KR101535186B1 - fullerene derivative having pyrrolidine and organic electronic devices containing them - Google Patents
fullerene derivative having pyrrolidine and organic electronic devices containing them Download PDFInfo
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Abstract
The present invention relates to a fullerene derivative and an organic electronic device containing the fullerene derivative. The fullerene derivative having a pyrrolidine group of the present invention improves the electrical and chemical properties of the organic electronic device employing the fullerene derivative to improve the efficiency.
Description
The present invention relates to a novel fullerene derivative and an organic electronic device including the fullerene derivative, and more particularly to a fullerene derivative having a pyrrolidine group and an organic solar cell element containing the fullerene derivative.
Fullerene has been of great interest because of its unique physico-chemical properties. Fullerene represented by C 60 and C 70 is a molecule having high symmetry due to a bond due to an intermolecular force. All carbon atoms in the molecule are equivalent, covalently bonded to each other, and are highly stable crystals.
Based on these properties, fullerene is expected to be applied to various applications as a new carbon-based material. Thus, it is the most potent and long-lived antioxidant, and has recently been attracting attention in biomedical fields due to its anticancer efficacy.
In particular, fullerene such as C 60 is attracting interest in applications of superconducting materials, catalyst materials, lubricant materials, biomaterials, and nonlinear optical materials due to metallic mechanical properties such as plastic deformation and work hardening properties.
Since fullerene molecules having a pentavalent carbon-carbon double bond and having hexagonal shape are not aromatic but have an alkene structure, a variety of new fullerene derivatives are produced through various alkene addition reactions to fullerene molecules Recently, there have been many attempts to develop fullerene-containing derivatives through chemical functionalization of fullerene as well as research on fullerene itself.
Further, by using the property of fullerene which has no change in structure due to electron transfer at the time of reduction, applicability as an electron acceptor can be expected. Through the increase of physicochemical properties of fullerene through chemical functionalization, Development is underway.
A typical example is a dielectric solar cell. BACKGROUND ART [0002] Oil-field type solar cells are new solar cells that have remarkably improved their technical possibilities in recent years. Oil-based solar cells have a junction structure of an electron donor and an electron acceptor. Is a very fast charge transfer phenomenon called photoinduced charge transfer (PICT), which manifests the photovoltaic effect.
The organic semiconductors used as the electron donors may include a material of polyparaphenylene vinylene (PPV) and a material of polythiophene (hereinafter referred to as PT) Various derivatives have been used. As the electron acceptor, C 60 fullerene itself or a C 60 fullerene derivative designed to dissolve C 60 fullerene in an organic solvent is used, and other monomers include perylene, 3,4,9,10- Perylene tetracarboxylic acid diimide, phthalocyanine, pentacene, and the like are used.
In order to increase the efficiency of the solar cell, the contact area between the electron donor and the electron acceptor must be large, and the two separated charges must be able to move to the electrode without loss of charge.
However, since C 60 fullerene has a low solubility in an organic solvent, phase separation occurs when it is mixed with a polymer, so that the efficiency of the outline is low overall. As a method for solving this problem, many attempts have been made to use a C 60 fullerene derivative having its side chain attached thereto in order to increase solubility of C 60 fullerene in an organic solvent. Such an attempt not only improves the solubility of C 60 fullerene but also allows the degree of mixing of the semiconductor polymer and C 60 fullerene to be very high compared with the conventional method, making it possible to develop a photovoltaic device with improved energy conversion efficiency.
In for example US Patent Publication No. 2006-0011233 call as an electron donor of poly (3-hexylthiophene) (P3HT) and an electron acceptor, [6,6] -phenyl -C 61 - butyric acid methyl ester (C 60 -PCMB ), And a photoelectric conversion layer is introduced by a spin coating method.
J. Peet et. .. al, Nature Mater, 6 , 497, 2007, the light absorbing ability is superior than the C 70 fullerene derivative C 60 fullerene [6,6] -phenyl -C 71 - butyric acid methyl ester (C 70 -PCMB) Photoelectric And introduced into the electron acceptor of the conversion layer to improve the photoelectric conversion performance.
However, in order to meet the requirements in the fields of superconducting materials, catalyst materials, lubricant materials, biomaterials and nonlinear optical materials, it is necessary to manufacture fullerene derivatives excellent in electrochemical stability and physicochemical properties while maintaining intrinsic properties of fullerene to be.
Accordingly, the present inventors have conducted studies to maximize the efficiency and the solubility of fullerene, to prepare a novel fullerene derivative having pyrrolidine bonded to the molecule of fullerene, It was confirmed that the electrochemical stability and physico-chemical properties were improved, especially, the thermal stability was improved due to the nature of the molecular structure in the production of the organic electronic device, and the energy conversion efficiency was improved due to high compatibility with the semiconductor polymer By confirming, the present invention has been completed.
An object of the present invention is to provide a novel fullerene derivative to which pyrrolidine is bonded and an organic electronic device containing the fullerene derivative. More particularly, the present invention relates to a pyrrolidine-bonded fullerene derivative, A battery, an organic thin film transistor, an organic memory or an organophotoreceptor.
In order to solve the above problems, the present invention provides a fullerene derivative represented by the following formula (1).
[Chemical Formula 1]
[In the above formula (1)
A is fullerene of C60, C70, C72, C76, C78 or C84;
R < 1 > is (C1-C20) alkyl;
R 2 and R 3 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, carboxylic acid, amino, cyano, nitro, (C 1 -C 20) alkyl, (C 1 -C 20) haloalkyl, C6-C20) aryl, (C6-C20) aralkyl (C 1 -C 30) alkyl, (C 1 -C 30) alkyl (C6-C20) aryl, (C6-C20) aralkyl (C 1 -C 30) alkoxy (C1-C20) alkylcarbonyl, (C1-C20) cycloalkyl, (C3-C20) heterocycloalkyl, mono- or di ) Alkoxycarbonyl;
and n is an integer of 1 to 9.]
According to an embodiment of the present invention, R 1 in the fullerene derivative is (C 1 -C 5) alkyl, R 2 and R 3 are each independently hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) and n is a fullerene derivative which is an integer of 1 to 5. [
According to one embodiment of the present invention, the fullerene derivative is a fullerene of the formula (1) wherein A is C60 or C70; R < 1 > is (C1-C5) alkyl; R 2 and R 3 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, carboxylic acid, amino, cyano, nitro, (C 1 -C 20) alkyl, (C 1 -C 20) haloalkyl, C6-C20) aryl, (C6-C20) aralkyl (C 1 -C 30) alkyl, (C 1 -C 30) alkyl (C6-C20) aryl, (C6-C20) aralkyl (C 1 -C 30) alkoxy (C1-C20) alkylcarbonyl, (C1-C20) cycloalkyl, (C3-C20) heterocycloalkyl, mono- or di ) Alkoxycarbonyl; and n may be an integer of 1 to 9.
According to one embodiment of the present invention, the fullerene derivative may be more preferably selected from the following structures.
The present invention relates to a process for preparing a compound represented by the formula (1) by reacting a compound represented by the following formula (5), a fullerene and a compound represented by the following formula (6) The present invention provides a method for producing a fullerene derivative.
[Chemical Formula 5]
[Chemical Formula 6]
[Chemical Formula 1]
[In the formulas (1), (5) and (6)
A is fullerene of C60, C70, C72, C76, C78 or C84;
R < 1 > is (C1-C20) alkyl;
R 2 and R 3 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, carboxylic acid, amino, cyano, nitro, (C 1 -C 20) alkyl, (C 1 -C 20) haloalkyl, C6-C20) aryl, (C6-C20) aralkyl (C 1 -C 30) alkyl, (C 1 -C 30) alkyl (C6-C20) aryl, (C6-C20) aralkyl (C 1 -C 30) alkoxy (C1-C20) alkylcarbonyl, (C1-C20) cycloalkyl, (C3-C20) heterocycloalkyl, mono- or di ) Alkoxycarbonyl;
and n is an integer of 1 to 9.]
The compound represented by Formula 5, fullerene, and the compound represented by Formula 6 are dissolved in an organic solvent and refluxed at 100 to 150 ° C to prepare a compound represented by Formula 1 according to an embodiment of the present invention It can be one.
According to one embodiment of the present invention, a compound represented by the following formula (5) is produced by reacting a compound represented by the following formula (2) and a compound represented by the following formula (3) to prepare a compound represented by the formula (4) And reacting a compound represented by the following formula (4) with a compound represented by the following formula (5) through a hydrogenation reaction; . ≪ / RTI >
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[In the above Chemical Formulas 2 to 5,
X is halogen;
R < 1 > is (C1-C20) alkyl;
and n is an integer of 1 to 9.]
The present invention provides an organic electronic device containing the fullerene derivative.
According to an embodiment of the present invention, the organic electronic device may be an organic light emitting device, an organic solar cell, an organic transistor, an organic memory, or an organic photoconductor (OPC).
The fullerene derivative according to the present invention improves the solubility and the compatibility with the semiconductor polymer by introducing a pyrrolidine group into the fullerene.
In addition, the fullerene derivative according to the present invention has excellent electrochemical stability and physicochemical properties while maintaining intrinsic properties of fullerene, and can provide excellent thermal stability in the production of an organic electronic device containing the same, It is possible to provide an organic electronic device having improved energy conversion efficiency because it is possible to realize a high level of open circuit voltage (Voc) because it is excellent in compatibility with a polymer material as a donor.
1 is a schematic view of an organic solar cell according to the present invention.
Hereinafter, the present invention will be described in more detail. Unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the following description, And a description of the known function and configuration will be omitted.
The substituents comprising " alkyl ", " alkoxy " and other " alkyl " moieties described in this invention encompass both linear and branched forms. The term " aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and may be a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like. "Heteroaryl" in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon Means a 5 to 6 membered monocyclic heteroaryl and a polycyclic heteroaryl condensed with at least one benzene ring and may be partially saturated. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond.
The term "cycloalkyl" in the present invention means a saturated hydrocarbon ring, preferably an alicyclic ring having 5 to 7 members, and includes a case where an aromatic or alicyclic ring is fused.
"Heterocycloalkyl" in the present invention means an alicyclic ring containing oxygen, sulfur or nitrogen in the ring as a hetero atom, and the number of heteroatoms is 1-4, preferably 1-2. Cycloalkyl in heterocycloalkyl is preferably monocycloalkyl or bicycloalkyl, including those in which an aryl or heteroaryl which is an aromatic ring is fused.
The present invention provides pyrrolidine-coupled fullerene derivatives. This has the advantage of increasing the solubility while maintaining the inherent properties of the fullerene, and improving the thermal stability and electrical characteristics of the organic electronic device including the fullerene. At this time, the position of the pyrrolidine introduced into the fullerene derivative may be substituted at any position of the double bond of the fullerene, and may be a mixture with the isomers. The isomers have the same electrochemical or physicochemical properties.
In addition, the fullerene derivative improves the solubility by introducing a pyrrolidine group into fullerene, and is excellent in compatibility with the semiconductor polymer, thereby improving the energy conversion efficiency of the organic electronic device containing the pyrrolidine derivative.
The present invention provides a fullerene derivative represented by the following formula (1).
[Chemical Formula 1]
[In the above formula (1)
A is fullerene of C60, C70, C72, C76, C78 or C84;
R < 1 > is (C1-C20) alkyl;
R 2 and R 3 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, carboxylic acid, amino, cyano, nitro, (C 1 -C 20) alkyl, (C 1 -C 20) haloalkyl, C6-C20) aryl, (C6-C20) aralkyl (C 1 -C 30) alkyl, (C 1 -C 30) alkyl (C6-C20) aryl, (C6-C20) aralkyl (C 1 -C 30) alkoxy (C1-C20) alkylcarbonyl, (C1-C20) cycloalkyl, (C3-C20) heterocycloalkyl, mono- or di ) Alkoxycarbonyl;
and n is an integer of 1 to 9.]
In terms of solubility improvement, preferably, R 1 is (C 1 -C 5) alkyl, and n may be an integer of 1 to 5.
In the fullerene derivative, R 2 and R 3 may each independently be hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) alkoxy, which has a high LUMO energy level, Thereby providing an organic electronic device having improved energy conversion efficiency.
In order to have a higher high LUMO energy level, the fullerene derivative is a fullerene of the above formula (1) wherein A is C60 or C70; R < 1 > is (C1-C5) alkyl; R 2 and R 3 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, carboxylic acid, amino, cyano, nitro, (C 1 -C 20) alkyl, (C 1 -C 20) haloalkyl, C6-C20) aryl, (C6-C20) aralkyl (C 1 -C 30) alkyl, (C 1 -C 30) alkyl (C6-C20) aryl, (C6-C20) aralkyl (C 1 -C 30) alkoxy (C1-C20) alkylcarbonyl, (C1-C20) cycloalkyl, (C3-C20) heterocycloalkyl, mono- or di ) Alkoxycarbonyl; and n is a fullerene derivative which is an integer of 1 to 9.
The fullerene derivative may be one selected from the following structures having excellent energy conversion efficiency, but the present invention is not limited thereto.
The present invention also relates to a process for preparing a compound represented by the formula (4) by reacting a compound represented by the formula (2) and a compound represented by the formula (3) Preparing a compound represented by the following formula (5) through a hydrogenation reaction of a compound represented by the following formula (4); And reacting the compound represented by the following formula (5) with the fullerene and the compound represented by the following formula (6) to prepare a compound represented by the formula (1); . However, it is also possible to synthesize the fullerene derivative by a method that can be recognized by those of ordinary skill in the art.
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[Chemical Formula 6]
[Chemical Formula 1]
[In the above Chemical Formulas 1 to 6,
A is fullerene of C60, C70, C72, C76, C78 or C84;
X is halogen;
R < 1 > is (C1-C20) alkyl;
R 2 and R 3 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, carboxylic acid, amino, cyano, nitro, (C 1 -C 20) alkyl, (C 1 -C 20) haloalkyl, C6-C20) aryl, (C6-C20) aralkyl (C 1 -C 30) alkyl, (C 1 -C 30) alkyl (C6-C20) aryl, (C6-C20) aralkyl (C 1 -C 30) alkoxy (C1-C20) alkylcarbonyl, (C1-C20) cycloalkyl, (C3-C20) heterocycloalkyl, mono- or di ) Alkoxycarbonyl;
and n is an integer of 1 to 9.]
Of the pyrrolidine group can be prepared in the same manner as in the following reaction scheme, but it is needless to say that the fullerene derivative can also be synthesized by other methods known to those skilled in the art.
The present invention also provides an organic electronic device containing the fullerene derivative according to the present invention. Here, the organic electronic device may be an organic light emitting device, an organic solar cell, an organic transistor, an organic memory, or an organic photoconductor (OPC), and may be an organic solar cell or an organic transistor.
Hereinafter, an organic solar cell containing a novel fullerene derivative according to the present invention will be described in detail with reference to FIG. 1, but the present invention is not limited thereto.
The organic solar cell shown in FIG. 1 may be manufactured by stacking a
The
The
The
On the other hand, the
In addition, the
Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention, and the contents of the present invention are not limited by the following examples.
[Example 1] Synthesis of C 60 -fused N- (methyl butyrate) -2-phenylpyrrolidine
Step 1. Synthesis of methyl 4 - ((2- (benzyloxy) -2-oxoethyl) amino) butanoate.
Methyl 4-aminobutylate hydrochloride (10.0 g, 65.10 mmol) dissolved in 200 mL of 1,4-dioxane was added dropwise triethylamine (9.1 mL, 130.20 mmol) and the mixture was stirred at room temperature (25 ° C) for 15 minutes. The temperature of the reaction solution was lowered to 0 ° C, and a solution of benzyl bromoacetate (7.7 mL, 52.08 mmol) dissolved in 60 mL of 1,4-dioxane was slowly injected. The reaction temperature was raised to room temperature, stirred for 16 hours, concentrated, and water was added thereto, followed by extraction with EtOAc. The organic layer was dried over magnesium sulfate, concentrated by filtration and separated by silica column chromatography (Hex: MC = 1: 1) to recover 4.1 g of methyl 4 - ((2- (benzyloxy) -2-oxoethyl) amino) butanoate (40.0%).
1 H NMR (CDCl3, 300MHz) : δ 7.35 (s, 5H), 5.16 (s, 2H), 3.66 (3H, s), 3.44 (s, 2H), 2.65 (t, J = 7.0Hz, 2H), 2.38 (t, J = 7.3Hz, 2H), 2.04 (s, 1H), 1.81 (q, J = 7.2Hz, 2H)
Step 2. Synthesis of 2 - ((4-Methoxy-4-oxobutyl) amino) acetic acid
5% Pd / C (10% w / w) was added to the solution, and the solution was stirred while methanol was added to the solution. The reaction vessel was filled with H 2 gas. After stirring for 2 hours, the mixture was filtered and concentrated to give a white solid. The white solid was recrystallized from a mixed solvent of methanol and ether to obtain 1.2 g of 2 - ((4-methoxy-4-oxobutyl) amino) acetic acid (61.0%).
1 H NMR (MeOD, 300MHz) : δ 3.70 (s, 3H), 3.51 (s, 2H), 3.07 (t, J = 7.7Hz, 2H), 2.50 (t, J = 7.1Hz, 2H), 1.99 ( q, J = 7.6 Hz, 2H)
Step 3. Synthesis of C 60 -fused N- (methyl butyrate) -2-phenylpyrrolidine
C 60 (1.0g, 1.39mmol), and then stirring the solution in Toluene 500mL, 2 - ((4 -methoxy-4-oxobutyl) amino) acetic acid (243mg, 1.39mmol) and benzaldehyde (705μL, 6.94mmol) to . The reaction mixture was refluxed at 115 [deg.] C for 2 hours. Fulleropyrrolidine (350 mg) was obtained by silica column chromatography (Toluene) after concentration of the reaction solution to about 25 mL (30.8%).
1 H NMR (CDCl3, 300MHz) : δ 7.80 (broad s, 2H), 7.49-7.31 (m, 3H), 5.15 (d, J = 9.4Hz, 1H), 5.10 (1H, s), 4.14 (d, J = 9.3Hz, 1H), 3.77 (s, 3H), 3.36-3.19 (m, 1H), 2.92-2.59 (m, 3H), 2.46-2.13 (m, 3H)
[Example 2] Synthesis of C 60 -fused N- (methyl butyrate) -2- (2-methoxyphenyl) pyrrolidine
4-methoxy-4-oxobutyl) aminoacetic acid (158 mg, 0.90 mmol) obtained in Step 2 of Example 1 was added to a solution of C 60 (650 mg, 0.90 mmol) And 2-Methoxybenzaldehyde (614 mg, 4.51 mmol). The reaction mixture was refluxed at 115 [deg.] C for 2 hours. The reaction solution was concentrated to about 250 mL, and 284 mg of 2-OMe-C4-fulleropyrrolidine (32.5%) was obtained through silica column chromatography (Toluene).
MS (MALDI): m / z 1934.208 (M +), 719.944 (C60).
1 H NMR (CDCl3, 300MHz) : δ 7.96 (dd, J = 1.4Hz, 7.5Hz, 1H), 7.33-7.26 (m, 1H), 7.06 (t, J = 7.4Hz, 1H), 6.92 (d, J = 7.9Hz, 1H), 5.71 (s, 1H), 5.11 (d, J = 9.2Hz, 1H), 4.14 (d, J = 9.2Hz, 1H), 3.73 (d, J = 13.8Hz, 6H) , 3.34-3.18 (m, 1 H), 2.89-2.57 (m, 3H), 2.41-2.13 (m, 2H).
14 C NMR (CDCl 3, 300 MHz): δ 174.04, 158.26, 156.97, 155.05, 154.22, 154.07, 147.31, 147.29, 146.75, 146.52, 146.25, 146.22, 146.17, 146.11, 146.06, 145.95, 145.91, 145.72, 145.58, 145.32, 145.30, 145.26, 145.23, 145.09, 145.03, 144.59, 144.42, 144.38, 143.06, 142.99, 142.64, 142.56, 142.54, 142.31, 142.26, 142.19, 142.17, 142.10, 142.08, 141.98, 141.82, 141.71, 141.54, 140.21, 140.15, 139.41, 136.53, 136.41, 136.12, 134.54, 129.93, 129.05, 125.66, 121.12, 111.10, 75.93, 74.22, 69.15, 66.57, 55.22, 52.30, 51.74, 32.07, 23.60.
[Example 3] Synthesis of C 60 -fused N- (methyl butyrate) -2- (2-hexyloxyphenyl) pyrrolidine
C 60 (575mg, 0.80mmol) of the compound obtained in Step 2 was stirred in a solution in Toluene 260 mL, Example 1 2 - ((4-methoxy -4-oxobutyl) amino) acetic acid (140mg, 0.80mmol) And 2- (hexyloxy) benzaldehyde (824 mg, 4.00 mmol). The reaction mixture was refluxed at 115 [deg.] C for 2 hours. After removing about 190 mL of the reaction solution, it was separated and concentrated using silica column chromatography (Toluene). The obtained compound was recrystallized using a mixed solvent of CHCl 3 and MeOH to obtain 260 mg of 2-Ohexyl-C4-fulleropyrrolidine (32%).
MS (FAB): 1040 (M < + >).
1 H NMR (CDCl3, 300MHz) : δ 7.95 (d, J = 8.2Hz, 1H), 7.23 (d, J = 6.5Hz, 1H), 7.04 (t, J = 7.5Hz, 1H), 6.89 (d, J = 8.1Hz, 1H), 5.71 (s, 1H), 5.11 (d, J = 9.3Hz, 1H), 4.14 (d, J = 9.4Hz, 1H), 3.99 (q, J = 7.3Hz, 1H) , 3.80-3.65 (m, 4H), 3.35-3.20 (m, 1H), 2.90-2.56 (m, 3H), 2.45-2.11 m, 5H), 0.90 (t, J = 6.5 Hz, 3H).
14 C NMR (CDCl 3, 300 MHz): δ 174.05, 157.77, 157.02, 155.40, 154.31, 154.06, 147.31, 147.28, 146.79, 146.75, 146.27, 146.24, 146.22, 146.17, 146.09, 146.06, 145.95, 145.91, 145.74, 145.57, 145.31 145.29 145.26 145.23 145.09 144.58 144.45 144.38 143.06 143.00 142.63 142.56 142.53 142.32 142.28 142.27 142.20 142.16 142.09 141.98 141.83 141.72 141.70 141.56 140.20, 140.14, 139.44, 139.40, 136.57, 136.38, 136.07, 134.49, 129.86, 129.00, 125.53, 120.83, 111.57, 75.94, 74.40, 69.13, 68.05, 66.53, 52.35, 51.76, 32.08, 31.70, 29.15, 25.74, 23.66, 22.62, 14.19.
[Example 4] Synthesis of C 60 -fused N- (methyl butyrate) -2- (2,3-dimethoxyphenyl) pyrrolidine
C 60 (350mg, 0.49mmol) of the compound obtained in Step 2 was stirred in a 170mL solution in Toluene, Example 1 2 - ((4-methoxy -4-oxobutyl) amino) acetic acid (85mg, 0.49mmol) and 2,3-dimethoxybenzaldehyde (404 mg, 2.43 mmol) was added. The reaction mixture was refluxed at 115 [deg.] C for 2 hours. After removing about 190 mL of the reaction solution, it was separated and concentrated using silica column chromatography (Toluene). The obtained compound was recrystallized using a mixed solvent of CHCl 3 and MeOH to obtain 164 mg of 2,3-diOMe-C4-fulleropyrrolidine (34%).
MS (FAB): 1000 (M < + >).
1 H NMR (CDCl3, 300MHz) : δ 7.57 (d, J = 6.6Hz, 1H), 7.13 (t, J = 7.6Hz, 1H), 6.87 (d, J = 8.1Hz, 1H), 5.65 (s, 1H), 5.09 (d, J = 9.3 Hz, 1H), 4.25 (d, J = 8.4 Hz, 1H), 3.89 (s, 2.87-2.73 (m, 1H), 2.70-2.55 (m, 2H), 2.39-2.25 (m, 1H), 2.23-2.10 (m, 1H).
13 C NMR (CDCl 3, 300 MHz): δ 174.03, 156.78, 154.41, 154.16, 153.90, 152.68, 148.85, 147.30, 146.62, 146.54, 146.28, 146.25, 146.21, 146.12, 146.08, 145.96, 145.74, 145.57, 145.56, 145.34, 145.30, 145.29, 145.23, 145.20, 145.10, 144.67, 144.60, 144.44, 144.37, 143.11, 142.99, 142.64, 142.60, 142.57, 142.54, 142.31, 142.27, 142.18, 142.14, 142.04, 141.99, 141.85, 141.76, 141.71, 141.60, 140.16, 139.97, 139.47, 136.72, 136.50, 136.05, 135.17, 130.48, 124.14, 122.11, 111.80, 76.07, 74.69, 69.21, 66.46, 61.27, 55.63, 52.18, 51.74, 32.01, 23.49.
[Example 5] Synthesis of C 60 -fused N- (methyl butyrate) -2- (2,3-dihexyloxyphenyl) pyrrolidine
C 60 (350mg, 0.49mmol) of the compound obtained in Step 2 was stirred in a 170mL solution in Toluene, Example 1 2 - ((4-methoxy -4-oxobutyl) amino) acetic acid (85mg, 0.49mmol) and 2,3-bis (hexyloxy) benzaldehyde (745 mg, 2.43 mmol) was added. The reaction mixture was refluxed at 115 [deg.] C for 2 hours. After removing about 100 mL of the reaction solution, it was separated by silica column chromatography (Hex: Toluene = 1: 1 ~ 1: 3) and concentrated. The concentrated compound was recrystallized using a mixed solvent of CHCl 3 and MeOH to obtain 150 mg of 2,3-diOHexyl-C4-fulleropyrrolidine (27%).
MS (FAB): 1141 (M < + >).
1 H NMR (CDCl3, 300MHz) : δ 7.55 (d, J = 7.9Hz, 1H), 7.07 (t, J = 8.0Hz, 1H), 6.83 (d, J = 8.0Hz, 1H), 5.65 (s, 1H), 5.09 (d, J = 9.2 Hz, 1H), 4.10 (q, J = 15.6 Hz, 1H), 4.01-3.91 (m, 3H), 3.75 ), 2.87-2.70 (m, 1H), 2.68-2.50 (m, 2H), 2.40-2.25 (m, 12H), 1.00-0.82 (m, 6H).
13 C NMR (CDCl 3, 300 MHz): δ 174.07, 156.83, 154.67, 154.25, 154.09, 152.35, 148.39, 147.30, 146.81, 146.64, 146.30, 146.27, 146.24, 146.21, 146.12, 146.08, 146.06, 145.94, 145.76, 145.59, 145.55, 145.34, 145.29, 145.26, 145.22, 145.18, 145.09, 144.64, 144.62, 144.45, 144.35, 143.10, 142.98, 142.63, 142.60, 142.55, 142.52, 142.30, 142.27, 142.21, 142.17, 142.14, 142.11, 142.05, 141.98, 141.85, 141.73, 141.68, 141.59, 140.13, 139.83, 139.48, 136.65, 136.58, 135.92, 135.00, 130.55, 123.79, 122.02, 112.93, 76.12, 74.89, 31.18, 31.58, 30.37, 29.29, 25.94, 25.87, 23.58, 22.83, 22.62, 14.23, 14.05.
[Example 6] Synthesis of C 60 -fused N- (methyl butyrate) -2- (2,6-dimethoxyphenyl) pyrrolidine
C 60 (600mg, 0.83mmol) of the compound obtained in Step 2 was stirred in a 280mL solution in Toluene, Example 1 2 - ((4-methoxy -4-oxobutyl) amino) acetic acid (146mg, 0.83mmol) and 2,6-dimethoxybenzaldehyde (692 mg, 4.17 mmol) was added. The reaction mixture was refluxed at 115 [deg.] C for 2 hours. After removing about 100 mL of the reaction solution, it was separated and concentrated using silica column chromatography (Toluene). The obtained compound was recrystallized from a mixed solvent of CHCl 3 and MeOH to obtain 121 mg of 2,6-diOMe-C4-fulleropyrrolidine (15%).
MS (FAB): 1000 (M < + >).
1 H NMR (CDCl3, 300MHz) : δ 7.26 (t, J = 8.4Hz, 1H), 6.58 (q, J = 10.4Hz, 2H), 5.93 (s, 1H), 5.05 (d, J = 9.1Hz, 1H), 3.99 (d, J = 8.9 Hz, 1H), 3.75 (d, J = 4.2 Hz, 1H) ), 2.72-2.60 (m, 2H), 2.40-2.22 (m, 1H), 2.20-2.05 (m, 6H).
14 C NMR (CDCl 3, 300 MHz): δ 174.57, 159.94, 159.84, 157.28, 155.55, 154.95, 154.86, 148.28, 147.21, 146.72, 146.27, 146.17, 146.15, 146.08, 145.98, 145.95, 145.91, 145.85, 145.79, 145.65, 144.50, 145.27, 145.24, 145.22, 145.14, 145.03, 144.90, 144.68, 144.45, 144.41, 143.11, 143.04, 142.59, 142.55, 142.53, 142.44, 142.35, 142.30, 142.10, 142.04, 142.01, 141.78, 141.63, 141.34, 139.99, 139.96, 139.74, 139.07, 136.88, 136.69, 135.98, 134.47, 129.94, 112.46, 104.83, 104.17, 75.71, 74.12, 69.81, 66.30, 55.96, 54.84, 51.97, 51.58, 31.88, 29.72, 23.24.
[Example 7] Synthesis of C 60 -fused N- (methyl hexanoate) -2- (2,6-dimethoxyphenyl) pyrrolidine
Step 1. Synthesis of Methyl 6 - ((2- (benzyloxy) -2-oxoethyl) amino) hexanoate
Methyl 6-aminohexanoate hydrochloride (20.0 g, 110.1 mmol) dissolved in 340 mL of 1,4-dioxane was added dropwise triethylamine (31 mL, 220.19 mmol), and the mixture was stirred at room temperature for 15 minutes. The reaction solution was cooled to 0 ° C and a solution of benzyl bromoacetate (13 mL, 88.08 mmol) dissolved in 100 mL of 1,4-dioxane was slowly injected. The reaction temperature was raised to room temperature (25 ° C), stirred for 15 hours, and concentrated. Water was added and extracted with EtOAc. The organic layer was dried over magnesium sulfate, concentrated by filtration and purified by silica column chromatography (Hex: MC = 1: 1) to give methyl 6 - ((2- (benzyloxy) -2-oxoethyl) amino) hexanoate 14 g was recovered (73%).
1 H NMR (CDCl3, 300MHz) : δ 7.35 (s, 5H), 5.16 (s, 2H), 3.66 (3H, s), 3.44 (s, 2H), 2.65 (t, J = 7.1Hz, 2H), 2.30 (t, J = 7.5 Hz, 2H), 1.69-1.55 (m, 3H), 1.55-1.29 (m, 4H)
Step 2. Synthesis of 2 - ((6-methoxy-6-oxohexyl) amino) acetic acid
2 - ((4-methoxy- 4-oxobutyl) amino) acetic acid (14.0g, 47.72mmol) was dissolved in methanol 100 mL, 5% Pd / C (10% w / w) while stirring into a H 2 The reaction vessel was filled with gas. After stirring for 2 hours, the mixture was filtered and concentrated to give a white solid. The white solid was recrystallized from a mixed solvent of methanol and ether to obtain 9.3 g of 2 - ((6-methoxy-6-oxohexyl) amino) acetic acid (96%).
1 H NMR (CDCl3, 300MHz) : δ 3.66 (s, 3H), 3.95 (s, 2H), 3.01 (t, J = 7.7Hz, 2H), 2.32 (t, J = 7.3Hz, 2H), 41.90- 1.77 (m, 2H), 1.72-1.60 (m, 2H), 1.49-1.32 (m, 2H).
Step 3. Synthesis of C 60 -fused N- (methyl hexanoate) -2- (2,6-dimethoxyphenyl) pyrrolidine
C 60 (1.0g, 1.39mmol) and then the stirring was sufficiently filled with nitrogen gas while dissolving in Toluene 480mL, 2 - ((6 -methoxy-6-oxohexyl) amino) acetic acid (282mg, 1.39mmol), 2, 3-dimethoxybenzaldehyde (1.2 g, 6.94 mmol). The mixture was refluxed at 115 [deg.] C for 3 hours. About 350 mL of the reaction solution was removed using an evaporator, and the reaction solution was separated and concentrated using silica column chromatography (Toluene). The obtained compound was recrystallized from CHCl3 and MeOH to obtain 50 mg (10%) of 2,6-diOMe-C6-fulleropyrrolidine.
MS (FAB): 1028 (M < + >).
1 H NMR (CDCl3, 300MHz) : δ 7.31-7.22 (m, 1H), 6.59 (t, J = 9.4Hz, 2H), 5.92 (s, 1H), 5.02 (d, J = 9.1Hz, 1H), (D, J = 9.0 Hz, 1H), 3.76 (d, J = 2.7 Hz, 6H), 3.69 (s, 3H), 3.23-3.12 (t, J = 7.3 Hz, 2H), 2.10-1.73 (m, 6H).
14 C NMR (CDCl 3, 300 MHz): δ 174.29, 159.95, 159.91, 157.28, 155.72, 155.12, 155.02, 147.28, 147.20, 146.74, 146.30, 146.27, 145.49, 145.24, 145.21, 145.13, 145.03, 144.90, 144.68, 144.46, 144.40, 143.11, 143.03, 142.58, 142.54, 142.52, 142.44, 142.38, 142.36, 142.30, 142.10, 142.03, 141.79, 141.68, 141.63, 141.34, 139.98, 139.94, 139.74, 139.10, 136.96, 136.73, 135.96, 134.44, 129.86, 112.67, 104.92, 104.16, 75.78, 74.09, 69.89, 66.57, 55.98, 54.94, 52.74, 51.53, 34.26, 27.57, 27.22, 25.10.
[Example 8] Synthesis of C 60 -fused N- (methyl hexanoate) -2- (hexyloxyphenyl) pyrrolidine
(6-methoxy-6-oxohexyl) aminoacetic acid (282 mg, 1.39 mmol) obtained in the step 2 of Example 7 was stirred and then the solution obtained by dissolving C 60 (1.0 g, 14.39 mmol) in 480 mL of toluene was stirred. ) And 2- (hexyloxy) benzaldehyde (1.4 g, 6.94 mmol). The reaction mixture was refluxed at 115 [deg.] C for 2 hours. After removing about 250 mL of the reaction solution, it was separated and concentrated using silica column chromatography (Toluene). The obtained compound was recrystallized using a mixed solvent of CHCl 3 and MeOH to obtain 581 mg of 2-Ohexyl-C6-fulleropyrrolidine (39%).
MS (FAB): 1068 (M < + >).
1 H NMR (CDCl3, 300MHz) : δ 7.98 (dd, J = 1.5Hz, 7.6Hz, 1H), 7.23 (dd, J = 1.6Hz, 9.2Hz, 1H), 7.05 (t, J = 7.4Hz, 1H ), 6.89 (d, J = 8.0Hz, 1H), 5.68 (s, 1H), 5.07 (d, J = 9.2Hz, 1H), 4.15 (d, J = 9.2Hz, 1H), 3.99 (q, J = 7.3Hz, 1H), 3.78-3.65 ( m, 4H), 3.26 (q, J = 9.5Hz, 1H), 2.62-2.48 (m, 1H), 2.43 (t, J = 7.3Hz, 2H), 2.10 -1.49 (m, 8H), 1.48-1.19 (m, 6H), 0.90 (t, J = 6.7 Hz, 3H).
14 C NMR (CDCl 3, 300 MHz):? 174.20, 157.71, 157.18, 155.54,154.44,154.18,147.29,146.82,146.31,146.23,146.21,146.16,146.08,146.05,145.93,145.91,145.74,145.60,145. 145.25, 145.22, 145.09, 145.06, 144.60, 144.46, 144.37, 143.05, 143.00, 142.63, 142.58, 142.56, 142.53, 142.34, 142.31, 142.18, 142.09, 141.97, 141.85, 141.72, 141.70, 141.56, 140.18, 140.12, 139.42, 136.32, 136.40, 136.09, 134.48, 129.93, 128.92, 125.73, 120.83, 111.53, 76.03, 74.51, 69.18, 68.03, 66.72, 52.98, 51.58, 34.16, 31.71, 29.15, 28.21, 27.11, 25.75, 25.08, 22.64, 14.21.
[Example 9] Synthesis of C 60 -fused N- (methyl hexanoate) -2- (2,6-dimethoxyphenyl) pyrrolidine
The mixture of 2 - ((6-methoxy-6-oxohexyl) amino) acetic acid (282 mg, 1.39 mmol) obtained in Step 2 of Example 7 was added to a solution of C 60 (1.0 g, 1.39 mmol) ) And 2,6-dimethoxybenzaldehyde (1.2 g, 6.94 mmol) were added. The reaction mixture was refluxed at 115 [deg.] C for 2 hours. After removing about 350 mL of the reaction solution, it was separated and concentrated using silica column chromatography (Toluene). The obtained compound was recrystallized using a mixed solvent of CHCl 3 and MeOH to obtain 50 mg of 2,6-diOMe-C6-fulleropyrrolidine (10%).
MS (FAB): 1028 (M < + >).
1 H NMR (CDCl3, 300MHz) : δ 7.31-7.22 (m, 1H), 6.59 (t, J = 9.4Hz, 2H), 5.92 (s, 1H), 5.02 (d, J = 9.1Hz, 1H), (D, J = 9.0 Hz, 1H), 3.76 (d, J = 2.7 Hz, 6H), 3.69 (s, 3H), 3.23-3.12 (t, J = 7.3 Hz, 2H), 2.10-1.73 (m, 6H).
14 C NMR (CDCl 3, 300 MHz): δ 174.29, 159.95, 159.91, 157.28, 155.72, 155.12, 155.02, 147.28, 147.20, 146.74, 146.30, 146.27, 145.49, 145.24, 145.21, 145.13, 145.03, 144.90, 144.68, 144.46, 144.40, 143.11, 143.03, 142.58, 142.54, 142.52, 142.44, 142.38, 142.36, 142.30, 142.10, 142.03, 141.79, 141.68, 141.63, 141.34, 139.98, 139.94, 139.74, 139.10, 136.96, 136.73, 135.96, 134.44, 129.86, 112.67, 104.92, 104.16, 75.78, 74.09, 69.89, 66.57, 55.98, 54.94, 52.74, 51.53, 34.26, 27.57, 27.22, 25.10.
[Example 10] Production of organic solar cell
BATRON-P (PEDOT: PSS) (Bayer, Germany) dissolved in aqueous solution was spin-coated on ITO glass at 4000 rpm for 30 seconds and then heat-treated at 150 ° C for 10 minutes. Thereafter, a solution was prepared by dissolving the conductive polymer (electron donor, poly 3-hexylthiophene (P3HT)): Example 1 (electron acceptor) in 1 ml of chlorobenzene at a weight ratio of 1: 0.8 to prepare a solution, Coated for 15 seconds, and maintained at room temperature for 1 hour. Thereafter, aluminum was deposited at a thickness of 200 nm in the evaporator, and then heat-treated at 150 ° C for 30 minutes to produce an organic solar cell.
The evaluation of the characteristics of the organic solar cell manufactured by the above method is proceeded and shown in Table 1 below. In the following Table 1, V oc (V) and J sc (mA / cm 2 ) show the voltage and current when the current is 0 and the current and voltage when the voltage is 0 Value.
In addition, FF (fill factor) can be calculated from the following equation (1).
[Equation 1]
In the above equation (1), V mpp and J mpp represent voltage and current values at a point indicating the maximum uniformity in the current-voltage measurement of the fabricated device, and V oc (V) and J sc (mA / cm 2 ) represents the current value when the current is 0 and the voltage value when the current is 0 and the current value when the voltage is 0, respectively.
Further, the photoelectric conversion efficiency (%) can be calculated from the following equation (2).
&Quot; (2) "
In the above equation (2), FF, Voc and J sc is as defined in Equation (1), and P in represents the total energy of light incident on the device.
[Examples 11 to 18] Manufacture of organic solar cell
An organic solar cell was prepared in the same manner as in Example 10, except that each of Examples 2 to 9 was used instead of Example 1 in Example 10.
Further, the evaluation of the characteristics of the organic solar cell manufactured by the above method is proceeded, and it is shown in Table 1 above.
[Comparative Example 1]
An organic solar cell was prepared in the same manner as in Example 10, except that [6,6] -phenyl C 61 -butanoate methyl ester (PC 61 BM) was used instead of Example 1 in Example 10.
Further, the evaluation of the characteristics of the organic solar cell manufactured by the above method is proceeded, and it is shown in Table 1 above.
As a result, as shown in Table 1, the fullerene derivative according to the present invention is relatively in contrast to [6,6] -phenyl C61-butanoic acid methyl ester (PC61BM) of Comparative Example 1 having no pyrrolidine group It can be confirmed that the energy conversion efficiency is improved by exhibiting the characteristics of high open circuit voltage and it has an advantage that it can be widely used for the production of organic electronic devices because of its excellent solubility characteristic in organic solvent.
Claims (9)
[Chemical Formula 1]
[In the above formula (1)
A is fullerene of C60, C70, C72, C76, C78 or C84;
R < 1 > is (C1-C5) alkyl;
R 2 and R 3 are each independently hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) alkoxy;
and n is an integer of 1 to 5.]
In the above formula (1), A is C60 or C70 fullerene; R < 1 > is (C1-C5) alkyl; R 2 and R 3 are each independently hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) alkoxy; and n is an integer of 1 to 5.
Wherein the fullerene derivative is selected from the following structures.
[Chemical Formula 5]
[Chemical Formula 6]
[Chemical Formula 1]
[In the formulas (1), (5) and (6)
A is fullerene of C60, C70, C72, C76, C78 or C84;
R < 1 > is (C1-C5) alkyl;
R 2 and R 3 are each independently hydrogen, (C 1 -C 10) alkyl or (C 1 -C 10) alkoxy;
and n is an integer of 1 to 5.]
Wherein the compound represented by Formula 5, fullerene, and the compound represented by Formula 6 are dissolved in an organic solvent, and the compound represented by Formula 1 is prepared by refluxing reaction at 100 to 150 ° C.
The compound represented by the following general formula (5)
Reacting a compound represented by Formula 2 and a compound represented by Formula 3 to prepare a compound represented by Formula 4; And
Preparing a compound represented by the following formula (5) through a hydrogenation reaction of a compound represented by the following formula (4); ≪ / RTI > by weight of the fullerene derivative.
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
[In the above Chemical Formulas 2 to 5,
X is halogen;
R < 1 > is (C1-C5) alkyl;
and n is an integer of 1 to 5.]
Wherein the organic electronic device is an organic light emitting device, an organic solar cell, an organic transistor, an organic memory, or an organic photoconductor (OPC).
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| KR20090113607A (en) * | 2008-04-28 | 2009-11-02 | 한국화학연구원 | Methanofullerene Compounds Having Etyleneoxy Substituents and Its Use for Organic Electronics |
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| KR20090113607A (en) * | 2008-04-28 | 2009-11-02 | 한국화학연구원 | Methanofullerene Compounds Having Etyleneoxy Substituents and Its Use for Organic Electronics |
| KR20120119414A (en) * | 2011-04-21 | 2012-10-31 | 한국과학기술연구원 | Methanofullerene derivatives and the organic solar cell device comprising the derivatives |
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