KR100907753B1 - Metanofullerene compound substituted with fluorine group and organic electronic device using same - Google Patents

Abstract

The present invention relates to a novel metafullerene compound (methanofullerene) represented by the following formula (1) and an organic electronic device comprising the same.

[Formula 1]

[A is a fullerene derivative, selected from C60, C72, C76, C78 or C84.]

The novel fluorinated methanofullerene compounds according to the present invention have improved solubility in organic solvents, electrochemical mobility of electrons, and self-organization of fluorine periods. Therefore, even without additional heat treatment, excellent photoelectric conversion efficiency can be obtained. These materials are also applicable to n -type semiconductor materials in active components of photovoltaics, organic thin film transistors (OTFTs), OLEDs and organic memory devices.

Fluorinated, metaoprene, acceptor, electron acceptor, n-type, organic semiconductor, C60, C70, C76, C78, C84, self-organizing, self-organizable

Description

Methanofullerene Compounds Having Fluorinated Substituents and Its Use for Organic Electronics

Figure 1-Schematic diagram that can improve the aggregation between the electron acceptor material through the introduction of fluorine groups

2-UV absorption spectra of metanofullerene derivatives having fluorine groups (PCBTFE, PCBPFP, PCBPFB, PCBPFBZ and PCBDDFH) and PCBM prepared in Preparation Examples 1 to 5

3-PL spectra of metanofullerene derivatives having fluorine groups (PCBTFE, PCBPFP, PCBPFB, PCBPFBZ and PCBDDFH) prepared in Preparation Examples 1 to 5 and PCBM

Figure 4-Electrochemical properties through the CV of the Metanofullerene derivatives (PCBTFE, PCBPFP, PCBPFB and PCBPFBZ) having the fluorine group prepared in Preparation Examples 1 to 4 and PCBM

5-Current-voltage curves of organic solar cell devices using metanofullerene derivatives (PCBTFE, PCBPFP, PCBPFB, PCBPFBZ and PCBDDFH) having fluorine groups prepared in Preparation Examples 1 to 5 and PCBM as electron acceptors

6-Changes in current-voltage curves of annealing time of the device using the metanofullerene compound (PCBTFE) prepared in Preparation Example 1 as an electron acceptor material and P3HT.

7-Changes in annealing time-current curves of devices using the metanofullerene compound (PCBPFB) and P3HT prepared in Preparation Example 3 as electron acceptor materials.

8-Surface characteristic analysis results using AFM for the annealing time of the device using the meta-no fullerene compound (PCBPFB) and PCBM prepared in Preparation Example 3 as the electron acceptor material ((a), (b), (c) and (d ): Annealing time 0, 5, 15 and 60 minutes in P3HT / PCBM film; (e), (f), (g) and (h): annealing time 0, 5, in P3HT / PCBPFB (Preparation 3) film 15 and 60 minutes)

The present invention relates to a methafullerene compound substituted with a novel fluorine group and an organic electronic device including the same.

Organic semiconductor materials using single molecules and polymers have made great strides in the past 25 years. Conventional inorganic semiconductor materials have excellent characteristics and reliability, but it is true that due to manufacturing shortcomings and difficulties in the device fabrication process, the role is gradually transferred to organic semiconductor materials. Compared with inorganic semiconductor materials, organic semiconductor materials are simpler in manufacturing process and can be inexpensive in device fabrication, and due to the characteristics of organic materials, it is easy to develop materials expressing superior characteristics through simple structure changes. Can be.

On the other hand, another example in which the organic semiconductor material is used is an organic solar cell. In general, a photovoltaic cell includes a semiconductor layer and an electrode in a basic configuration. In the photovoltaic cell, electrons and holes are generated inside the semiconductor layer by light from the outside, and the potential difference between the P pole and the N pole is generated due to the movement of charges to the P and N poles, respectively. It is a device using the principle that current flows when a load is connected to a battery. However, as described above, the semiconductor layer of the photovoltaic cell also has a tendency to apply an organic semiconductor material rather than an inorganic material that requires a high price, high temperature vacuum process. In particular, when applied to a solar cell device, not only the device can be manufactured by a spin coating process, but also the development of a semiconductor compound in which battery efficiency does not decrease as the amount of light increases.

In addition, conventional organic semiconductor materials show a big difference in the mobility of holes and electrons, and in most cases, the mobility of holes is reported to be 10 to 1000 times faster than electron mobility. Therefore, relatively little results have been reported for n -type materials using electron transfer among acceptors of organic semiconductors and organic photovoltaic cells used as channel materials such as OTFT. Representative n -type organic semiconductor materials include materials having the following structure.

Fred Wudl's group introduced the {6} -1- (3- (methoxycarbonyl) propyl)-{5} -1-phenyl [5,6] C61 (1995), a metafullerene derivative well known as PCBM. {6} -l- (3- (Methoxycarbonyl) propyl)-{5} -l-phenyl [5,6] C61) was reported. ( J. Org. Chem . , 1995 , 60 , 532). The PCBM can be used as an organic solar cell by mixing with polymer donor materials such as MEH-PPV, MDMO-PPV, and P3HT. Shows high energy conversion efficiency of more than about 4% through annealing device manufactured by mixing with P3HT at high temperature or controlling evaporation rate of solvent when organic thin film is formed. However, such a post-treatment process is difficult to guarantee reproducibility, and when the device is left at a high temperature, the morphology of the organic film is changed, which is likely to have a fatal effect on efficiency or other device characteristics.

Accordingly, the present inventors have studied to solve the above problems, and as a result, by introducing a fluorine group to the methaoprene, a novel n -type organic semiconductor compound capable of partially improving solubility and increasing electron mobility electrochemically Newly discovered, the present invention has been found to be applicable to the use as an active component of organic photovoltaic and organic thin film transistors (OTFT).

Accordingly, it is an object of the present invention to provide a metafluorene compound into which a novel fluorine group is introduced, and also by introducing a fluorine group into the metafluorene compound, thereby having an excellent electron mobility in a thin film state and having an excellent n-type organic compound. It is to provide a material that can have the characteristics of a semiconductor.

In addition, the present invention is a novel fluorine group-introduced meta-no fullerene compound is a polymer donor, that is, when mixed with the electron donor material, the interaction of the functional period containing the fluorine group is more active, such as after annealing (annealing) There is another purpose to implement a device having better characteristics even without the treatment process.

In addition, another object of the present invention is to provide an acceptor for an organic solar cell, that is, an electron acceptor material, having a high energy conversion efficiency through a combination with a general donor, that is, an electron donor material.

The present invention relates to a novel metafullerene compound represented by the following formula (1) and an organic electronic device comprising the same.

[Formula 1]

[Wherein,

R ¹ is (C ₆ -C ₃₀ ) aryl or (C ₄ -C ₃₀ ) heteroaryl, wherein the aryl or heteroaryl is straight or branched (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy , (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) Ar (C ₁ -C ₃₀ ) alkoxy, (C ₄ -C ₃₀ ) heteroaryl, hydroxy, carboxyl, amino, mono or di (C ₁ -C ₃₀ ) alkylamino, (C ₁ -C ₃₀ ) alkyl Carbonyl, (C ₁ -C ₃₀ ) alkoxycarbonyl, benzoyl, phenoxy, cyano, nitro or fluorine groups may be further substituted with one or more substituents selected from the above alkyl, alkoxy, aryl, aralkyl, aralkoxy , Heteroaryl, alkylcarbonyl or alkoxycarbonyl may be further substituted with one or more fluorine groups;

R ² is straight or substituted (C ₁ -C ₃₀ ) alkyl substituted with one or more fluorine groups, (C ₆ -C ₃₀ ) aryl substituted with one or more fluorine groups, straight or substituted (C ₁ ) substituted with one or more fluorine groups -C ₃₀₎ alkyl (C ₆ -C ₃₀₎ aryl, substituted with one or more fluorinated (C ₆ -C ₃₀₎ aralkyl (C ₁ -C ₃₀₎ a (C ₄ -C ₃₀ alkyl substituted with one or more fluorine) (C ₄ -C ₃₀ ) heteroaryl (C ₁ -C ₃₀ ) alkyl substituted with heteroaryl or one or more fluorine groups;

A is a fullerene derivative, C60, C72, C76, C78 or C84;

n is an integer of 1 to 7.]

Specific examples of the (C ₆ -C ₃₀ ) aryl include phenyl (phenyl; -C ₆ H ₅ ), naphthyl (-C ₁₀ H ₇ ), biphenyl (biphenyl; -C ₁₂ H ₉ ), fluorenyl (fluorenyl; -C ₁₃ H ₉ ), phenanthrenyl (-C ₁₄ H ₉ ), anthracenyl (-C ₁₄ H ₉ ), triphenylenyl (-C ₁₈ H ₁₁ ), pyrenyl aromatic groups such as (pyrenyl; -C ₁₆ H ₉ ), chrysenyl (-C ₁₈ H ₁₁ ), naphthacenyl (-C ₁₈ H ₁₁ ).

The (C ₄ -C ₃₀ ) heteroaryl means an aryl group containing 1 to 3 heteroatoms selected from N, O, P or S as an aromatic ring skeleton atom, and the remaining aromatic ring skeleton atoms are carbon. The heteroaryl includes divalent aryl groups in which heteroatoms in the ring are oxidized or quaternized, for example to form N-oxides or quaternary salts. Representative examples include furyl (C ₄ H ₃ O), isobenzofuranyl (C ₈ H ₅ O), pyrrolyl (C ₄ H ₄ N), imidazolyl; C ₃ H ₃ N ₂ ), pyrazolyl (-C ₃ H ₃ N ₂ ), isothiazolyl (-C ₃ H ₂ NS), isoxazolyl (-C ₃ H ₂ NO), Tetrazolyl (tetrazolyl; -CHN ₄ ), pyridinyl (-C ₅ H ₄ N), pyrazinyl (-C ₄ H ₃ N ₂ ), pyrimidinyl (-C ₄ H ₃ N ₂₎ ), Pyridazinyl (-C ₄ H ₃ N ₂ ), indolizinyl (-C ₈ H ₆ N), isoindolyl (-C ₈ H ₆ N), indolyl (indolyl; -C ₈ H ₆ N), indazolyl (-C ₇ H ₅ N ₂ ), isoquinolinyl (-C ₉ H ₆ N), quinolinyl (-C ₉ H ₆ N), kava Carbazolyl (-C ₁₂ H ₈ N), phenanthridinyl (-C ₁₃ H ₈ N) and their corresponding N -oxides (e.g. pyridyl N -oxides, quinolyl N -oxides) , Quaternary salts thereof, etc. It is not limited to this.

The aryl or heteroaryl of R ¹ is a monocyclic or fused ring, for each ring (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkoxy, (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl, (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkoxy, (C ₄ -C ₃₀ ) heteroaryl, hydroxy, carboxyl, amino, mono or di (C ₁ -C ₃₀ ) alkylamino, (C ₁ -C ₃₀ ) alkylcarbonyl, (C ₁ -C ₃₀ ) alkoxycarbonyl One or more substituents selected from benzoyl, phenoxy, cyano, nitro or fluorine groups may be substituted, and specifically, may be exemplified as the following aryl or heteroaryl compounds, but the following aryl or heteroaryl compounds may be used in the present invention. It does not limit the scope of.

[Wherein X, Y and Z are independently of each other hydrogen, straight chain or tricyclic (C ₁ -C ₃₀ ) alkyl, (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl or (C ₁ -C ₃₀ ) alkyl (C ₆ -C ₃₀ ) aryl; m is an integer from 1 to 5; n is an integer from 1 to 3; p is an integer from 1 to 4; q is an integer from 1 to 3; r is an integer of 1 or 2; s is an integer of 1 to 3.]

In Formula 1, R ² is a straight-chain or branched (C ₁ -C ₃₀ ) alkyl substituted with one or more fluorine groups, (C ₆ -C ₃₀ ) aryl substituted with one or more fluorine groups or (C ₆ substituted with one or more fluorine groups -C ₃₀ ) ar are selected from (C ₁ -C ₃₀ ) alkyl.

The metano fullerene compound according to the present invention includes the [5,6] isomer and the [6,6] isomer, and specifically, may be exemplified as the following compound, but the following compounds limit the scope of the present invention. no.

The method for preparing the metano fullerene compound of Chemical Formula 1 according to the present invention is illustrated in the following Scheme 1, for example, metano fullerene of C60, as shown in Scheme 1 below, aryl or heteroaryl substituted oxocarboxyl after the alcohol yudochegwa sulfuric acid substituted with at least one fluorine (H ₂ SO ₄₎ esterification reaction in which the catalyst, p - toluenesulfonyl hydrazide through reaction of (p -toluenesulfonyl hydrazide) p - tosyl hydrazone (p -tosylhydrazone) derivatives. When fullerene is added and heated under pyridine, p -tosylhydrazone derivatives are decomposed and carbene formed through the azide form is reacted with fullerene to give fullerene carbon number. [5,6] -isomers (compound a ) in the form of bonds to junctions of five and six rings can be prepared. In addition, the resulting [5,6] -isomer (Compound a ) was refluxed in a 1,2-dichlorobenzene solvent to prepare the [6,6] -Isomer (Compound b ) in a form bonded to a junction between six rings. can do.

Scheme 1

The organic electronic device including the meta-no fullerene compound of Formula 1 according to the present invention is characterized in that it is selected from the group consisting of an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), an organic memory and an organic transistor.

Hereinafter, for the detailed understanding of the present invention, the meta-no fullerene compound according to the present invention will be described for the representative compounds of the present invention, and methods for preparing the same, and the characteristics of the device, which are merely intended to illustrate the embodiments of the present invention. It does not limit the scope of.

Preparation Example 1 Preparation of Compound PCBTFE [6,6] -Isomer

Preparation of 2,2,2-Trifluoroethyl 4-benzoylbutyrate

In a three-necked 100 ml round bottom flask, 4.00 g (20.8 mmol) of 4-benzoylbutyryl acid, 2.50 g (25.0 mmol) of trifluoroethanol and 0.41 g (5.0 mmol) of concentrated sulfuric acid were added to 30 ml of toluene for 24 hours. Reaction at reflux. The reaction solution was cooled, 100 ml of ethyl acetate was added, washed three times with 10% sodium carbonate solution (80 mL), and three times with distilled water (80 ml). The organic layer was separated, dried over magnesium sulfate, and the solvent was removed under vacuum. The mixed solution (2/1) of methane dichloride and hexane was subjected to column chromatography to give 2,2,2-trifluoroethyl 4-benzoylbutyrate ( 3.22 g, 56%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.95 (d, ArH, 2H, J = 7.5 Hz), 7.60-7.54 (m, ArH, 1H), 7.49-7.44 (m, ArH, 2H), 4.48 ( q, -OCH _2- , 2H, J = 9 Hz), 3.07 (t, -O = CH _2- , 2H, J = 7 Hz), 2.57 (t, -CH ₂ CO _2- , 2H, J = 7.2 Hz), 2.09 (m, -CH ₂ CH ₂ CH _2- ).

¹³ C-NMR (125 MHz, CDCl ₃ = 77.00 ppm) δ 198.99, 171.601, 136.64, 133.14, 128.59, 127.92, 60.59, 60.33, 60.30, 60.00, 37.02, 32.64, 18.93.

¹⁹ F-NMR (CFCl ₃ ) δ −74.31.

FABMS m / z : 274 (M ⁺ H): calcd. (C ₁₃ H ₁₃ F ₃ O ₃ ), 274.24.

2,2,2-trifluoroethyl 4-benzoylbutyrate p-tosylhydrazone (2,2,2- Trifluoroethyl 4-benzoylbutyrate p -tosylhydrazone)

2,2,2-trifluoroethyl 4-benzoyl butyrate 3.00 g (10.94 mmol), p - Tolo yen sulfonyl hydrazide (p -toluenesulfonyl hydrazide) 2.47 g dissolved in (13.24 mmol) in methanol (20 mL) The reaction was refluxed for 5 hours. After further reacting at room temperature for one day, the mixture was cooled to −15 ° C. and filtered. Washing with cold methanol gave 2,2,2-trifluoroethyl 4-benzoylbutyrate p -tosylhydrazone (3.14 g, 71%).

¹ H-NMR (300 MHz, CDCl ₃ ) δ 8.85 (s, NH, 1H), 7.91 (d, HArSO _2- , 2H, J = 8.5 Hz), 7.67-7.63 (m, ortho HPh, 2H), 7.37 -7.33 (m, 3H), 7.29 (d, HAr SO _2- , 2H, J = 8.5 Hz), 4.53 (q, -OCH _2- , 2H, J = 8.3 Hz), 2.67-2.62 (m, -N = CCH _2- , 2H), 2.49-2.45 (t, -CH ₂ CO _2- , 2H, J = 6.0 Hz), 2.41 (s, ArCH ₃ , 3H), 1.80-1.70 (m, -CH ₂ CH ₂ CH _2- , 2H).

¹³ C-NMR (125 MHz CDCl ₃ ) δ 172.59, 153.78, 143.97, 135.99, 135.21, 129.98, 129.60, 129.45, 127.91, 126.18, 61.09, 60.81, 60.51, 60.29, 31.99, 25.63, 21.54, 20.56.

¹⁹ F-NMR (CFCl ₃ ) δ −74.24 (CF ₃ , 3F).

FABMS m / z : 444 (M ⁺ H): calcd. (C ₂₀ H ₂₁ F ₃ N ₂ O ₄ S), 442.45.

{6} -l- (3- (2 ', 2', 2'- Trifluoroethyloxycarbonyl ) Propyl)-{5} -l- Phenyl [5.6] -C61 ({6} -l- (3- (2 ', 2', 2'- Trifluoroethyloxycarbonyl ) propyl )-{5} -l- phenyl  [5.6] -C61) Synthesis

Nitrogen-substituted 100 mL 3 2,2,2 gu, round bottom flask-trifluoroethyl butyrate, 4-benzoyl-p-tosyl hydrazone (2,2,2-Trifluoroethyl 4-benzoylbutyrate p -tosylhydrazone, 1.77 g, 4.0 mmol) was dissolved in 10 mL of dried pyridine and stirred. NaOMe (225 mg, 5.0 mmol) was slowly added thereto for 15 minutes, and then fullerene (Fullerene, 1.44 g, 2 mmol) was dissolved in 100 mL of 1,2-dichlorobenzene and reacted at 70 ° C. for 22 hours. I was. After the reaction was completed, the solvent was concentrated to 70 mL under reduced pressure, and then expanded using a silica gel (40 x 10 cm) using a 1: 5 mixed solvent of methane dichloride and hexane to form a brown solid {6}. -l- (3- (2 ', 2', 2'-trifluoroethyloxycarbonyl) propyl)-{5} -l-phenyl- [5.6] -C61 (350 mg, 18%) was obtained.

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.93 (d, 2H, arom, J = 7.5 Hz), 7.59-7.53 (m, 2H, arom), 7.51-7.48 (m, 1H, arom), 4.47 ( q, 2H, OCH ₂ , J = 9 Hz), 2.24 (t, 2H, CH ₂ CO ₂ , J = 7.5 Hz), 1.66-1.63 (m, 2H, CH ₂ CH ₂ CO ₂ ), 1.53-1.47 ( m, 2H; PhCCH ₂ ).

{6} -l- (3- (2 ', 2', 2'- Trifluoroethyloxycarbonyl ) Propyl)-{5} -l- Phenyl [6.6]- C61  ({6} -l- (3- (2 ', 2', 2'-Trifluoroethyloxycarbonyl) propyl)-{5} -l-phenyl [6.6]- C61 ) (Compound PCBTFE  [6,6] -isomers)

300 mg of {6} -l- (3- (2 ', 2', 2'-trifluoroethyloxycarbonyl) propyl)-{5} -l- in a 100 mL two-neck round bottom flask under nitrogen atmosphere A dark purple solution of phenyl [6.6] -C61 in 1,2-dichlorobenzene solvent (50 mL) was refluxed for 24 hours to convert the [5,6] isomer to the [6,6] isomer through isomerization. It became. After the temperature was lowered to room temperature, the solvent was concentrated to about 15 mL under reduced pressure, 150 mL of methanol solvent was poured out to precipitate, and centrifuged. The separated solid was dissolved in 10 mL of 1,2-dichlorobenzene, 100 mL of methanol was added to precipitate again, and centrifuged to obtain pure {6} -l- (3- (2 ', 2', 2'-trifluoro). Roethyloxycarbonyl) propyl)-{5} -l-phenyl [6.6] -C61 (93%).

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.93 (d, 2H, arom, J = 7.5 Hz), 7.59-7.53 (m, 2H, arom), 7.51-7.48 (m, 1H, arom), 4.47 (q , 2H, OCH ₂ , J = 9 Hz), 2.27-2.19 (m, 2H; PhCCH ₂ ), 1.52 (t, 2H, CH ₂ CO ₂ , J = 7.5 Hz), 1.66-1.63 (m, 2H, CH ₂ CH ₂ CO ₂ ).

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 171.42, 148.68, 147.62, 145.19, 145.15, 145.03, 144.79, 144.66, 144.50, 143.75, 143.03, 142.99, 142.92, 142.20, 142.15, 142.11, 142.11. 132.06, 128.48, 128.32, 121.78, 79.71, 60.75, 60.46, 60.16, 59.87, 51.59, 33.48, 33.36, 29.70, 22.04.

¹⁹ F-NMR (CFCl ₃ ) δ 74.12, -74.15, -74.18.

FABMS m / z : 979 (M ⁺ H): calcd. (C ₁₈ H ₁₅ F ₅ O ₂ ), 978.25.

Preparation Example 2 Preparation of Compound PCBPFP [6,6] -Isomer

Preparation of 2,2,3,3,3-pentafluoropropyl 4-benzoylbutyrate (2,2,3,3,3-Pentafluoro propyl 4-benzoylbutyrate)

In a three-necked 100 ml round bottom flask, 10.0 g (52.0 mmol) of 4-benzoylbutyryl acid, 9.37 g (62.4 mmol) of 2,2,3,3,3-pentafluoropropanol and 0.51 g (5.2 mmol) of concentrated sulfuric acid were added. 2,2,3,3,3-pentafluoropropyl 4-benzoylbutyrate (12.4 g, 74%) was obtained in the same manner as in Preparation Example 1 above.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.95 (d, ArH, 2H, J = 7.5 Hz), 7.55 (m, ArH, 1H), 7.47 (m, ArH, 2H), 4.56 (t, -OCH ₂ -, 2H, J = 12 Hz), 3.07 (t, -O = CH _2- , 2H, J = 7 Hz), 2.57 (t, -CH ₂ CO _2- , 2H, J = 7.2 Hz), 2.09 ( m, -CH ₂ CH ₂ CH _2- ).

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 198.97, 171.58, 136.64, 133.15, 128.59, 127.92, 59.19, 58.97, 58.75, 37.00, 32.65, 18.87.

¹⁹ F-NMR (CFCl ₃ ) δ −84.35, —124.02.

FABMS m / z : 326 (M ⁺ H): calcd. (C ₁₄ H ₁₃ F ₅ O ₃ ), 324.24.

2,2,3,3,3-pentafluoropropyl 4-benzoylbutyrate p Tosylhydrazone (2,2,3,3,3-Pentafluoropropyl 4-benzoylbutyrate p -tosylhydrazone)

2,2,3,3,3-pentafluoropropyl 4-benzoyl-butyrate 6.2 g (19.1 mmol), p - Tolo yen sulfonyl high methanol the dry Zaid (p -toluenesulfonyl hydrazide) 3.92 g ( 21.0 mmol) (20 2,2,3,3,3-pentafluoropropyl 4-benzoylbutyrate p -tosylhydrazone (7.85 g, 87%) was obtained in the same manner as in Preparation Example 1, except that the residue was dissolved in mL).

¹ H-NMR 300 MHz (CDCl ₃ ) δ 8.74 (s, NH, 1H), 7.91 (d, HArSO _2- , 2H, J = 8.5 Hz), 7.67-7.64 (m, ortho HPh, 2H), 7.37- 7.33 (m, 3H), 7.29 (d, HAr SO _2- , 2H, J = 8.5 Hz), 4.64 (t, -OCH _2- , 2H, J = 13 Hz), 2.66-2.61 (m, -N = CCH _2- , 2H), 2.49-2.43 (t, -CH ₂ CO _2- , 2H, J = 6.0 Hz), 2.41 (s, ArCH ₃ , 3H), 1.80-1.70 (m, -CH ₂ CH ₂ CH _2- , 2H).

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 172.64, 153.71, 143.97, 135.19, 135.21, 129.98, 129.60, 129.45, 127.91, 126.18, 59.72, 59.50, 59.29, 31.97, 25.60, 21.54, 20.52.

¹⁹ F-NMR (CFCl ₃ ) δ −84.30 (d, CF ₃ , 3F, J = 15 Hz), −124.00 (t, CF ₂ , 3F, J = 15 Hz).

FABMS m / z : 495 (M ⁺ H): calcd. (C ₂₁ H ₂₁ F ₅ N ₂ O ₄ S), 492.46.

{6} -l- (3- (2 ', 2', 3 ', 3', 3'-pentafluoropropoxycarbonyl) propyl)-{5} -l-phenyl [5.6] -C61 ({ Preparation of 6} -l- (3- (2 ', 2', 3 ', 3', 3'-Pentafluoropropoxycarbonyl) propyl)-{5} -l-phenyl [5.6] -C61)

2,2,3,3,3-pentafluoropropyl 4-benzoylbutyrate p -tosylhydrazone (2,2,3,3,3, -Pentafluoropropyl 4- in a 100 mL three-neck round bottom flask with nitrogen substitution Benzoylbutyrate p -tosylhydrazone, 1.97 g, 4.0 mmol) was dissolved in 10 mL of dried pyridine and stirred in the same manner as in Preparation Example 1 to give {6} -l- (3- (2 ', 2 ', 3', 3 ', 3'-pentafluoropropoxycarbonyl) propyl)-{5} -l-phenyl- [5.6] -C61 (490 mg, 24%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.92 (d, 2H, arom, J = 7.5 Hz), 7.56-7.53 (m, 2H, arom), 7.51-7.48 (m, 1H, arom), 4.55 (t , 2H, OCH ₂ , J = 12 Hz), 2.23 (t, 2H, CH ₂ CO ₂ , J = 7 Hz), 1.65-1.62 (m, 2H, CH ₂ CH ₂ CO ₂ ), 1.52-1.48 (m , 2H; PhCCH ₂ ).

{6} -l- (3- (2 ', 2', 3 ', 3', 3'-pentafluoropropoxycarbonyl) propyl)-{5} -l-phenyl [6.6] -C61 ({6} -l- (3- (2 ', 2', 3 ', 3', 3'-Pentafluoropropoxycarbonyl) propyl)-{5} -l-phenyl [6.6] -C61) ( Preparation of Compound PCBPFP [6,6] -isomer)

300 mg of {6} -l- (3- (2 ', 2', 3 ', 3', 3'-pentafluoropropyloxycarbonyl) propyl)-in a 100 mL two-necked round bottom flask under nitrogen atmosphere A dark purple solution of {5} -l-phenyl [6.6] -C61 in 1,2-dichlorobenzene solvent (50 mL) was refluxed for 24 hours, whereby the [5,6] isomers were subjected to isomerization [6 , 6] isomers. After the temperature was lowered to room temperature, the solvent was concentrated to about 15 mL under reduced pressure, 150 mL of methanol solvent was poured out to precipitate, and centrifuged. The separated solid was dissolved in 10 mL of 1,2-dichlorobenzene, 100 mL of methanol was added to precipitate again, and centrifuged to obtain pure {6} -l- (3- (2 ', 2', 3 ', 3'). , 3'-pentafluoropropoxycarbonyl) propyl)-{5} -l-phenyl [6.6] -C61 (91%).

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.92 (d, 2H, arom, J = 7.5 Hz), 7.56-7.53 (m, 2H, arom), 7.51-7.48 (m, 1H, arom), 4.55 (t , 2H, OCH ₂ , J = 12 Hz), 2.95-2.90 (m, 2H; PhCCH ₂ ), 2.63 (t, 2H, CH ₂ CO ₂ , J = 7 Hz), 2.45-2.19 (m, 2H, CH ₂ CH ₂ CO ₂ ).

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 171.36, 147.61, 145.79, 145.19, 145.15, 145.03, 144.78, 144.65, 144.50, 143.74, 143.03, 142.99, 142.91, 142.19, 142, 15, 142.15. 128.48, 128.33, 79.70, 59.34, 59.12, 58.90, 51.59, 33.48, 33.39, 22.04.

¹⁹ F-NMR (CFCl ₃ ) δ 84.24, -123.83, -123.88, -123.93.

FABMS m / z : 1029 (M ⁺ H): calcd. (C ₁₄ H ₁₅ F ₅ O ₂ ), 1028.26.

[ Production Example  3] compound PCBPFB  Preparation of [6,6] -isomers

Preparation of 3,3,4,4,4-pentafluorobutyl 4-benzoylbutyrate (3,3,4,4,4-Pentafluoro butyl 4-benzoylbutyrate)

In a three neck 100 ml round bottom flask, 3.00 g (15.6 mmol) of 4-benzoylbutyryl acid, 3.07 g (18.7 mmol) of 3,3,4,4,4-pentafluorobutanol and 0.31 g (3.2 mmol) of concentrated sulfuric acid were added. Except for the use, 3,3,4,4,4-pentafluoropropyl 4-benzoylbutyrate (2.6 g, 50%) was obtained in the same manner as in Preparation Example 1.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.96 (d, ArH, 2H, J = 7.5 Hz), 7.55 (m, ArH, 1H), 7.47 (m, ArH, 2H), 4.37 (t, -OCH ₂ -, 1H, J = 6.5 Hz), 4.16 (t, -OCH _2- , 1H, J = 6.5 Hz), 3.07 (t, -O = CH _2- , 2H, J = 7 Hz), 2.47 (t, -CH ₂ C0 _2- , 2H, J = 7.2 Hz), 2.17-2.04 (m, -CH ₂ CH ₂ CH _2- , CH ₂ CF ₂ , 4H).

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 199.24, 173.01, 136.71, 133.10, 128.57, 127.94, 62.81, 37.26, 33.10, 19.86, 19.01.

¹⁹ F-NMR (CFCl ₃ ) δ −86.24, 118.04.

FABMS m / z : 338 (M ⁺ H): calcd. (C ₁₄ H ₁₃ F ₅ O ₃ ), 338.27.

3,3,4,4,4-pentafluorobutyl 4-benzoylbutyrate p Tosylhydrazone (3,3,4,4,4-Pentafluorobutyl 4-benzoylbutyrate p -tosylhydrazone)

3,3,4,4,4- pentafluorophenyl bupil 4-benzoyl butyrate 5.00 g (14.8 mmol), p - Tolo yen sulfonyl hydrazide (p -toluenesulfonyl hydrazide) 3.03 g ( 16.3 mmol) in methanol (20 3,3,4,4,4-pentafluoropropyl 4-benzoylbutyrate p -tosylhydrazone (4.20 g, 60%) was obtained in the same manner as in Preparation Example 1, except that the residue was dissolved in mL).

¹ H-NMR 300 MHz (CDCl ₃ ) δ 9.14 (s, NH, 1H), 7.91 (d, HArSO _2- , 2H, J = 8.5 Hz), 7.67-7.62 (m, ortho HPh, 2H), 7.37- 7.33 (m, 3H), 7.28 (d, HAr SO _2- , 2H, J = 8.5 Hz), 4.27 (t, -OCH _2- , 2H, J = 6 Hz), 2.66-2.61 (m, -N = CCH _2- , 2H), 2.40 (s, ArCH ₃ , 3H), 2.39-2.34 (t, -CH ₂ CO _2- , 2H, J = 6.0 Hz), 2.01-1.96 (m, CH ₂ CF ₂ , 2H ), 180-1.70 (m, -CH ₂ CH ₂ CH _2- , 2H).

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 174.27, 153.55, 143.76, 136.11, 135.31, 133.112, 129.93, 129.54, 128.23, 126.17, 63.73, 32.10, 25.80, 21.54, 20.80.

¹⁹ F-NMR (CFCl ₃ ) δ −81.02 (−CF ₃ , 3F), −128.19 (−CF ₂ −, 2F).

FABMS m / z : 507 (M ⁺ H): calcd. (C ₂₂ H ₂₃ F ₅ N ₂ O ₄ S), 506.49.

{6} -l- (3- (3 ', 3', 4 ', 4', 4'-pentafluorobutoxycarbonyl) propyl)-{5} -l-phenyl [5.6] -C61 ({ 6} -l- (3- (3 ', 3', 4 ', 4', 4'- Pentafluorobutoxycarbonyl ) propyl )-{5} -l-phenyl [5.6] -C61)

3,3,4,4,4-pentafluorobutyl 4-benzoylbutyrate p -tosylhydrazone (3,3,4,4,4-Pentafluorobutyl 4-benzoylbutyrate in a 100 mL three-neck round-bottom flask with nitrogen substitution p- tosylhydrazone, 2.03 g, 4.00 mmol) was dissolved in 10 mL of dried pyridine and stirred in the same manner as in Preparation Example 1, except for {6} -l- (3- (3 ', 3) ', 4', 4 ', 4'-pentafluorobutoxycarbonyl) propyl)-{5} -l-phenyl- [5.6] -C61 (370 mg, 18%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.92 (d, 2H, arom, J = 7.5 Hz), 7.57-7.53 (m, 2H, arom), 7.50-7.48 (m, 1H, arom), 4.15 (t , 2H, OCH ₂ , J = 6.5 Hz), 2.14 (t, 2H, CH ₂ CO ₂ , J = 7 Hz), 1.93-1.90 (m, 2H, CH ₂ CH ₂ CF ₂ CF ₃ ), 1.65-1.63 (m, 2H, CH ₂ CH ₂ CO ₂ ), 1.50-1.46 (m, 2H; PhCCH ₂ ).

{6} -l- (3- (3 ', 3', 4 ', 4', 4'-pentafluorobutoxyoxycarbonyl) propyl)-{5} -l-phenyl [6.6] -C61 ( {6} -l- (3- (3 ', 3', 4 ', 4', 4'-Pentafluorobutoxycarbonyl) propyl)-{5} -l-phenyl [6.6] -C61) (Compound PCBPFB [6,6 ] -Isomer)

300 mg of {6} -l- (3- (2 ', 2', 3 ', 3', 3'-pentafluorobutoxycarbonyl) propyl)-in a 100 mL two-neck round bottom flask under nitrogen atmosphere A dark purple solution of {5} -l-phenyl [6.6] -C61 in 1,2-dichlorobenzene solvent (50 mL) was refluxed for 24 hours, whereby the [5,6] isomers were subjected to isomerization [6 , 6] isomers. After the temperature was lowered to room temperature, the solvent was concentrated to about 15 mL under reduced pressure, 150 mL of methanol solvent was poured out to precipitate, and centrifuged. The separated solid was dissolved in 10 mL of 1,2-dichlorobenzene, 100 mL of methanol was added to precipitate again, and centrifuged to obtain pure {6} -l- (3- (2 ', 2', 3 ', 3'). , 3'-pentafluorobutoxycarbonyl) -propyl)-{5} -l-phenyl [6.6] -C61 (93%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.92 (d, 2H, arom, J = 7.5 Hz), 7.57-7.53 (m, 2H, arom), 7.50-7.48 (m, 1H, arom), 4.15 (t , 2H, OCH ₂ , J = 6.5 Hz), 2.95-2.89 (m, 2H; PhCCH ₂ ), 2.54 (t, 2H, CH ₂ CO ₂ , J = 7 Hz), 2.21-2.15 (m, 2H, CH ₂ CH ₂ CO ₂ ), 1.97-1.94 (m, 2H, CH ₂ CH ₂ CF ₂ CF ₃ ).

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 172.83, 148.72, 145.17, 145.13, 145.02, 144.77, 144.63, 144.48, 143.73, 143.02, 142.97, 142.91, 142.89, 142.17, 142.15, 142.10, 142.10. 132.05, 128.43, 128.26, 79.78, 62.98, 51.74, 33.88, 33.60, 29.68, 27.75, 27.57, 27.39, 22.27, 22.15, 19.89.

¹⁹ F-NMR (CFCl ₃ ) δ 80.94, -80.97, -81.0, -115.68, -115.69, -115.70, -115.71, -115.73, -115.75, -115.76, -115.78, -115.80, 115.81, -115.83,- 115.84, -115.86, -117.92, -128.12, -128.13.

FABMS m / z : 1043 (M ⁺ H): calcd. (C ₁₅ H ₁₇ F ₅ O ₂ ), 1042.3.

Preparation Example 4 Preparation of Compound PCBPFBZ [6,6] -Isomer

Preparation of Pentafluorobenzyl 4-benzoyl butyrate

3.00 g (15.61 mmol) of 4-benzoylbutyryl acid, 3.67 g (18.7 mmol) of pentafluorobenzyl alcohol and 0.31 g (3.2 mmol) of concentrated sulfuric acid were used in a three-neck 100 ml round bottom flask. In the same manner pentafluorobenzyl 4-benzoylbutyrate (5.7 g, 98%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.94 (d, ArH, 2H, J = 7.5 Hz), 7.55 (m, ArH, 1H), 7.47 (m, ArH, 2H), 6.23 (t, CHF ₂ , 1H, J = 5 Hz), 6.06 (t, CHF ₂ , 1H, J = 5 Hz), 5.88 (t, CHF ₂ , 1H, J = 5 Hz), 4.61 (t, -OCH _2- , 2H, J = 13.5 Hz), 3.07 (t, -O = CH _2- , 2H, J = 7 Hz), 2.57 (t, -CH ₂ CO _2- , 2H, J = 7.2 Hz), 2.14-2.09 (m,- CH ₂ CH ₂ CH _2- , 2H).

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 199.32, 171.75, 136.63, 133.20, 128.59, 127.93, 59.34, 37.02, 32.64, 18.90.

¹⁹ F-NMR (CFCl ₃ ) δ -120.17 to -120.31, -132.80 to -122.99, -124.12 to -124.31, -130.14 to -130.32, -137.73 to -137.98.

FABMS m / z : 508 (M ⁺ H): calcd. (C ₁₈ H ₁₄ F ₁₂ O ₃ ), 506.28.

Pentafluorobenzyl  4- Benzoylbutyrate p - Tosylhydrazone  ( Pentafluorobenzyl  4-benzoylbutyrate p - tosylhydrazone Manufacturing

Pentafluoroethyl-benzyl-4-benzoyl-butyrate 5.00 g (13.4 mmol), p - , except that dissolved in Tolo yen sulfonyl hydrazide (p -toluenesulfonyl hydrazide) 2.75 g ( 14.8 mmol) in methanol (20 mL) Preparative Example Pentafluorobenzyl 4-benzoylbutyrate p -tosylhydrazone (6.30 g, 90%) was obtained in the same manner as in 1.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 8.99 (s, NH, 1H), 7.91 (d, HArSO _2- , 2H, J = 8.5 Hz), 7.66-7.62 (m, ortho HPh, 2H), 7.36- 7.33 (m, 3H), 7.28 (d, HAr SO 2 -, 2H, J = 8.5 Hz), 5.31 (s, -OCH 2 -, 2H), 2.67-2.61 (m, -N = CCH 2 -, 2H ), 2.41 (s, ArCH ₃ , 3H), 2.40-2.35 (t, -CH ₂ CO _2- , 2H, J = 6.0 Hz), 1.77-1.70 (m, -CH ₂ CH ₂ CH _2- , 2H) .

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 173.61, 153.62, 143.86, 136.07, 135.83, 133.14, 129.93, 129.54, 128.23, 126.17, 53.94, 32.08, 25.73, 21.57, 20.71.

¹⁹ F-NMR (CFCl ₃ ) δ −142.27 (ArF, 2F), 152.48 (ArF, 1F), 161.75 (ArF, 2F).

FABMS m / z : 541 (M ⁺ H): calcd. (C ₂₅ H ₂₁ F ₅ N ₂ O ₄ S), 540.5.

{6} -l- (3- (pentafluorobenzoxycarbonyl) propyl)-{5} -l-phenyl [5.6] -C61 ({6} -l- (3- (Pentafluorobenzoxycarbonyl) propyl)-{ 5} -l-phenyl [5.6] -C61)

By dissolving the tosyl hydrazone (Pentafluorobenzyl 4-benzoylbutyrate p -tosylhydrazone, 2.16 g, 4.00 mmol) in dry pyridine in 10 mL - 4-benzoyl-benzyl butyrate p pentafluorophenyl a 100 mL 3-neck round bottom flask purged with nitrogen {6} -l- (3- (pentafluorobenzoxycarbonyl) propyl)-{5} -l-phenyl- [5.6] -C61 in the same manner as in Preparation Example 1 except for stirring (290 mg, 14%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 8.99 (s, NH, 1H), 7.91 (d, HArSO _2- , 2H, J = 8.5 Hz), 7.66-7.62 (m, ortho HPh, 2H), 7.36- 7.33 (m, 3H), 7.28 (d, HAr SO 2 -, 2H, J = 8.5 Hz), 5.31 (s, -OCH 2 -, 2H), 2.67-2.61 (m, -N = CCH 2 -, 2H ), 2.41 (s, ArCH ₃ , 3H), 2.40-2.35 (t, -CH ₂ CO _2- , 2H, J = 6.0 Hz), 1.77-1.70 (m, -CH ₂ CH ₂ CH _2- , 2H) .

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 173.61, 153.62, 143.86, 136.07, 135.83, 133.14, 129.93, 129.54, 128.23, 126.17, 53.94, 32.08, 25.73, 21.57, 20.71.

¹⁹ F-NMR (CFCl ₃ ) δ −142.27 (ArF, 2F), 152.48 (ArF, 1F), 161.75 (ArF, 2F).

FABMS m / z : 541 (M ⁺ H): calcd. (C ₂₅ H ₂₁ F ₅ N ₂ O ₄ S), 540.5.

{6} -l- (3- (pentafluorobenzoxyoxycarbonyl) propyl)-{5} -l-phenyl [6.6] -C61 ({6} -l- (3- (Pentafluorobenzoxycarbonyl) propyl)- Preparation of {5} -l-phenyl [6.6] -C61) (Compound PCBPFBZ [6,6] -isomer)

In a 100 mL two-neck round bottom flask under nitrogen atmosphere, 250 mg of {6} -l- (3- (pentafluorobenzoxycarbonyl) propyl)-{5} -l-phenyl [6.6] -C61 A dark purple solution dissolved in 2-dichlorobenzene solvent (50 mL) was refluxed for 24 hours to convert the [5,6] isomer to the [6,6] isomer through an isomerization reaction. After the temperature was lowered to room temperature, the solvent was concentrated to about 15 mL under reduced pressure, 150 mL of methanol solvent was poured out to precipitate, and centrifuged. The solid thus separated was dissolved in 10 mL of 1,2-dichlorobenzene, 100 mL of methanol was added to precipitate again, and centrifuged to obtain pure {6} -l- (3- (pentafluorobenzoxoxycarbonyl) -propyl). -{5} -l-phenyl [6.6] -C61 (89%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.93 (d, 2H, arom, J = 7.5 Hz), 7.57-7.52 (m, 2H, arom), 7.49-7.44 (m, 1H, arom), 5.20 (s , 2H, OCH ₂ ), 2.18 (t, 2H, CH ₂ CO ₂ , J = 7 Hz), 1.62-1.61 (m, 2H, CH ₂ CH ₂ CO ₂ ), 1.50-1.47 (m, 2H; PhCCH ₂ ).

Preparation Example 5 Preparation of Compound PCBDDFH [6,6] -Isomer

3,3,4,4,5,5,6,6,7,7,7- Dodecafluoroheptyl  4- Benzoylbutyrate (3,3,4,4,5,5, 6,6,7,7,7- Dodecafluoroheptyl  4- benzoylbutyrate Manufacturing

10.0 g (52.0 mmol) of 4-benzoylbutyryl acid, 17.8 g of 3,3,4,4,5,5,6,6,7,7,7-dodecafluoroheptanol in a three-necked 100 ml round bottom flask (62.4 mmol) and 1.27 g (13.0 mmol) of concentrated sulfuric acid were used in the same manner as in Preparation Example 3, except that 3,3,4,4,5,5,6,6,7,7,7-dodeca Fluoroheptyl 4-benzoylbutyrate (19 g, 73%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.94 (d, ArH, 2H, J = 7.5 Hz), 7.55 (m, ArH, 1H), 7.47 (m, ArH, 2H), 6.23 (t, CHF ₂ , 1H, J = 5 Hz), 6.06 (t, CHF ₂ , 1H, J = 5 Hz), 5.88 (t, CHF ₂ , 1H, J = 5 Hz), 4.61 (t, -OCH _2- , 2H, J = 13.5 Hz), 3.07 (t, -O = CH _2- , 2H, J = 7 Hz), 2.57 (t, -CH ₂ CO _2- , 2H, J = 7.2 Hz), 2.14-2.09 (m,- CH ₂ CH ₂ CH _2- , 2H).

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 199.32, 171.75, 136.63, 133.20, 128.59, 127.93, 59.34, 37.02, 32.64, 18.90.

¹⁹ F-NMR (CFCl ₃ ) δ -120.17 to -120.31, -132.80 to -122.99, -124.12 to -124.31, -130.14 to -130.32, -137.73 to -137.98.

FABMS m / z : 508 (M ⁺ H): calcd. (C ₁₈ H ₁₄ F ₁₂ O ₃ ), 506.28.

3,3,4,4,5,5,6,6,7,7,7-dodecafluoroheptyl 4-benzoylbutyrate p Tosylhydrazone (3,3,4,4,5,5,6,6,7,7,7-Dodecafluoroheptyl 4-benzoylbutyrate p -tosyl hydrazone)

3,3,4,4,5,5,6,6,7,7,7-dodecafluoroheptyl 4-benzoylbutyrate 10.0 g (19.8 mmol), p -toloenesulfonyl hydrazide ( p- 3,3,4,4,5,5,6,6,7,7,7- in the same manner as in Preparation Example 1, except that 4.41 g (23.7 mmol) of toluenesulfonyl hydrazide) was dissolved in methanol (20 mL). Dodecafluoroheptyl 4-benzoylbutyrate p -tosylhydrazone (7.00 g, 54%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ ¹ H-NMR 300 MHz (CDCl ₃ ) δ 8.82 (s, NH, 1H), 7.91 (d, HArSO _2- , 2H, J = 8.5 Hz), 7.66-7.62 (m, ortho HPh, 2H), 7.36-7.33 (m, 3H), 7.28 (d, HAr SO _2- , 2H, J = 8.5 Hz), 6.07 (m, -CF ₂ H, 1H), 4.68 (s _{, -OCH 2 -, 2H),} 2.67-2.61 (m, -N = CCH 2 -, 2H), 2.50-2.46 (t, -CH 2 CO 2 -, 2H, J = 6.0 Hz), 2.41 (s, ArCH ₃ , 3H), 1.78-1.73 (m, -CH ₂ CH ₂ CH _2- , 2H).

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 173.51, 162.32, 141.64, 136.75, 134.10, 131.71, 129.43, 129.25, 128.90, 127.22, 122.58, 117.63, 115.34, 114.15, 114.51, 112.11, 62.72, 34.0 , 22.66, 18.56.

FABMS m / z : 675 (M ⁺ H): calcd. (C ₂₅ H ₂₁ F ₅ N ₂ O ₄ S), 674.5.

{6} -l- (3- (3 ', 3', 4 ', 4', 5 ', 5', 6 ', 6', 7 ', 7', 7'-dodecafluoroheptyloxycar Carbonyl) propyl)-{5} -l-phenyl [5.6] -C61 ({6} -l- (3- (3 ', 3', 4 ', 4', 5 ', 5', 6 ', 6 Preparation of ', 7', 7 ', 7'-Dodecafluoro heptyloxycarbonyl) propyl)-{5} -l-phenyl [5.6] -C61)

3,3,4,4,5,5,6,6,7,7,7-dodecafluoroheptyl p -tosylhydrazone (3,3,4) , 4,5,5,6,6,7,7,7-dodecafluoroheptyl 4-benzoylbutyrate p -tosylhydrazone, 2.70 g, 4.00 mmol) was dissolved in 10 mL of dried pyridine and was stirred. {6} -l- (3- (3 ', 3', 4 ', 4', 5 ', 5', 6 ', 6', 7 ', 7', 7'- Dodecafluoroheptyloxycarbonyl) propyl)-{5} -l-phenyl [5.6] -C61 (290 mg, 14%) was obtained.

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.93 (d, 2H, arom, J = 7.5 Hz), 7.59-7.56 (m, 2H, arom), 7.49-7.45 (m, 1H, arom), 5.89 (m , -CF ₂ H, 1H), 4.86 (s, 2H, OCH ₂ ), 2.10 (t, 2H, CH ₂ CO ₂ , J = 7 Hz), 1.63-1.61 (m, 2H, CH ₂ CH ₂ CO ₂ ), 1.51-1.47 (m, 2H; PhCCH ₂ ).

{6} -l- (3- (3 ', 3', 4 ', 4', 5 ', 5', 6 ', 6', 7 ', 7', 7'-dodecafluoroheptyloxycar Carbonyl) propyl)-{5} -l-phenyl [6.6] -C61 ({6} -l- (3- (3 ', 3', 4 ', 4', 5 ', 5', 6 ', Preparation of 6 ', 7', 7 ', 7'-Dodecafluoro heptyloxycarbonyl) propyl)-{5} -l-phenyl [6.6] -C61) (Compound PCBDDFH [6,6] -isomer)

In a 100 mL two-neck round bottom flask under nitrogen atmosphere, 250 mg of {6} -l- (3- (3 ', 3', 4 ', 4', 5 ', 5', 6 ', 6', 7 ' , 7 ', 7'-dodecafluoroheptyloxycarbonyl) propyl)-{5} -l-phenyl [6.6] -C61 in dark purple solution (50 mL) At reflux for 24 hours, the [5,6] isomer was converted to the [6,6] isomer through an isomerization reaction. After the temperature was lowered to room temperature, the solvent was concentrated to about 15 mL under reduced pressure, 150 mL of methanol solvent was poured out to precipitate, and centrifuged. The separated solid was dissolved in 10 mL of 1,2-dichlorobenzene, 100 mL of methanol was added to precipitate again, and centrifuged to obtain pure {6} -l- (3- (3 ', 3', 4 ', 4'). , 5 ', 5', 6 ', 6', 7 ', 7', 7'-dodecafluoroheptyloxycarbonyl) -propyl)-{5} -l-phenyl [6.6] -C61 (91% )

¹ H-NMR 300 MHz (CDCl ₃ ) δ 7.93 (d, 2H, arom, J = 7.5 Hz), 7.59-7.56 (m, 2H, arom), 7.49-7.45 (m, 1H, arom), 5.99 (m , -CF ₂ H, 1H), 4.49 (s, 2H, OCH ₂ ), 2.87-2.85 (m, 2H; PhCCH ₂ ), 2.56 (t, 2H, CH ₂ CO ₂ , J = 7 Hz), 2.20- 2.17 (m, 2H, CH ₂ CH ₂ CO ₂ ), 1.97-1.94 (m, 2H, -CH ₂ CF _2- ).

¹³ C-NMR 500 MHz (CDCl ₃ = 77.00 ppm) δ 173.16, 148.67, 147.32, 145.19, 145.78, 145.03, 144.88, 144.75, 144.60, 143.14, 143.13, 142.99, 142.92, 142.29, 142.25, 142.21. 128.40, 128.21, 79.85, 59.34, 59.12, 58.90, 51.59, 33.48, 33.61, 22.38.

¹⁹ F-NMR (CFCl ₃ ) δ 84.24, -123.83, -123.88, -123.93.

FABMS m / z : 1211 (M ⁺ H): calcd. (C ₁₄ H ₁₅ F ₅ O ₂ ), 1210.3.

Example 1 Optical and Electrochemical Properties of Metanofullerene Compounds According to the Present Invention

In order to observe the optical properties of the fluorinated metaoprene compound (PCBTFE, PCBPFP, PCBPFB, PCBPFBZ and PCBDDFH) prepared in Preparation Examples 1 to 5 of the present invention using the UV / Vis spectrometer and PL spectroscope Figure 2 and Figure UV absorption spectrum and PL spectrum are shown in FIG. 3.

In addition, to observe the electrochemical properties of the fluorinated metaoprene compound (PCBTFE, PCBPFP, PCBPFB, PCBPFBZ and PCBDDFH) prepared in Preparation Examples 1 to 5, the oxidation / reduction characteristics using a cyclovoltameter were observed. CV equipment was used BAS 100 cyclovoltametry, 0.1M Bu ₄ NBF ₄ was used as acetonitrile solvent, the sample was dissolved in 1,2, -dichlorobenzene at a concentration of 10 ^-3 M. Measured at a scan rate of 100 mW / s under Ar at room temperature, glass carbon electrodes (0.3 mm in diameter) were used as working electrodes, and Pt and Ag / AgCl electrodes were used as counter electrodes and reference electrodes. 4 is shown.

In the UV absorption spectrum of FIG. 2, the fluorinated metanofullerene derivatives of the present invention showed almost the same absorption characteristics as conventional PCBM ([6,6] phenyl-C61-butyric acid methyl ester), a kind of methanofullerene). On the PL spectrum of 3, the light emission characteristics were shown at almost the same wavelength, but the light emission efficiency was relatively lower. Through the above results, it was confirmed that the metanofullerene compound according to the present invention has a possibility of transferring light or electric energy absorbed more easily than the PCBM toward the electrode.

In addition, the meta-no fullerene compounds according to the present invention from Figure 4 showed three quasireversible reduction levels similar to PCBM in the interval of 0V to -2.0V, showed a somewhat positive value compared to the PCBM. These results are due to the electron withdrawing characteristics of the fluorine group introduced, it was confirmed that the excellent n-type organic semiconductor material through the excellent electron affinity, the characteristics that can receive electrons through this. In addition, it is expected that the electron transfer characteristics can be improved.

Example 2 Fabrication of Organic Solar Cell Device Containing Metanofullerene Compound and Measurement of Energy Conversion Efficiency According to the Present Invention

After spin coating PEDOT-PSS (Bayer Baytron P, Al 4083) by 40 nm on the washed ITO glass substrate, poly (3-hexylthiophene) [Poly-3- (hexylthiophene)] and the present invention prepared One of the fluorine-substituted C ₆₀ derivatives (PCBTFE, PCBPFP, PCBPFB, PCBPFBZ and PCBDDFH) is selected and dissolved in 1,2-dichlorobenzene, chlorobenzene, chloroform alone or a mixed solvent thereof and spin-coated. A thin film was formed. LiF / Al was deposited on the organic film thus formed under vacuum with an electrode, and then sealed with a glass cap with a moisture absorbent.

In general, power conversion efficiency (PCE) of a solar cell can be obtained through Equation 1 below.

[Equation 1]

[Equation 1,

Voc is an open circuit voltage (V) and represents a voltage in a state in which no current flows;

Jsc is short circuit current (mA / cm ² ) and represents the current density at 0 V;

FF is the fill factor, the maximum power divided by the product of Voc and Jsc ;

Pinc represents the light intensity (mW / cm ² ) split.]

[Table 1] Comparison of characteristics of organic solar cell devices manufactured by mixing with P3HT.

As shown in Table 1, in the case of the device using the fluorinated meta-no fullerene compound of the present invention, it was confirmed that shows a higher efficiency than the conventional PCBM in the state without a separate annealing. In particular, when the electron acceptor materials of Examples 1 and 3 were used, high efficiency of 3.2% or more was obtained.

Example 3 Annealing and Thermal Stability Comparison of Organic Solar Cell Devices Containing Metanofullerene Compounds According to the Present Invention

In order to examine the characteristics change and thermal stability through the annealing of the organic solar cell device fabricated in Example 2, the heat treatment was performed at 150 ° C. for 5 minutes, 15 minutes, 30 minutes, and 60 minutes, and the IV characteristics of the device were investigated. . In the case of PCBM, the energy conversion efficiency was 1.8% before heat treatment, and after increasing the heat treatment time at 150 ° C, the highest efficiency was obtained after 5 minutes treatment at 3.1%, 2.2%, and 1.4%, respectively. Showed characteristics. However, in the case of the fluorinated meta-no fullerene derivatives of the present invention, the Voc was slightly increased as the heat treatment time was increased, and it was found that almost the same energy conversion efficiency was maintained even after 60 minutes of treatment. Among these, experimental results using the materials of PCBTFE (Production Example 1) and PCBPFB (Production Example 3) are shown in FIGS. 6 and 7, respectively.

Example 4 Comparison of Surface Changes Before and After Annealing of an Organic Solar Cell Device Containing a Metanofullerene Compound According to the Present Invention

Among the organic solar cell devices fabricated in Example 2, the surface before and after annealing of the device using the PCBPFB compound of Preparation Example 3 and the device using the PCBM was analyzed using AFM, and the results are shown in FIG. 8. . Through the above experiments, in the case of the fluorinated metanofullerene derivatives of the present invention, the surface roughness was lower than that of the PCBM, and only minute changes were observed until 30 minutes during annealing. However, when PCBM is used, when the heat treatment is performed under the same conditions, it can be confirmed that the surface roughness changes more rapidly, which may be related to the deterioration of device characteristics after the heat treatment after 15 minutes.

As described above, the novel fluorinated metanofullerene derivative according to the present invention improves solubility by introducing fluorinated substituents into fullerene, and more effectively improves electron mobility by self-assembly during the fluorine substitution period. Could. These new compounds are useful for use as electron transport layers of organic light emitting devices, electron acceptors of organic solar cells, electron transport layers of organic photoconductors (OPCs), n -type organic semiconductors of organic memories and organic transistors, and the like.

Claims (7)

The metano fullerene compound represented by following formula (1). [Formula 1]

[Wherein, R ¹ is (C ₆ -C ₃₀ ) aryl or (C ₄ -C ₃₀ ) heteroaryl, which aryl or heteroaryl can be further substituted with straight or branched (C ₁ -C ₃₀ ) alkyl; R ² is straight or branched (C ₁ -C ₃₀ ) alkyl substituted with one or more fluorine groups, or (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl substituted with one or more fluorine groups; A is a fullerene derivative, C60, C72, C76, C78 or C84; n is an integer of 1 to 7.] The method of claim 1, R ¹ is selected from the following structures:

[Wherein X and Z are independently of each other hydrogen or straight chain or branched (C ₁ -C ₃₀ ) alkyl; m is an integer from 1 to 5; s is an integer of 1 to 3.] The method of claim 1, R ² is a meta or straight chain or substituted (C ₁ -C ₃₀ ) alkyl substituted with one or more fluorine groups or (C ₆ -C ₃₀ ) ar (C ₁ -C ₃₀ ) alkyl substituted with one or more fluorine groups Nofullerene compound. The method of claim 3, wherein A metano fullerene compound, characterized in that it is selected from the following compounds.

The method of claim 3, wherein A metano fullerene compound, characterized in that it is selected from the following compounds.

An organic electronic device comprising the metano fullerene compound according to any one of claims 1 to 5. The method of claim 6, The organic electronic device is an organic electronic device, characterized in that selected from the group consisting of an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), an organic memory and an organic transistor.

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