen to make the flame grow to a certain height (the outer flame is 4/5 of the height of the combustion chamber), unscrew the switch of the benzene flow meter, and slowly increase the flow rate to introduce benzene vapor, slowly adjust it down and turn it off Acetylene gas, and make the flame burn stably. Finally, the flow rate of benzene vapor is controlled at 800mL/min, the flow rate of oxygen is 700-750mL/min, and the vacuum degree of the system is about 15Torr. At this time, the bottom of the flame is blue and white, and soot is produced in the upper part, and the flame can continue to burn stably for more than 15 hours. At the end of the experiment, turn off the benzene vapor and oxygen until the flame is completely extinguished, then open the ventilation valve to let in air, and finally turn off the mechanical pump and cooling water. Use a brush to sweep down the carbon ash on the walls of the two chambers and the filter screen, and synthesize about 1-1.5g of carbon ash each time. Repeat this, and finally collect about 350g of carbon ash to be separated and detected.

(2) Synthesis of C ₅₀ H ₁₀ using a stainless steel device

Turn on the power supply of the incubator, set the temperature to 35° C., and start heating the benzene-containing container and gas supply pipeline. Check the airtightness of the device. Adjust the distance between the combustion nozzle and the tip of the copper electrode, so that the discharge can be sustained after ignition. Open the ventilation valve on the furnace body, close the vacuum ball valve, and start to pass cooling water. Turn on the ignition switch to make a discharge between the copper electrode and the combustion nozzle. Turn on the acetylene mass flow meter and adjust the flow rate of acetylene to 0.5-0.6L/min. When the acetylene passes through the combustion nozzle, it is ignited by electric sparks. Then turn on the oxygen flow meter and adjust the flow rate of oxygen to 1.0-1.1L/min. Turn on the mechanical pump, slowly open the vacuum ball valve, start pumping the system, and adjust the gas flow rate of the vent valve so that the vacuum degree of the system is close to 15Torr. Then turn on the switch of the benzene steam rotameter, and adjust the flow rate of the benzene steam to 1.0-1.2 L/min. Fine-tune the vacuum ball valve and vent valve to keep the system vacuum at about 15 Torr. After stabilization, the lower part of the flame is bright yellow, and the upper part is brownish yellow, with soot generated. Combustion synthesis begins. The continuous burning time can reach 8-10 hours, and the soot output can reach more than 2g/h. At the end of the experiment, first turn off the benzene vapor, then turn off the acetylene and oxygen, and the flame goes out. Open the vent valve to put in air, turn off the mechanical pump, and wait until the system pressure is equal to the external atmospheric pressure before closing the vacuum ball valve and cooling water. After the temperature of the furnace body drops, clean and collect the soot in the filter tank and combustion furnace for extraction and separation detection.

Put the collected carbon ash into a stoppered brown jar (capacity 2L), add toluene, put it into an ultrasonic cleaner for ultrasonic extraction at room temperature, let it settle, and transfer the supernatant by siphon ;Continuously change the solvent until the extract is colorless or light yellow (approximately 8 times of ultrasonic extraction, each ultrasonic 30min). The extract was concentrated under reduced pressure to 3 L for later use.

The multistage high performance liquid chromatography separation chromatograms of the C ₅₀ H ₁₀ are shown in FIGS. 1-6 . The entire high-performance liquid chromatography separation and purification process of the target product was completed through six rounds, of which the last three rounds were separated by circulation mode, and the separation operations were all carried out at room temperature with toluene as the mobile phase. The flow rate of the first round was 10 mL/min, and the flow rates of the second to sixth rounds were all 4 mL/min. Fig. 1 is the first round of separation chromatograms on the self-made preparative pyrenyl butyric acid-silica gel preparative column, Fig. 2 is the second round of separation chromatograms on the semi-preparative Cosmosil 5PBB column, Fig. 3 is the semi-preparative Figure 4 is the chromatogram of the fourth cycle separation on the semi-preparative Cosmosil 5PBB column, and Figure 5 is the fifth cycle separation on the semi-preparative Cosmosil Buckyprep column Chromatogram, Figure 6 is the sixth round of purification and separation chromatogram on the semi-preparative Cosmosil5PBB column.

The atmospheric pressure chemical ionization (APCI) mass spectrum of the C ₅₀ H ₁₀ is shown in FIG. 7 .

The ¹ HNMR (600M, CDCl ₃ ) of the C ₅₀ H ₁₀ is shown in FIG. 8 .

¹³ ClNMR (600M, CDCl ₃ ) of the C ₅₀ H ₁₀ is shown in FIG. 9 .

The infrared spectrum of the C ₅₀ H ₁₀ is shown in FIG. 10 .

The Raman spectrum of the C ₅₀ H ₁₀ is shown in FIG. 11 .

See Figure 12 for the ultraviolet-visible spectrum of the C ₅₀ H ₁₀ in n-hexane solution.

Refer to FIG. 13 for the atmospheric pressure chemical ionization mass spectrum of the oxide of C ₅₀ H ₁₀ .

Example 2 Separation and Characterization of Non-IPR Fullerene C ₅₀ H ₁₀

On the Shimadzu preparative chromatograph, the first-stage preparative separation was performed on 3L of the extract, and each run was about 60min. A pyrenyl butyric acid-silica gel column (20×250mm) was used to prepare the column, with toluene as the mobile phase, the flow rate was 10mL/min, the injection volume was 8mL, and the components were collected for 10.0-12.5min for the next round of separation. A semi-preparative Cosmosil 5PBB column (5 μm, 10×250 mm) was used for the second round of separation, with toluene as the mobile phase at a flow rate of 4 mL/min, and the fractions were collected for 9.8 to 12.3 minutes for the third round of separation. A semi-preparative Cosmosil Buckyprep column (5 μm, 10 × 250 mm) was used for the third round of separation. Toluene was used as the solvent at a flow rate of 4 mL/min. Fractions were collected for 3.7 to 8.8 minutes for the next round of separation. semi-preparative

The Cosmosil 5PBB column (5μm, 10×250mm) was used for the fourth cycle of separation, and the fraction with a molecular weight of 610.1 was collected. Then use a semi-preparative Cosmosil Buckyprep column (5 μm, 10 × 250mm) to carry out the fifth round of separation cycle separation, and collect components with a molecular weight of 610.1; finally use a semi-preparative Cosmosil 5PBB column (5 μm, 10 × 250mm) for the sixth round After rounds of circular separation and purification, the first and last impurity components are cut off, and finally the target product with a purity of about 99% is collected.

The product was detected by atmospheric pressure chemical ionization (APCI) mass spectrometry to obtain APCI-MS of C ₅₀ H ₁₀ : 610.1 (M).

The product was characterized by NMR, which showed that its symmetry was D _5h , and its structure was determined.

The IR, Raman and UV-Vis spectra of the product further confirmed its structure.

The product C ₅₀ H ₁₀ has high chemical activity and is prone to oxidation reaction to generate C ₅₀ H ₁₀ O _x (x=1-5).

Study on the electrochemical properties of Example 3C ₅₀ H ₁₀

Cyclic voltammetry test using CHI660c electrochemical workstation, dissolving C ₅₀ H ₁₀ in anhydrous 1,2-o-dichlorobenzene, the concentration is 8×10 ^-4 mol/L, TBAPF ₆ as electrolyte, in anhydrous and oxygen-free Under the test conditions, the platinum disk electrode was used as the working electrode, the platinum wire was used as the counter electrode and the reference electrode respectively, and ferrocene was used as the internal standard, and the scanning was performed at a rate of 50mV/s between -2.5 and 0.3V. The results are shown in Figure 14 and Figure 14. 15. The electrochemical properties of C ₅₀ Cl ₁₀ were studied in a similar way. From Figure 14 and Figure 15, it can be seen that the redox peak of C ₅₀ H ₁₀ is irreversible, and four reduction peaks appear when scanning in the positive direction, and the potentials relative to Fc/Fc ⁺ are: -1.45V, -1.65V, -1.93V, -2.21V. It can be seen from Figure 16 and Figure 17 that the redox peak of C ₅₀ Cl ₁₀ is irreversible, and an obvious reduction peak appears when scanning in the positive direction, and the potential relative to Fc/Fc ⁺ is -0.94V. Compared with C ₆₀ (E ¹ _red =-0.98V, E ² _red =-1.37V) and C ₅₀ Cl ₁₀ (-0.94V), the first reduction potential of C ₅₀ H ₁₀ is lower than their first reduction potential around 0.5V, indicating that the LUMO orbital of C ₅₀ H ₁₀ is higher than that of C ₆₀ and C ₅₀ Cl ₁₀ . If C ₅₀ H ₁₀ is used in solar cells, the open circuit voltage of the device increases.

Example 4 Organic solar cell based on C ₅₀ H ₁₀

The solar cell structure (see FIG. 18 ) is: ITO/PEDOT:PSS/P ₃ HT:C ₅₀ H ₁₀ /LiF/Al, as shown in FIG. 17 . First prepare o-dichlorobenzene solutions of P ₃ HT and C ₅₀ H ₁₀ with a concentration of 20 mg/ml, and mix the two at a mass ratio of 1:1 after dissolving. Sonicate the ITO glass in detergent, deionized water, acetone, and isopropanol for 20 min each, and then dry it overnight. Clean the cleaned ITO glass with ultraviolet ozone for 10 minutes, then spin-coat a layer of PEDOT:PSS (Baytron P VPAI 4083) with a thickness of 40 nm, and anneal at 140 ° C for 10 minutes. Spin-coat the P ₃ HT:C ₅₀ H ₁₀ active layer in a glove box with a thickness of about 100nm, and then anneal at 150°C. Finally, put the battery into a vacuum coating apparatus to evaporate a layer of LiF with a thickness of 0.8nm and a layer of aluminum with a thickness of 100nm. After the whole battery is finished, it is packaged with epoxy resin, and the measured open circuit voltage is about 1.2V.

Example 5C ₅₀ H ₁₀ derivatization reaction to prepare C ₅₀ Cl ₁₀ O and its application as solar cell n-type material

C ₅₀ H ₁₀ can be further synthesized into other new materials based on C ₅₀ through derivatization reactions. Taking the preparation of C ₅₀ Cl ₁₀ O as an example, the reaction process is: put C ₅₀ H ₁₀ solid in a glass tube and excess ICl (Iodine Monochloride, about 10 molar ratio in excess), vacuumize and seal the tube, react at 180°C for 24h, cool to room temperature and remove ICl to obtain a yellow solid substance, dissolve in toluene to form a yellow solution, feed oxygen and Oxidation under natural light conditions, and then the solvent is volatilized to obtain orange crystal particles. Characterized by a single crystal X-ray diffractometer, it was proved that the obtained product was C ₅₀ Cl ₁₀ O. Crystallographic studies confirmed the structural characteristics of the product (as shown in Figure 19): after the derivatization reaction, 10 hydrogen atoms were replaced by chlorine atoms, And an oxygen atom is added to a pair of adjacent six-membered ring carbon atoms with less electron shielding to form a structure similar to oxirane, in which the two sp ³ hybridized carbon atoms involved are still bonded , this structural form is beneficial to maintain the electrochemical properties of C ₅₀ . The addition position of the oxygen atom shows that the substitution reaction of C ₅₀ X ₁₀ (X=H or Cl) will be easier to carry out on the carbon atoms of a pair of adjacent six-membered rings with less electronic shielding, which will have It is beneficial for C ₅₀ H ₁₀ to not only maintain its own excellent properties, but also create conditions for its further derivatization reaction to add other functional groups.

Electrochemical cyclic voltammetry studies show that C ₅₀ Cl ₁₀ O has a first reduction potential comparable to that of C ₅₀ Cl ₁₀ and C ₆₀ derivatives, and its chemical properties are more stable than C ₅₀ Cl ₁₀ , indicating that the product can be used in n type electron acceptor material to make ITO/PEDOT:PSS/P ₃ HT:C ₅₀ Cl ₁₀ O/LiF/Al solar cells, the specific process is as follows: firstly prepare P ₃ HT and C ₅₀ Cl with a concentration of 20mg/ml ₁₀ O o-dichlorobenzene solution, and then mix the two at a mass ratio of 1:1. Sonicate the ITO glass in detergent, deionized water, acetone, and isopropanol for 20 min each, and then dry it overnight. Clean the cleaned ITO glass with ultraviolet ozone for 10 minutes, then spin-coat a layer of PEDOT:PSS (Baytron P VP AI 4083) with a thickness of 40 nm, and anneal at 140 ° C for 10 minutes. Spin-coat P ₃ HT:C ₅₀ Cl ₁₀ O active layer in a glove box with a thickness of about 100nm, and then anneal at 150°C. Finally, put the battery into a vacuum coating apparatus to evaporate a layer of LiF with a thickness of 0.8nm and a layer of aluminum with a thickness of 100nm. After the battery is fabricated, it is encapsulated with epoxy resin.

Claims (14)

1. Non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ , characterized in that its structural formula is:

2. the synthetic method of non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ as claimed in claim 1, is characterized in that comprising the following steps: (1) Synthesis of C ₅₀ H ₁₀ using a glass device 1) Place the container holding the liquid benzene at a constant temperature in an oven; 2) Start the mechanical pump, turn on the cooling water, and check whether the device is leaking; 3) Take out the combustion head, inject acetylene gas, and ignite; then open the valve of the oxygen cylinder, open the ventilation valve, insert the combustion head into the grinding port at the lower end of the cavity, then close the ventilation valve, and make the flame burn stably; 4) Turn off the benzene vapor and oxygen until the flame is completely extinguished, then open the vent valve to put in the air, then turn off the mechanical pump and cooling water, and collect the carbon ash on the wall of the cavity and the filter; 5) Put the collected carbon ash in a brown jar with a stopper, add toluene, put it into an ultrasonic cleaner for ultrasonic extraction, let it settle, and transfer the supernatant until the extract is colorless or light yellow. Yes, concentrate the extract under reduced pressure; (2) Synthesis of C ₅₀ H ₁₀ using a stainless steel device 1) Turn on the power supply of the incubator, start heating the container containing benzene and the gas supply pipeline, check the air tightness of the device, adjust the distance between the combustion nozzle and the tip of the copper electrode, so that the discharge can continue after ignition, and open the ventilation valve on the furnace body , close the vacuum ball valve, and start to pass cooling water; 2) Turn on the ignition switch, discharge between the copper electrode and the combustion nozzle, and pass in acetylene. When acetylene passes through the combustion nozzle, it is ignited by an electric spark, and then oxygen is passed in; 3) Turn on the mechanical pump, slowly open the vacuum ball valve, start pumping air into the system, then turn on the switch of the benzene steam rotameter, adjust the flow rate of benzene steam, fine-tune the vacuum ball valve and vent valve, so that the system maintains a certain degree of vacuum, and the lower part of the flame is stabilized It is bright yellow, the upper part is brownish yellow, and there is soot. Combustion synthesis starts; 4) At the end of the experiment, first turn off the benzene vapor, then turn off the acetylene and oxygen, extinguish the flame, open the ventilation valve to put in air, turn off the mechanical pump, wait until the system pressure is equal to the external atmospheric pressure, and then turn off the vacuum ball valve and cooling water; After the temperature of the furnace body drops, clean and collect the soot in the filter tank and the combustion furnace for extraction and separation detection; (3) Separation of products 1) Separation of the concentrated solution by high performance liquid chromatography. The first round of separation is prepared by pyrenylbutyric acid-silica gel column, with toluene as the mobile phase, the flow rate is 10mL/min, the injection volume is 8mL, and the components are collected for 10-12.5min Carry out the next round of separation; 2) The second round of separation uses a semi-preparative Cosmosil 5PBB column with toluene as the mobile phase at a flow rate of 4mL/min, and collects components for 9.8 to 12.3 minutes for the next round of separation; 3) The third round of separation uses a semi-preparative Cosmosil Buckyprep column, with toluene as the solvent, and a flow rate of 4mL/min. The components are collected for 3.7 to 8.8 minutes for the next round of separation; 4) The fourth round of separation uses a semi-preparative Cosmosil 5PBB column (5μm, 10×250mm), toluene is used as the solvent, and the flow rate is 4mL/min. The component with a molecular weight of 610.1 is collected for the next round of separation; 5) Use a semi-preparative Cosmosil Buckyprep column (5μm, 10×250mm) for the fifth round of separation cycle separation, toluene as solvent, flow rate 4mL/min, collect components with a molecular weight of 610.1 for the next round of separation; 6) Use semi-preparative Cosmosil 5PBB column (5μm, 10×250mm) for the sixth round of circular separation and purification, toluene as solvent, flow rate 4mL/min, cut off the first and last impurity components, and finally collect the target product. 3. The synthetic method of non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ as claimed in claim 2, characterized in that in part 1) of step (1), the temperature of the oven is 40 to 70 °C, the time for constant temperature is 10-20 minutes. 4. the synthetic method of non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ as claimed in claim 2, is characterized in that in step (1) part 3), described feeds acetylene gas, ignites, After feeding acetylene gas, adjust and control the gas flow rate to be 30-80mL/min, preferably 50mL/min; the condition for making the flame stable combustion is to control the benzene vapor flow rate at 500-1200mL/min, preferably 800mL/min, The oxygen flow rate is 700-750mL/min, preferably 720mL/min, and the vacuum degree of the system is 10-20Torr, preferably 15Torr. 5. The synthetic method of non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ as claimed in claim 2, characterized in that in step (1) part 5), the transfer supernatant is until the extract It is colorless or light yellow, and the supernatant is transferred by siphoning, and the solvent toluene is constantly replaced until the extract is colorless or light yellow. 6. The method for synthesizing the non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ according to claim 2, characterized in that in step (2) part 1), the temperature of the oven is set to 35°C. 7. the synthetic method of non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ as claimed in claim 2, is characterized in that in the 2) of step (2) part, feeds acetylene, regulates the flow rate of acetylene to be 0.5 ~0.6L/min; After ignition, oxygen is introduced to adjust the oxygen flow rate to 1.0~1.1L/min. 8. The synthetic method of non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ as claimed in claim 2, characterized in that in part 3) of step (2), the flow rate of benzene vapor is adjusted to be 1.0 to 1.2 L/min, the system vacuum is about 15Torr. 9. Use of the non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ as claimed in claim 1 in the preparation of organic solar cells. 10. as the application of claim 9, it is characterized in that its concrete method is as follows: 1) Prepare o-dichlorobenzene solutions of P ₃ HT and C ₅₀ H ₁₀ with a concentration of 20 mg/ml, and mix the two with a mass ratio of 1:1 after dissolving; 2) Sonicate the ITO glass in detergent, deionized water, acetone, and isopropanol in sequence, and then dry it overnight; 3) Clean the cleaned ITO glass with ultraviolet ozone; 4) Spin-coat a layer of PEDOT:PSS (Baytron P VP AI 4083) on the UV-ozone-treated ITO and then anneal; 5) Put the battery into a glove box, spin-coat the active layer P ₃ HT/C ₅₀ H ₁₀ , and then anneal; 6) Put the battery into the vacuum coating apparatus to evaporate the LiF layer, and then evaporate the aluminum layer; 7) Encapsulating the whole battery with epoxy resin to obtain an organic solar battery. 11. The application according to claim 10, characterized in that in step 4), the thickness of the spin-coated layer of PEDOT:PSS (Baytron P VP AI 4083) is 40nm, and the annealing is annealing at 140°C for 10min ; In step 5), the thickness of the spin-coated active layer P ₃ HT/C ₅₀ H ₁₀ is 100nm, and the annealing temperature is 150°C; in step 6), the thickness of the LiF layer is 0.8nm , the thickness of the aluminum layer is 100nm. 12. The non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ derivative C ₅₀ Cl ₁₀ O as claimed in claim 1, characterized in that its structural formula is:

13. The synthesis method of derivative C ₅₀ Cl ₁₀ O of non-independent five-membered ring fullerene hydride C ₅₀ H ₁₀ as claimed in claim 12, characterized in that the specific steps are as follows: Put 10mg of C ₅₀ H ₁₀ solid and 220mg of iodine monochloride into a glass tube, vacuum seal the tube, then react at 180°C for 24h, then cool to room temperature, remove iodine monochloride by rotary evaporator, and obtain The yellow solid substance is dissolved in toluene to form a yellow solution, which is passed through oxygen and oxidized for 2 hours under natural light conditions, and then the solvent is evaporated to obtain an orange-yellow solid substance, which is separated and purified by high-performance liquid chromatography, then dissolved in toluene, and allowed to The solution was slowly evaporated to dryness to obtain C ₅₀ Cl ₁₀ O crystal particles. 14. Use of C ₅₀ Cl ₁₀ O, a derivative of the dependent five-membered ring fullerene hydride C ₅₀ H ₁₀ as claimed in claim 12, in the preparation of organic solar cells.

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