JP5979710B2 - Fullerene derivative and organic solar cell using the same - Google Patents
Fullerene derivative and organic solar cell using the same Download PDFInfo
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- JP5979710B2 JP5979710B2 JP2012090738A JP2012090738A JP5979710B2 JP 5979710 B2 JP5979710 B2 JP 5979710B2 JP 2012090738 A JP2012090738 A JP 2012090738A JP 2012090738 A JP2012090738 A JP 2012090738A JP 5979710 B2 JP5979710 B2 JP 5979710B2
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- sugar
- fullerene derivative
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims description 58
- -1 p-methoxybenzyl group Chemical group 0.000 claims description 45
- 239000010409 thin film Substances 0.000 claims description 28
- 125000001153 fluoro group Chemical group F* 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 150000002430 hydrocarbons Chemical group 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 6
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 5
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 claims description 3
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 3
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 claims description 3
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- XILIYVSXLSWUAI-UHFFFAOYSA-N 2-(diethylamino)ethyl n'-phenylcarbamimidothioate;dihydrobromide Chemical compound Br.Br.CCN(CC)CCSC(N)=NC1=CC=CC=C1 XILIYVSXLSWUAI-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
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- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 10
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- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 9
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- CYAYKKUWALRRPA-RGDJUOJXSA-N [(2r,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-bromooxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@H]1O[C@H](Br)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O CYAYKKUWALRRPA-RGDJUOJXSA-N 0.000 description 8
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- 150000002332 glycine derivatives Chemical class 0.000 description 7
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
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- 239000012298 atmosphere Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 5
- 229910003472 fullerene Inorganic materials 0.000 description 5
- 125000000625 hexosyl group Chemical group 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- CDLMQSSFJCERSO-YMQHIKHWSA-N [(2r,3r,4s,5r,6s)-3,4,5-triacetyloxy-6-(4-formylphenoxy)oxan-2-yl]methyl acetate Chemical compound CC(=O)O[C@@H]1[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(=O)C)O[C@H]1OC1=CC=C(C=O)C=C1 CDLMQSSFJCERSO-YMQHIKHWSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 0 C*(C)COC(C1O*)OCC1O Chemical compound C*(C)COC(C1O*)OCC1O 0.000 description 3
- YOXPJRKJOJIWCY-WSGIOKLISA-N CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)OC2=CC=C(C=C2)C3=CC4=C(O3)CCN4)OC(=O)C)OC(=O)C)OC(=O)C Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)OC2=CC=C(C=C2)C3=CC4=C(O3)CCN4)OC(=O)C)OC(=O)C)OC(=O)C YOXPJRKJOJIWCY-WSGIOKLISA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- NUZWLKWWNNJHPT-UHFFFAOYSA-N anthralin Chemical compound C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O NUZWLKWWNNJHPT-UHFFFAOYSA-N 0.000 description 3
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- 229960002311 dithranol Drugs 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
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- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001805 pentosyl group Chemical group 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
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- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 108010077895 Sarcosine Proteins 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003525 allosyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 125000000089 arabinosyl group Chemical group C1([C@@H](O)[C@H](O)[C@H](O)CO1)* 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
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- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
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- 125000006017 1-propenyl group Chemical group 0.000 description 1
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- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 description 1
- MDHYEMXUFSJLGV-UHFFFAOYSA-N beta-phenethyl acetate Natural products CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 1
- 150000001602 bicycloalkyls Chemical group 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000006309 butyl amino group Chemical group 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000006310 cycloalkyl amino group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 125000004914 dipropylamino group Chemical group C(CC)N(CCC)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- OAMZXMDZZWGPMH-UHFFFAOYSA-N ethyl acetate;toluene Chemical compound CCOC(C)=O.CC1=CC=CC=C1 OAMZXMDZZWGPMH-UHFFFAOYSA-N 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- BJHIKXHVCXFQLS-UYFOZJQFSA-N fructose group Chemical group OCC(=O)[C@@H](O)[C@H](O)[C@H](O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000001245 hexylamino group Chemical group [H]N([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000002190 incident photon conversion efficiency spectrum Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229940031993 lithium benzoate Drugs 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 238000000074 matrix-assisted laser desorption--ionisation tandem time-of-flight detection Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000004894 pentylamino group Chemical group C(CCCC)N* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000004351 phenylcyclohexyl group Chemical group C1(=CC=CC=C1)C1(CCCCC1)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000005629 sialic acid group Chemical group 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000007970 thio esters Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Saccharide Compounds (AREA)
- Photovoltaic Devices (AREA)
Description
本発明は、フラーレン誘導体およびこれを用いた有機太陽電池に関する。 The present invention relates to a fullerene derivative and an organic solar cell using the same.
有機太陽電池は、活性層や電荷輸送物質に有機物を使用した有機太陽電池であり、1991年にM.グレッツェルによって開発された色素増感太陽電池と、1986年にコダックのC.W.タンによって開発された有機薄膜太陽電池とがよく知られている。
いずれも軽量・薄膜で、フレキシブル化可能である点、ロール・トゥ・ロールでの生産が可能である点など、現在主流の無機系太陽電池とは異なる特長を持っていることから、新たな市場形成が期待されている。
中でも有機薄膜太陽電池は、電解質フリー、重金属化合物フリー等の特長を持つうえに、最近、Y.Liangらによって変換効率7.4%の報告がなされたことなどの理由から、大きな注目を集めている(非特許文献1参照)。
The organic solar cell is an organic solar cell using an organic substance as an active layer or a charge transport material. Dye-sensitized solar cells developed by Gretzell and Kodak ’s C.I. W. Organic thin-film solar cells developed by Tan are well known.
All are lightweight, thin film, flexible, roll-to-roll, and other features that are different from the current mainstream inorganic solar cells. Formation is expected.
In particular, organic thin film solar cells have features such as electrolyte-free and heavy metal compound-free. Much attention has been paid to the reason that Liang et al. Reported that the conversion efficiency was 7.4% (see Non-Patent Document 1).
有機薄膜太陽電池の活性層には、正孔輸送性を有するp型半導体材料と、電子輸送性を有するn型半導体材料とを組み合わせて用いられることが多い。通常、p型半導体材料は電子供与性を有し、n型半導体材料は電子受容性を有することから、それぞれドナー材料、アクセプター材料ともいわれる。
例えば、p型半導体材料とn型半導体材料とを混合した溶液を調製し、塗布法によって活性層を形成することで、得られる太陽電池の変換効率が大幅に上昇することが報告されている(非特許文献2参照)。この手法によって得られる活性層は、ドナー/アクセプター界面が、活性層のバルク全体に形成されることから、一般的にバルクへテロジャンクション層と呼ばれる。
また、ドナー/アクセプター界面面積が極大化され、かつ、それぞれが完全に分離して、発生したキャリアの再結合を抑制しつつ高移動度を発現する構造が理想であると言われ、ドナー/アクセプター界面を高密度に形成させる超階層ナノ構造も提案されている(非特許文献3参照)。
The active layer of an organic thin film solar cell is often used in combination with a p-type semiconductor material having a hole transporting property and an n-type semiconductor material having an electron transporting property. In general, a p-type semiconductor material has an electron donating property, and an n-type semiconductor material has an electron accepting property. Therefore, they are also referred to as a donor material and an acceptor material, respectively.
For example, it is reported that the conversion efficiency of the resulting solar cell is significantly increased by preparing a mixed solution of a p-type semiconductor material and an n-type semiconductor material and forming an active layer by a coating method ( Non-patent document 2). The active layer obtained by this method is generally called a bulk heterojunction layer because the donor / acceptor interface is formed in the entire bulk of the active layer.
In addition, it is said that a donor / acceptor interface area is maximized, and each of the donor / acceptor interface areas is completely separated and suppresses the recombination of the generated carriers and expresses high mobility. Super-hierarchical nanostructures that form interfaces at high density have also been proposed (see Non-Patent Document 3).
有機薄膜太陽電池用のn型半導体材料としては、高電子受容性および高電荷分離能、高電子移動度、高耐熱性等の特長から、フラーレンおよびその誘導体がよく用いられ、塗布型材料としてはC60またはC70−PCBMが標準的に用いられている(非特許文献4〜6参照)。 As n-type semiconductor materials for organic thin-film solar cells, fullerenes and their derivatives are often used because of their high electron acceptability, high charge separation, high electron mobility, high heat resistance, etc. C60 or C70-PCBM is used as standard (see Non-Patent Documents 4 to 6).
しかしながら、PCBMは、溶解性が低い、単体での成膜均一性が悪い、結晶化温度が高過ぎる(195℃)等の種々の問題を有している。
溶解性が低い場合、使用できる溶媒の種類や濃度に制限が発生するために、適用できる塗布方式が限られる、混合できる材料が限られる、厚膜化が困難等の問題が生じる。
単体での成膜均一性が悪い場合、理想の微細構造を目指す等の理由から単体での成膜を試みた際に膜に空孔や大きな凸面が生じる結果、素子の電流リークが発生する、素子寿命が低下する、素子の再現性や歩留まりが悪くなる等の問題が発生する。
結晶化温度が高すぎる場合、他の素材の耐熱性の観点から結晶への転移を生じさせることが困難となり、特に高い電子移動度の発現やナノ構造体を形成することが困難となる。
However, PCBM has various problems such as low solubility, poor single-layer deposition uniformity, and too high a crystallization temperature (195 ° C.).
When the solubility is low, the type and concentration of the solvent that can be used are limited, so that there are problems such as limited applicable coating methods, limited materials that can be mixed, and difficulty in increasing the film thickness.
When the film formation uniformity of a single unit is poor, when trying to form a single unit for the purpose of aiming at an ideal fine structure, etc., as a result of holes and large convex surfaces in the film, current leakage of the element occurs. Problems such as a decrease in element life and deterioration in element reproducibility and yield occur.
When the crystallization temperature is too high, it becomes difficult to cause transition to crystals from the viewpoint of heat resistance of other materials, and it becomes difficult to express particularly high electron mobility and to form nanostructures.
本発明者らは、糖類を含む置換基を有するフラーレン誘導体が種々の有機溶媒に対して非常に高い溶解性を示し、単体で均一な膜を形成できることを報告している(特許文献1参照)。
しかしながら、当該フラーレン誘導体は有機溶媒に対する溶解性が高い一方で、結晶性および電子移動度が不十分であり、これをn型半導体材料として用いたバルクヘテロジャンクション型有機薄膜太陽電池では発生した電荷の電極への輸送効率が低いため、光電変換効率は低い値に留まっており、その改善が求められている。
光電変換効率を向上するにはn型半導体の結晶性を上げて電子移動度を高くすることが求められる一方で、素子の再現性や歩留まりの観点から、有機溶媒等に対する溶解性を維持する必要がある。
このような観点から、良好な結晶性および溶解性を有する、n型半導体として使用可能な化合物の開発が求められている。
The present inventors have reported that a fullerene derivative having a substituent containing a saccharide exhibits very high solubility in various organic solvents and can form a uniform film by itself (see Patent Document 1). .
However, while the fullerene derivative has high solubility in an organic solvent, it has insufficient crystallinity and electron mobility, and an electrode having a charge generated in a bulk heterojunction organic thin film solar cell using the fullerene derivative as an n-type semiconductor material. The efficiency of photoelectric conversion is low, and the photoelectric conversion efficiency remains low, and there is a need for improvement.
In order to improve the photoelectric conversion efficiency, it is necessary to increase the crystallinity of the n-type semiconductor to increase the electron mobility, but it is necessary to maintain the solubility in organic solvents and the like from the viewpoint of device reproducibility and yield. There is.
From such a viewpoint, there is a demand for the development of a compound that has good crystallinity and solubility and can be used as an n-type semiconductor.
本発明は、上記事情に鑑みてなされたものであり、有機溶媒に可溶で、単体での均一成膜性が良好であり、かつ、適度な結晶化温度を有し、特に、これを有機太陽電池に適用することで、変換効率向上に寄与し得る新規フラーレン誘導体を提供することを目的とする。 The present invention has been made in view of the above circumstances, is soluble in an organic solvent, has a good uniform film forming property as a simple substance, and has an appropriate crystallization temperature. It aims at providing the novel fullerene derivative which can contribute to conversion efficiency improvement by applying to a solar cell.
本発明者らは、上記目的を達成するために鋭意検討した結果、糖類を置換基として含有するフラーレン誘導体において、フラーレンと糖類とを連結するスペーサの一部であるフェニレン基上にフッ素原子を導入した化合物が、高溶解性を示し、単体での高均一成膜が可能であり、種々の誘導体を利用することで結晶性をコントロールすることが可能であることから高い結晶性や適切な結晶化温度を有し、これを用いた有機太陽電池が優れた変換効率を示すことを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have introduced a fluorine atom on a phenylene group which is a part of a spacer for connecting a fullerene and a saccharide in a fullerene derivative containing a saccharide as a substituent. The high degree of crystallinity and appropriate crystallization are possible because the obtained compound exhibits high solubility, enables highly uniform film formation of a single substance, and allows control of crystallinity by using various derivatives. The present invention has been completed by finding that an organic solar cell having a temperature exhibits excellent conversion efficiency.
すなわち、本発明は、
1. 下記式(1)で表されることを特徴とするフラーレン誘導体、
2.前記R 3 が糖基または置換糖基で、R 1 、R 2 、R 4 及びR 5 がフッ素原子である1のフラーレン誘導体、
3. 前記置換糖基の置換基が、炭素数1〜10のアルキル基、ベンジル基、p−メトキシベンジル基、メトキシメチル基、2−テトラヒドロピラニル基、エトキシエチル基、アセチル基、ピバロイル基、ベンゾイル基、トリメチルシリル基、トリエチルシリル基、t−ブチルジメチルシリル基、トリイソプロピルシリル基、またはt−ブチルジフェニルシリル基である1または2のフラーレン誘導体、
4. 1〜3のいずれかのフラーレン誘導体を含む有機太陽電池、
5. 1〜3のいずれかのフラーレン誘導体を含む薄膜を備える有機太陽電池、
6. フラーレン誘導体を含む薄膜を備える有機太陽電池を製造する方法であって、前記薄膜を、下記式(1)で表されるフラーレン誘導体と有機溶媒とを含み、前記フラーレン誘導体が前記有機溶媒に溶解している均一系有機溶液を用いて作製することを特徴とする有機太陽電池の製造方法、
7. 1〜3のいずれかのフラーレン誘導体を含む固体撮像素子または光センサー
を提供する。
That is, the present invention
1. A fullerene derivative represented by the following formula (1):
2. 1 fullerene derivative in which R 3 is a sugar group or a substituted sugar group, and R 1 , R 2 , R 4 and R 5 are fluorine atoms;
3. The substituent of the substituted sugar group is an alkyl group having 1 to 10 carbon atoms, benzyl group, p-methoxybenzyl group, methoxymethyl group, 2-tetrahydropyranyl group, ethoxyethyl group, acetyl group, pivaloyl group, benzoyl group 1 or 2 fullerene derivatives which are a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a triisopropylsilyl group, or a t-butyldiphenylsilyl group,
4). An organic solar cell comprising any one of 1 to 3 fullerene derivatives,
5. An organic solar cell comprising a thin film containing any one of 1 to 3 fullerene derivatives,
6). A method of manufacturing an organic solar cell comprising a thin film containing fullerene derivative, the thin film comprises a fullerene derivative represented by the following formula (1) and the organic solvent, dissolving the fullerene derivative in the organic solvent A method for producing an organic solar cell , characterized in that the organic solar cell is produced using a homogeneous organic solution ,
7). Provided is a solid-state imaging device or an optical sensor comprising any one of 1 to 3 fullerene derivatives.
本発明のフラーレン誘導体は、有機溶媒に対して良好な溶解性を有しており、それを含む有機溶液を容易に調製することができるため、湿式塗布プロセスによって薄膜を作製することができる。これによって、真空蒸着法によるプロセスと比較して素子の大面積化が容易になるとともに、製造コストの低減が可能となる。
また、上記フラーレン誘導体は、溶液状態での保存時や塗布操作途中での凝集が生じないことから、高い均一性を有する薄膜を作製することができ、素子の歩留まり向上や寿命向上を可能にする。
さらに、上記フラーレン誘導体が高溶解性を有することから、ポリ(3−ヘキシルチオフェン)(P3HT)等の可溶性p層材料と混合して溶液を調製する際に、容易に高濃度化することができる。
また、塗布プロセスの条件によっては成膜面に微小な凹凸や細孔が形成されることから、積層法によってp層を隣接させた場合、p/n接合界面の面積を向上させ、太陽電池特性を向上させることができる。
特に、本発明の有機太陽電池に用いるフラーレン誘導体は、フェニレン基上に少なくとも1つフッ素原子を有しているため、これを適用した有機太陽電池、特に有機薄膜太陽電池のエネルギー変換効率をより向上し得る。
そして、上記フラーレン誘導体は、置換基および糖骨格を変更して種々の類縁体に容易に導くことができるため、微小な細孔の発生、適切な結晶性、結晶化温度の発現や、様々な物性のコントロールが可能である。上述のとおり、微小細孔や微結晶の形成によって、p,n積層構造素子におけるp/n接合界面の面積を向上させることができ、また、高い結晶性によってバルクへテロジャンクション素子(BHJ素子)におけるp/n混合層内での相分離を良好に発生させ、太陽電池特性を向上させることができる。
なお、本発明の有機太陽電池は、有機光電変換素子と同義であり、同様の素子構造を有しているCMOSイメージセンサー等の固体撮像素子や、光センサーへの応用も可能である。
The fullerene derivative of the present invention has good solubility in an organic solvent, and an organic solution containing the fullerene derivative can be easily prepared. Therefore, a thin film can be produced by a wet coating process. As a result, the area of the element can be easily increased and the manufacturing cost can be reduced as compared with the process using the vacuum deposition method.
In addition, since the fullerene derivative does not aggregate during storage in the solution state or during the coating operation, a thin film having high uniformity can be produced, and the yield of the device and the improvement of the lifetime can be achieved. .
Furthermore, since the fullerene derivative has high solubility, when preparing a solution by mixing with a soluble p-layer material such as poly (3-hexylthiophene) (P3HT), the concentration can be easily increased. .
In addition, depending on the conditions of the coating process, minute irregularities and pores are formed on the film formation surface. Therefore, when the p layer is adjacent by the lamination method, the area of the p / n junction interface is improved, and the solar cell characteristics Can be improved.
In particular, since the fullerene derivative used in the organic solar cell of the present invention has at least one fluorine atom on the phenylene group, the energy conversion efficiency of an organic solar cell to which this is applied, particularly an organic thin film solar cell, is further improved. Can do.
And since the fullerene derivative can be easily led to various analogs by changing substituents and sugar skeletons, generation of minute pores, appropriate crystallinity, expression of crystallization temperature, The physical properties can be controlled. As described above, the formation of micropores and microcrystals can improve the area of the p / n junction interface in the p and n stacked structure elements, and the bulk heterojunction element (BHJ element) due to high crystallinity. The phase separation in the p / n mixed layer can be satisfactorily generated, and the solar cell characteristics can be improved.
In addition, the organic solar cell of this invention is synonymous with an organic photoelectric conversion element, and the application to solid-state image sensors, such as a CMOS image sensor which has the same element structure, and an optical sensor is also possible.
以下、本発明についてさらに詳しく説明する。
本発明に係るフラーレン誘導体は、下記式(1)で表されるように、フッ素化フェニル置換ピロリジン骨格を有するC60化合物のフェニル基上に、糖基や置換糖基が少なくとも1つ付加した化合物である(以下、フラーレン誘導体(1)という場合もある)。
Hereinafter, the present invention will be described in more detail.
The fullerene derivative according to the present invention is a compound in which at least one sugar group or substituted sugar group is added to the phenyl group of a C60 compound having a fluorinated phenyl-substituted pyrrolidine skeleton, as represented by the following formula (1). Yes (hereinafter sometimes referred to as fullerene derivative (1)).
式(1)において、R1〜R5は、それぞれ独立して、水素原子、フッ素原子、糖基、または糖基の任意の水酸基が置換基によって置換された糖基である置換糖基を表し、R6は、炭素数1〜5のアルキル基を表すが、R1〜R5のうちの少なくとも1つは、糖基または置換糖基であり、かつ、R1〜R5のうちの少なくとも1つは、フッ素原子である。
中でも、得られる有機太陽電池の変換効率をより高めることを考慮すると、R1〜R5のうち、4つがフッ素原子で、1つが糖基または置換糖基のものが好ましく、R3(ピロリジン骨格に対してパラ位)またはR2もしくはR4(ピロリジン骨格に対してメタ位)が糖基または置換糖基で、その他が全てフッ素原子のものがより好ましく、R3(ピロリジン骨格に対してパラ位)が糖基または置換糖基で、その他が全てフッ素原子のものがより一層好ましい。
In formula (1), R 1 to R 5 each independently represents a hydrogen atom, a fluorine atom, a sugar group, or a substituted sugar group that is a sugar group in which an arbitrary hydroxyl group of the sugar group is substituted with a substituent. , R 6 represents an alkyl group having 1 to 5 carbon atoms, but at least one of R 1 to R 5 is a sugar group or a substituted sugar group, and at least one of R 1 to R 5 One is a fluorine atom.
Among these, in consideration of further improving the conversion efficiency of the obtained organic solar cell, among R 1 to R 5 , four are preferably fluorine atoms and one is a sugar group or a substituted sugar group, and R 3 (pyrrolidine skeleton) para to respect para) or R 2 or R 4 (meta to pyrrolidine skeleton) is a sugar group or substituted sugar groups, more preferably others are all fluorine atoms, R 3 (pyrrolidine skeleton It is even more preferable that the position) is a sugar group or a substituted sugar group and all others are fluorine atoms.
上記糖基または置換糖基としては、特に限定されるものではなく、任意のテトロース基、ペントース基、ヘキソース基およびそれらの任意の水酸基が置換された置換糖基を採用できる。
テトロース基としては、エリトロース基であるエリトロシル基等が挙げられる。
ペントース基としては、アラビノース基であるアラビノシル基、リキソース基であるリキソシル基、リボース基であるリボシル基、キシロース基であるキシロシル基等が挙げられる。
ヘキソース基としては、アロース基であるアロシル基、フルクトース基であるフルクトシル基、ガラクトース基であるガラクトシル基、グルコース基であるグルコシル基、グロース基であるグロシル基、マンノース基であるマンノシル基、タガロース基であるタガロシル基、タロース基であるタロシル基、シアル酸基等が挙げられる。
これらの中でも、本発明においては、ヘキソース基が好ましく、特に、ガラクトシル基、グルコシル基が好適である。
The sugar group or substituted sugar group is not particularly limited, and any tetrose group, pentose group, hexose group, and substituted sugar group in which any of these hydroxyl groups is substituted can be employed.
Examples of the tetrose group include an erythrosyl group which is an erythrose group.
Examples of the pentose group include an arabinose group that is an arabinose group, a lyxosyl group that is a lyxose group, a ribosyl group that is a ribose group, and a xylosyl group that is a xylose group.
The hexose group includes an allose group, an allosyl group, a fructose group, a fructosyl group, a galactose group, a galactosyl group, a glucose group, a glucosyl group, a growth group, a grosyl group, a mannose group, a mannosyl group, and a tagarose group. There may be mentioned a tagarosyl group, a tarose group, a tarosyl group, a sialic acid group, and the like.
Among these, a hexose group is preferable in the present invention, and a galactosyl group and a glucosyl group are particularly preferable.
より具体的には、式(2)〜(4)で示されるテトロース基、ペントース基、ヘキソース基が好適であり、特に、式(4)で示されるヘキソース基が好ましい。 More specifically, tetrose groups, pentose groups, and hexose groups represented by formulas (2) to (4) are preferred, and a hexose group represented by formula (4) is particularly preferred.
一価炭化水素基としては、例えば、メチル基,エチル基,n−プロピル基,i−プロピル基,n−ブチル基,i−ブチル基,t−ブチル基,n−ヘキシル基,n−オクチル基,2−エチルヘキシル基,デシル基等のアルキル基、シクロペンチル基,シクロヘキシル基等のシクロアルキル基、ビシクロヘキシル基等のビシクロアルキル基、ビニル基,1−プロペニル基,2−プロペニル基,イソプロペニル基,1−メチル−2−プロペニル基,1または2または3−ブテニル基,ヘキセニル基等のアルケニル基、フェニル基,キシリル基,トリル基,ビフェニル基,ナフチル基等のアリール基、ベンジル基,フェニルエチル基,フェニルシクロヘキシル基等のアラルキル基などや、これらの一価炭化水素基の水素原子の一部または全部がハロゲン原子(フッ素原子、塩素原子、臭素原子、ヨウ素原子)、水酸基、アルコキシ基(メトキシ基、エトキシ基等)などで置換されたものが挙げられる。 Examples of the monovalent hydrocarbon group include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, and n-octyl group. , 2-ethylhexyl group, alkyl group such as decyl group, cyclopentyl group, cycloalkyl group such as cyclohexyl group, bicycloalkyl group such as bicyclohexyl group, vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-methyl-2-propenyl group, 1 or 2 or 3-butenyl group, alkenyl group such as hexenyl group, phenyl group, xylyl group, tolyl group, biphenyl group, aryl group such as naphthyl group, benzyl group, phenylethyl group , Aralkyl groups such as phenylcyclohexyl groups, etc., and some or all of the hydrogen atoms of these monovalent hydrocarbon groups are halogenated. Atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, an alkoxy group (methoxy group, ethoxy group, etc.) include those substituted with such.
オルガノアミノ基としては、例えば、メチルアミノ基,エチルアミノ基,プロピルアミノ基,ブチルアミノ基,ペンチルアミノ基,ヘキシルアミノ基,ヘプチルアミノ基,オクチルアミノ基,ノニルアミノ基,デシルアミノ基,ラウリルアミノ基等のアルキルアミノ基、ジメチルアミノ基,ジエチルアミノ基,ジプロピルアミノ基,ジブチルアミノ基,ジペンチルアミノ基,ジヘキシルアミノ基,ジヘプチルアミノ基,ジオクチルアミノ基,ジノニルアミノ基,ジデシルアミノ基等のジアルキルアミノ基、シクロヘキシルアミノ基等のシクロアルキルアミノ基、モルホリノ基などが挙げられる。 Examples of the organoamino group include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, a decylamino group, and a laurylamino group. Dialkylamino groups such as alkylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group and didecylamino group, cyclohexyl Examples thereof include cycloalkylamino groups such as amino groups, morpholino groups, and the like.
オルガノシリル基としては、例えば、トリメチルシリル基、トリエチルシリル基、トリプロピルシリル基、トリブチルシリル基、トリペンチルシリル基、トリヘキシルシリル基、ペンチルジメチルシリル基、ヘキシルジメチルシリル基、オクチルジメチルシリル基、デシルジメチルシリル基等が挙げられる。
オルガノチオ基としては、例えば、メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基、ペンチルチオ基、ヘキシルチオ基、ヘプチルチオ基、オクチルチオ基、ノニルチオ基、デシルチオ基、ラウリルチオ基等のアルキルチオ基などが挙げられる。
アシル基としては、例えば、ホルミル基、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基、イソバレリル基、ベンゾイル基等が挙げられる。
Examples of the organosilyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, tripentylsilyl group, trihexylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, octyldimethylsilyl group, decyl Examples thereof include a dimethylsilyl group.
Examples of the organothio group include alkylthio groups such as methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, and laurylthio group.
Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, benzoyl group and the like.
また、R6は、炭素数1〜5のアルキル基であり、その具体例としては、メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、i−ブチル基、t−ブチル基、n−ペンチル基等が挙げられるが、特に、メチル基が好ましい。 R 6 is an alkyl group having 1 to 5 carbon atoms, and specific examples thereof include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t -Butyl group, n-pentyl group, etc. are mentioned, and a methyl group is particularly preferable.
特に、上記フラーレン誘導体の有機溶媒に対する溶解性をより向上させることを考慮すると、糖残基の有する水酸基の少なくとも1つが、任意の置換基によって置換されていることが好ましく、全ての水酸基が置換基によって置換されていることがより好ましい。
その具体例としては、R7〜R15で例示したものと同様の置換基が挙げられるが、特に、炭素数1〜10のアルキル基、ベンジル基、p−メトキシベンジル基、t−ブチル基、メトキシメチル基、2−テトラヒドロピラニル基、エトキシエチル基、アセチル基、ピバロイル基、ベンゾイル基、トリメチルシリル基、トリエチルシリル基、t−ブチルジメチルシリル基、トリイソプロピルシリル基、t−ブチルジフェニルシリル基等が好ましく、アセチル基がより好ましい。
In particular, in consideration of further improving the solubility of the fullerene derivative in an organic solvent, it is preferable that at least one hydroxyl group of the sugar residue is substituted with an arbitrary substituent, and all the hydroxyl groups are substituted. More preferably, it is substituted by.
Specific examples thereof include the same substituents as those exemplified for R 7 to R 15 , and in particular, an alkyl group having 1 to 10 carbon atoms, a benzyl group, a p-methoxybenzyl group, a t-butyl group, Methoxymethyl group, 2-tetrahydropyranyl group, ethoxyethyl group, acetyl group, pivaloyl group, benzoyl group, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, triisopropylsilyl group, t-butyldiphenylsilyl group, etc. Are preferable, and an acetyl group is more preferable.
上記フラーレン誘導体(1)は、下記スキームに示されるように、アルデヒド誘導体(5)とグリシン誘導体(6)とを反応させ、系内で中間体(7)を発生させ、さらに、この中間体(7)とフラーレンとを反応させることで製造できる。 As shown in the following scheme, the fullerene derivative (1) reacts with an aldehyde derivative (5) and a glycine derivative (6) to generate an intermediate (7) in the system, and this intermediate ( It can be produced by reacting 7) with fullerene.
上記反応において、アルデヒド誘導体(5)と、グリシン誘導体(6)との仕込み量は特に限定されるものではなく、アルデヒド誘導体(5)1molに対し、グリシン誘導体(6)0.5〜2.0mol程度とすることができるが、1.4〜1.6mol程度が好適である。
また、フラーレンの仕込み量も特に限定されるものではなく、アルデヒド誘導体(5)1molに対し、フラーレン0.7〜1.3mol程度とすることができるが、1.0〜1.1molが好適である。
上記反応においては、アルデヒド誘導体(5)と、グリシン誘導体(6)とが反応して生じる水を、Dean−Stark法により除去しながら反応を行うことで、効率的にフラーレン誘導体(1)を得ることができる。
In the above reaction, the amounts of the aldehyde derivative (5) and the glycine derivative (6) are not particularly limited, and the glycine derivative (6) is 0.5 to 2.0 mol with respect to 1 mol of the aldehyde derivative (5). About 1.4 to 1.6 mol is preferable.
Further, the amount of fullerene charged is not particularly limited, and may be about 0.7 to 1.3 mol of fullerene with respect to 1 mol of aldehyde derivative (5), but 1.0 to 1.1 mol is preferable. is there.
In the above reaction, the fullerene derivative (1) is efficiently obtained by carrying out the reaction while removing water produced by the reaction of the aldehyde derivative (5) and the glycine derivative (6) by the Dean-Stark method. be able to.
上記反応に用いる溶媒としては、反応に悪影響を及ぼさないものであれば特に限定されないが、効率的にフラーレン誘導体(1)を得るためには、上記原料化合物の溶解能に優れる溶媒が好ましく、例えば、ベンゼン、クロロベンゼン、o−ジクロロベンゼン、ニトロベンゼン、トルエン、o−キシレン、m−キシレン、p−キシレン、メシチレン、テトラリン等の芳香族炭化水素類が好適であり、特に、上述したDean−Stark法を用いることを考慮すると、反応を効率的に進めることができる温度を保つことができる、o−キシレン、m−キシレン、p−キシレンが好ましく、p−キシレンがより好ましい。
反応温度は、用いる溶媒の融点から沸点までの範囲で適宜設定すればよいが、50〜150℃程度が好ましい。
反応終了後は、常法に従って後処理をすることで、目的とするフラーレン誘導体(1)を得ることができる。
The solvent used in the reaction is not particularly limited as long as it does not adversely affect the reaction. However, in order to obtain the fullerene derivative (1) efficiently, a solvent excellent in solubility of the raw material compound is preferable. , Aromatic hydrocarbons such as benzene, chlorobenzene, o-dichlorobenzene, nitrobenzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, tetralin, etc. are preferred. In particular, the above-mentioned Dean-Stark method is used. In consideration of the use, o-xylene, m-xylene, and p-xylene are preferable, and p-xylene is more preferable, which can maintain a temperature at which the reaction can proceed efficiently.
The reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent to be used, but is preferably about 50 to 150 ° C.
After completion of the reaction, the desired fullerene derivative (1) can be obtained by post-treatment according to a conventional method.
上記フラーレン誘導体を用いた薄膜形成プロセスは特に限定されるものではなく、溶液法や真空蒸着法などの公知の各種方法を採用することができるが、蒸着法などと比較して簡便に薄膜を作製することができ、かつ、大面積化にも容易に対応できるため、当該フラーレン誘導体を含む有機溶液を用いるプロセスが好ましい。
この場合、有機溶液は、上述したフラーレン誘導体と有機溶媒とを含み、フラーレン誘導体が有機溶媒に溶解した均一系有機溶液である。
有機溶媒としては、上記フラーレン誘導体の溶解能を有するものであれば特に限定されるものではなく、例えば、ベンゼン、トルエン、キシレン、クロロベンゼン等の芳香族またはハロゲン化芳香族炭化水素溶媒;ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒、アセトン等のケトン系溶媒、酢酸エチル等のエステル系溶媒;ジクロロエタン、クロロホルム、ジクロロメタン等のハロゲン化炭化水素溶媒;二硫化炭素などを用いることができる。
有機溶液中のフラーレン誘導体の含有量は、有機溶媒に溶解する量であれば特に限定されるものではないが、塗布性等の操作性などを考慮すると、0.01〜20質量%が好ましく、0.5〜3質量%がより好ましい。
The thin film formation process using the fullerene derivative is not particularly limited, and various known methods such as a solution method and a vacuum evaporation method can be adopted. In addition, a process using an organic solution containing the fullerene derivative is preferable because it can easily cope with an increase in area.
In this case, the organic solution is a homogeneous organic solution containing the fullerene derivative and the organic solvent described above, and the fullerene derivative dissolved in the organic solvent.
The organic solvent is not particularly limited as long as it has the ability to dissolve the fullerene derivative. For example, an aromatic or halogenated aromatic hydrocarbon solvent such as benzene, toluene, xylene, chlorobenzene, diethyl ether, Ether solvents such as tetrahydrofuran and dioxane, ketone solvents such as acetone, ester solvents such as ethyl acetate; halogenated hydrocarbon solvents such as dichloroethane, chloroform and dichloromethane; carbon disulfide and the like can be used.
The content of the fullerene derivative in the organic solution is not particularly limited as long as it is an amount that dissolves in the organic solvent, but is preferably 0.01 to 20% by mass in consideration of operability such as coating properties, 0.5-3 mass% is more preferable.
以上で説明したフラーレン誘導体を含む有機溶液を基材上に塗布し、溶媒を蒸発させることで基材上にフラーレン誘導体を含む薄膜を形成させることができる。
塗布方法としては、特に限定されるものではなく、ディップ法、スピンコート法、転写印刷法、ロールコート法、刷毛塗り、インクジェット法、スプレー法等が挙げられる。
溶媒の蒸発法としては、特に限定されるものではなく、例えば、ホットプレートやオーブン等を用いて、適切な雰囲気下、すなわち、大気、窒素等の不活性ガス、真空中等で蒸発させればよい。
焼成温度は、溶媒を蒸発させることができれば特に限定されないが、80〜100℃が好ましい。
The thin film containing a fullerene derivative can be formed on a base material by apply | coating the organic solution containing the fullerene derivative demonstrated above on a base material, and evaporating a solvent.
The application method is not particularly limited, and examples thereof include a dipping method, a spin coating method, a transfer printing method, a roll coating method, a brush coating method, an ink jet method, and a spray method.
The method for evaporating the solvent is not particularly limited. For example, the solvent may be evaporated in an appropriate atmosphere using a hot plate, an oven, or the like, that is, in an inert gas such as air or nitrogen, or in a vacuum. .
Although a calcination temperature will not be specifically limited if a solvent can be evaporated, 80-100 degreeC is preferable.
本発明において、上記フラーレン誘導体を含む薄膜の膜厚は、特に限定されないが、50〜100nmが好適である。膜厚を変化させる方法としては、有機溶液中の固形分濃度を変化させたり、塗布時の基板上の溶液量を変化させたりする等の方法がある。
以上説明したフラーレン誘導体を含む薄膜は、有機太陽電池素子、特に有機薄膜太陽電池素子における活性層として好適に用いることができ、特にn層、すなわちアクセプター層として好適に用いることができる。
In the present invention, the thickness of the thin film containing the fullerene derivative is not particularly limited, but is preferably 50 to 100 nm. As a method of changing the film thickness, there are methods such as changing the solid content concentration in the organic solution, or changing the amount of the solution on the substrate at the time of coating.
The thin film containing the fullerene derivative described above can be suitably used as an active layer in an organic solar cell element, particularly an organic thin film solar cell element, and can be particularly suitably used as an n layer, that is, an acceptor layer.
本発明の有機太陽電池素子は、上述したフラーレン誘導体を用いることにその特徴があるため、素子を構成するその他の部材や、素子の作製方法などは特に限定されるものではない。
例えば、本発明のフラーレン誘導体を有機薄膜太陽電池素子に使用する場合、以下の方法を挙げることができる。
Since the organic solar cell element of the present invention is characterized by using the above-described fullerene derivative, other members constituting the element, a method for producing the element, and the like are not particularly limited.
For example, when using the fullerene derivative of this invention for an organic thin-film solar cell element, the following method can be mentioned.
まず、使用する電極基板は、洗剤、アルコール、純水等による液体洗浄を予め行って浄化しておくことが好ましく、例えば、陽極基板では使用直前にオゾン処理、酸素−プラズマ処理等の表面処理を行うことが好ましい。ただし陽極材料が有機物を主成分とする場合、表面処理を行わなくともよい。
陽極基板上に、陽極バッファ層材料を用いて塗布法または蒸着法によって陽極バッファ層薄膜を形成する。これをグローブボックス装置内に導入し、窒素等の不活性ガス雰囲気下、n型材料およびp型材料からなる活性層を形成する。この際、n型材料からなる薄膜であるn層と、p型材料からなる薄膜であるp層とを積層してもよく、各材料を混合してもよい。
すなわち、後述するp型材料と上記フラーレン誘導体とを混合して使用しても、それぞれを順次積層して使用してもよい。n層とp層とを積層させる場合、蒸着法によって本発明のフラーレン誘導体を含むn層上にp層を積層することができる。
First, the electrode substrate to be used is preferably cleaned in advance by cleaning with a liquid such as a detergent, alcohol, or pure water. For example, the anode substrate is subjected to surface treatment such as ozone treatment or oxygen-plasma treatment immediately before use. Preferably it is done. However, when the anode material is mainly composed of an organic material, the surface treatment may not be performed.
An anode buffer layer thin film is formed on the anode substrate by a coating method or a vapor deposition method using an anode buffer layer material. This is introduced into a glove box device, and an active layer made of an n-type material and a p-type material is formed in an inert gas atmosphere such as nitrogen. At this time, an n layer, which is a thin film made of an n-type material, and a p layer, which is a thin film made of a p-type material, may be laminated, or each material may be mixed.
That is, a p-type material described later and the fullerene derivative may be used in combination or may be used by sequentially laminating them. When the n layer and the p layer are laminated, the p layer can be laminated on the n layer containing the fullerene derivative of the present invention by an evaporation method.
活性層作製後、薄膜が形成された基板を真空蒸着装置内に導入し、陰極バッファ層、陰極金属を順次蒸着して有機薄膜太陽電池素子とする。
なお、光電流の整流性をコントロールするため、任意の層間にキャリアブロック層を設けてもよい。
After forming the active layer, the substrate on which the thin film is formed is introduced into a vacuum deposition apparatus, and the cathode buffer layer and the cathode metal are sequentially deposited to obtain an organic thin film solar cell element.
Note that a carrier block layer may be provided between arbitrary layers in order to control photocurrent rectification.
陽極材料としては、インジウム錫酸化物(ITO)、インジウム亜鉛酸化物(IZO)に代表される透明電極が挙げられ、平坦化処理を行ったものが好ましい。高電荷輸送性を有するポリチオフェン誘導体やポリアニリン誘導体を用いることもできる。
p型材料としては、P3HT等のポリアルキルチオフェン類、CuPC,ZnPC等のフタロシアニン類、テトラベンゾポルフィリン等のポルフィリン類、国際公開第2010/008672号や特開2009−158921号公報に記載されているような縮環型チオフェンユニット含有ポリマー類などが挙げられ、特に、P3HT等のポリアルキルチオフェン類が好適である。
Examples of the anode material include transparent electrodes typified by indium tin oxide (ITO) and indium zinc oxide (IZO), and those subjected to planarization treatment are preferable. Polythiophene derivatives and polyaniline derivatives having high charge transporting properties can also be used.
Examples of the p-type material include polyalkylthiophenes such as P3HT, phthalocyanines such as CuPC and ZnPC, porphyrins such as tetrabenzoporphyrin, and International Publication Nos. 2010/008672 and JP2009-158921. Examples thereof include polymers containing a condensed ring type thiophene unit, and polyalkylthiophenes such as P3HT are particularly suitable.
陰極バッファ層を形成する材料としては、酸化リチウム(Li2O)、酸化マグネシウム(MgO)、アルミナ(Al2O3)、フッ化リチウム(LiF)、フッ化マグネシウム(MgF2)、フッ化ストロンチウム(SrF2)、Liq、Li(acac)、酢酸リチウム、安息香酸リチウム等が挙げられる。
陰極材料としては、アルミニウム、マグネシウム−銀合金、アルミニウム−リチウム合金、リチウム、ナトリウム、カリウム、セシウム、カルシウム、バリウム、銀、金等が挙げられ、複数の陰極材料を積層したり、混合したりして使用することができる。
Materials for forming the cathode buffer layer include lithium oxide (Li 2 O), magnesium oxide (MgO), alumina (Al 2 O 3 ), lithium fluoride (LiF), magnesium fluoride (MgF 2 ), and strontium fluoride. (SrF 2 ), Liq, Li (acac), lithium acetate, lithium benzoate and the like.
Examples of the cathode material include aluminum, magnesium-silver alloy, aluminum-lithium alloy, lithium, sodium, potassium, cesium, calcium, barium, silver, and gold. A plurality of cathode materials may be laminated or mixed. Can be used.
上記で例示した方法によって作製された有機薄膜太陽電池素子は、大気による素子劣化を防ぐために、再度グローブボックス内に導入して窒素等の不活性ガス雰囲気下で封止操作を行い、封止された状態で太陽電池としての機能を発揮させたり、太陽電池特性の測定を行ったりすることができる。
封止法としては、端部にUV硬化樹脂を付着させた凹型ガラス基板を、不活性ガス雰囲気下、有機薄膜太陽電池素子の成膜面側に付着させ、UV照射によって樹脂を硬化させる方法や、真空下、スパッタリング等の手法によって膜封止タイプの封止を行う方法などが挙げられる。
The organic thin-film solar cell element produced by the method exemplified above is sealed by introducing it again into the glove box and performing a sealing operation under an inert gas atmosphere such as nitrogen in order to prevent element deterioration due to the atmosphere. In such a state, the function as a solar cell can be exhibited, or the characteristics of the solar cell can be measured.
As a sealing method, a concave glass substrate with a UV curable resin attached to the end is attached to the film forming surface side of the organic thin film solar cell element in an inert gas atmosphere, and the resin is cured by UV irradiation. Examples of the method include performing a film sealing type sealing by a technique such as sputtering under vacuum.
以下、合成例、実施例および比較例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。なお、実施例で用いた分析装置等は下記のとおりである。
(1)融点:微量融点測定装置((株)柳本製作所製、MP-S3)
(2)NMR:超伝導核磁気共鳴スペクトル装置(日本電子(株)製、JNM-EX270およびJNM-ECS 400)
(3)IR:フーリエ変換赤外分光光度計(日本分光(株)製、JASCO FT/IR-7000)
(4)MS:質量分析計(日本電子(株)製、JMS-AX500、およびBRUKER製、autoflex II MALDI TOF/TOF MS)
(5)旋光度:旋光計(日本分光(株)製、DIP-1000型)
(6)UV−VISスペクトル:紫外可視赤外分光光度計(日本分光(株)製、V-670分光光度計)
(7)HPLC:高速液体クロマトグラフ装置((株)日立製作所製、L-6000形日立高速液体クロマトグラフ、検出波長341nm)
(8)示差走査熱量分析(DSC):(株)リガク製、Thermo Plus 2シリーズ DSC8240
(9)XRD:PANalytial社製 X線回折装置 X’Pert PRO-MPD PW3040/60 DY2425
(10)グローブボックス:山八物産(株)製、VACグローブボックスシステム
(11)蒸着装置:アオヤマエンジニアリング(株)製、真空蒸着装置
(12)ソーラーシミュレータ:分光計器(株)製、OTENTOSUN−III、AM1.5Gフィルター、放射強度:100mW/cm2
(13)ソースメジャーユニット:ケースレーインスツルメンツ(株)製、2612A
(14)IPCEスペクトル:分光計器(株)製、ハイパーモノライトシステム SM−250
Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. The analyzers used in the examples are as follows.
(1) Melting point: Trace melting point measuring device (manufactured by Yanagimoto Seisakusho, MP-S3)
(2) NMR: Superconducting nuclear magnetic resonance spectrometer (manufactured by JEOL Ltd., JNM-EX270 and JNM-ECS 400)
(3) IR: Fourier transform infrared spectrophotometer (JASCO FT / IR-7000, JASCO Corporation)
(4) MS: Mass spectrometer (manufactured by JEOL Ltd., JMS-AX500, and BRUKER, autoflex II MALDI TOF / TOF MS)
(5) Optical rotation: Polarimeter (manufactured by JASCO Corporation, DIP-1000 type)
(6) UV-VIS spectrum: UV-visible infrared spectrophotometer (manufactured by JASCO Corporation, V-670 spectrophotometer)
(7) HPLC: High performance liquid chromatograph (manufactured by Hitachi, Ltd., L-6000 Hitachi high performance liquid chromatograph, detection wavelength 341 nm)
(8) Differential scanning calorimetry (DSC): Rigaku Corporation, Thermo Plus 2 series DSC8240
(9) XRD: X-ray diffractometer X'Pert PRO-MPD PW3040 / 60 DY2425 manufactured by PANalytial
(10) Glove box: manufactured by Yamahachi Bussan Co., Ltd., VAC glove box system (11) Vapor deposition device: manufactured by Aoyama Engineering Co., Ltd., vacuum vapor deposition device (12) Solar simulator: manufactured by Spectrometer Co., Ltd., OTENTOUN-III AM1.5G filter, radiation intensity: 100 mW / cm 2
(13) Source measure unit: 2612A, manufactured by Keithley Instruments
(14) IPCE spectrum: manufactured by Spectrometer Co., Ltd., Hypermonolite System SM-250
[合成例1]4−(2’,3’,4’,6’−テトラ−O−アセチル−β−D−グルコピラノシルオキシ)−2,3,5,6−テトラフルオロベンズアルデヒド[2]の合成
窒素気流下、2,3,5,6−テトラフルオロ−4−ヒドロキシベンズアルデヒド(97mg,0.5mmol)のキノリン溶液(2.5mL)に、2,3,4,6−テトラ−O−アセチル−α−D−グルコピラノシルブロミド[1](308mg,0.75mmol)、および酸化銀(173mg,0.75mmol)を加え、室温で75分間撹拌した。反応終了後、クロロホルム(20mL)で抽出し、不溶物をろ別した。
次に、抽出液を1%塩酸(20mL)で5回洗浄した後、1%炭酸水素ナトリウム水溶液(20mL)で5回洗浄した。有機層を硫酸マグネシウムで乾燥後、減圧濃縮して褐色粘性オイル(426mg)を得た。
残渣をシリカゲルカラムクロマトグラフィーに付し、ヘキサン−酢酸エチル(2:1(v/v))溶出分より、無色粘性オイル(243mg,93%)を得た。これをヘキサン−酢酸エチル(3:1(v/v))から再結晶し、無色針状晶[2](210mg,85%)を得た。得られた生成物の分析結果は以下に示す。
Under a nitrogen stream, 2,3,4,6-tetra-O-acetyl- was added to a quinoline solution (2.5 mL) of 2,3,5,6-tetrafluoro-4-hydroxybenzaldehyde (97 mg, 0.5 mmol). α-D-Glucopyranosyl bromide [1] (308 mg, 0.75 mmol) and silver oxide (173 mg, 0.75 mmol) were added, and the mixture was stirred at room temperature for 75 minutes. After completion of the reaction, the mixture was extracted with chloroform (20 mL), and insoluble matters were filtered off.
Next, the extract was washed 5 times with 1% hydrochloric acid (20 mL) and then 5 times with 1% aqueous sodium hydrogen carbonate solution (20 mL). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a brown viscous oil (426 mg).
The residue was subjected to silica gel column chromatography, and colorless viscous oil (243 mg, 93%) was obtained from the fraction eluted with hexane-ethyl acetate (2: 1 (v / v)). This was recrystallized from hexane-ethyl acetate (3: 1 (v / v)) to obtain colorless needle crystals [2] (210 mg, 85%). The analysis results of the obtained product are shown below.
Colorless needles [Hexane - Ethyl acetate (3:1) ], mp.124-125 ℃.
IR (KBr) 2940, 2878 (CH), 1752, 1719 (C=O), 1649, 1491 (C=C),
1241, 1224, 1079, 1038 (O-C=O or CF), 806 cm-1 (CH).
1H NMR (400 MHz, CDCl3) δ 2.05 (6H, s, CH3), 2.07 (3H, s, CH3), 2.10 (3H, s, CH3),
3.81 (1H, ddd, J = 2.3, 5.0, 9.6 Hz, 5'-H), 4.13 (1H, dd, J = 2.3, 12.4 Hz, 6'-H),
4.25 (1H, dd, J = 5.0, 12.4 Hz, 6'-H), 5.17-5.33 (4H, m, 1', 2', 3', 4'-H),
10.25 (1H, s, CHO).
13C NMR (100.5 MHz, CDCl3) δ 20.57 (CH3×4), 61.33 (6'-C), 67.79 (4'-C),
71.20 (2'-C), 72.26 (3'-C), 72.70 (5'-C),
100.96 (1'-C), 110.85 (1-C, disappeared by DEPT 135),
139.27 (4-C, disappeared by DEPT 135),
140.52 (d, J = 263.40 Hz, 3, 5-C), 147.33 (d, J = 263.40 Hz, 2, 6-C),
169.08, 169.25, 170.09, 170.44 (CH3 CO, disappeared by DEPT 135),
181.85 (CHO).
MALDI-TOF-MS (Pos., DHB) m/z 547 ([M+Na]+), 563 ([M+K]+).
Colorless needles [Hexane-Ethyl acetate (3: 1)], mp.124-125 ° C.
IR (KBr) 2940, 2878 (CH), 1752, 1719 (C = O), 1649, 1491 (C = C),
1241, 1224, 1079, 1038 (OC = O or CF), 806 cm -1 (CH).
1 H NMR (400 MHz, CDCl 3 ) δ 2.05 (6H, s, CH 3 ), 2.07 (3H, s, CH 3 ), 2.10 (3H, s, CH 3 ),
3.81 (1H, ddd, J = 2.3, 5.0, 9.6 Hz, 5'-H), 4.13 (1H, dd, J = 2.3, 12.4 Hz, 6'-H),
4.25 (1H, dd, J = 5.0, 12.4 Hz, 6'-H), 5.17-5.33 (4H, m, 1 ', 2', 3 ', 4'-H),
10.25 (1H, s, CHO).
13 C NMR (100.5 MHz, CDCl 3 ) δ 20.57 (CH 3 × 4), 61.33 (6'-C), 67.79 (4'-C),
71.20 (2'-C), 72.26 (3'-C), 72.70 (5'-C),
100.96 (1'-C), 110.85 (1-C, disappeared by DEPT 135),
139.27 (4-C, disappeared by DEPT 135),
140.52 (d, J = 263.40 Hz, 3, 5-C), 147.33 (d, J = 263.40 Hz, 2, 6-C),
169.08, 169.25, 170.09, 170.44 (CH 3 C O, disappeared by DEPT 135),
181.85 (CHO).
MALDI-TOF-MS (Pos., DHB) m / z 547 ([M + Na] + ), 563 ([M + K] + ).
[合成例2]4−(2’,3’,4’,6’−テトラ−O−アセチル−β−D−グルコピラノシルオキシ)ベンズアルデヒド[3]の合成
窒素気流下、p−ヒドロキシベンズアルデヒド(123mg,1.0mmol)のキノリン溶液(2.0mL)に、2,3,4,6−テトラ−O−アセチル−α−D−グルコピラノシルブロミド[1](822mg,2.0mmol)、および酸化銀(464mg,2.0mmol)を加え、室温で75分間撹拌した。反応終了後、ベンゼン(60mL)で抽出し、不溶物をろ別した。
次に、抽出液を1%塩酸(20mL)で10回洗浄した後、1%炭酸水素ナトリウム水溶液(20mL)で10回洗浄した。有機層を硫酸マグネシウムで乾燥後、減圧濃縮して黄色粘性オイル(702mg)を得た。
残渣をシリカゲルカラムクロマトグラフィーに付し、ヘキサン−酢酸エチル(3:2(v/v))溶出分より、無色粘性オイル(417mg)を得た。これをエタノールから再結晶して無色針状晶[3](375mg,83%)を得た。得られた生成物の分析結果を以下に示す。
Under a nitrogen stream, 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide [1] was added to a quinoline solution (2.0 mL) of p-hydroxybenzaldehyde (123 mg, 1.0 mmol). ] (822 mg, 2.0 mmol) and silver oxide (464 mg, 2.0 mmol) were added, and the mixture was stirred at room temperature for 75 minutes. After completion of the reaction, the mixture was extracted with benzene (60 mL), and insoluble matters were filtered off.
Next, the extract was washed 10 times with 1% hydrochloric acid (20 mL) and then 10 times with 1% aqueous sodium hydrogen carbonate solution (20 mL). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give a yellow viscous oil (702 mg).
The residue was subjected to silica gel column chromatography, and a colorless viscous oil (417 mg) was obtained from the fraction eluted with hexane-ethyl acetate (3: 2 (v / v)). This was recrystallized from ethanol to obtain colorless needle crystals [3] (375 mg, 83%). The analysis result of the obtained product is shown below.
Colorless needles (Ethanol), mp.147-148 ℃ (lit. mp.144 ℃).
IR (KBr) 2995, 2966, 2854, 2752 (CH) 1754, 1735, 1694 (C=O), 1603, 1508 (C=C),
1236, 1085, 1056, 1035 (O-C=O), 849 cm-1 (CH).
1H NMR (400 MHz, CDCl3) δ 2.05 (3H, s, CH3), 2.062 (3H, s, CH3),
2.064 (3H, s, CH3), 2.08 (3H, s, CH3),
3.93 (1H, ddd, J = 2.3, 5.5, 9.6 Hz, 5'-H),
4.18 (1H, dd, J = 2.3, 12.4 Hz, 6'-H), 4.29 (1H, dd, J = 5.5, 12.4 Hz, 6'-H),
5.14-5.25 (2H, m, 2', 4'-H), 5.28-5.36 (2H, m, 1', 3'-H),
7.10 (2H, d, J = 8.7 Hz, 3, 5-H),
7.85 (2H, d, J = 8.7 Hz, 2, 6-H), 9.92 (1H, s, CHO).
13C NMR (100.5 MHz, CDCl3) δ 20.61 (CH3×3), 20.67 (CH3), 61.83 (6'-C),
68.05 (4'-C), 70.94 (2'-C), 72.26 (3'-C), 72.48 (5'-C), 97.98 (1'-C),
116.70 (3, 5-C), 131.78 (1, 2, 6-C, reduced by DEPT 135),
161.15 (4-C, disappeared by DEPT 135),
169.17, 169.32, 170.14, 170.43 (CH3 CO, disappeared by DEPT 135),
190.64 (CHO).
FAB-MS (m-NBA) m/z 452 (M+), 451 ([M-H]+).
MALDI-TOF-MS (Pos., Dithranol) m/z 453 ([M+H]+), 475 ([M+Na]+), 491 ([M+K]+).
Found : C, 55.66 ; H, 5.37%.
Colorless needles (Ethanol), mp.147-148 ℃ (lit. mp.144 ℃).
IR (KBr) 2995, 2966, 2854, 2752 (CH) 1754, 1735, 1694 (C = O), 1603, 1508 (C = C),
1236, 1085, 1056, 1035 (OC = O), 849 cm -1 (CH).
1 H NMR (400 MHz, CDCl 3 ) δ 2.05 (3H, s, CH 3 ), 2.062 (3H, s, CH 3 ),
2.064 (3H, s, CH 3 ), 2.08 (3H, s, CH 3 ),
3.93 (1H, ddd, J = 2.3, 5.5, 9.6 Hz, 5'-H),
4.18 (1H, dd, J = 2.3, 12.4 Hz, 6'-H), 4.29 (1H, dd, J = 5.5, 12.4 Hz, 6'-H),
5.14-5.25 (2H, m, 2 ', 4'-H), 5.28-5.36 (2H, m, 1', 3'-H),
7.10 (2H, d, J = 8.7 Hz, 3, 5-H),
7.85 (2H, d, J = 8.7 Hz, 2, 6-H), 9.92 (1H, s, CHO).
13 C NMR (100.5 MHz, CDCl 3 ) δ 20.61 (CH 3 × 3), 20.67 (CH 3 ), 61.83 (6'-C),
68.05 (4'-C), 70.94 (2'-C), 72.26 (3'-C), 72.48 (5'-C), 97.98 (1'-C),
116.70 (3, 5-C), 131.78 (1, 2, 6-C, reduced by DEPT 135),
161.15 (4-C, disappeared by DEPT 135),
169.17, 169.32, 170.14, 170.43 (CH 3 C O, disappeared by DEPT 135),
190.64 (CHO).
FAB-MS (m-NBA) m / z 452 (M + ), 451 ([MH] + ).
MALDI-TOF-MS (Pos., Dithranol) m / z 453 ([M + H] + ), 475 ([M + Na] + ), 491 ([M + K] + ).
Found: C, 55.66; H, 5.37%.
[実施例1]2−[4’−(2”,3”,4”,6”−テトラ−O−アセチル−β−D−グルコピラノシルオキシ)−2’,3’,5’,6’−テトラフルオロフェニル]フレロピロリジン[5]の合成
窒素気流下、C60(288mg,0.4mmol)の乾燥p−キシレン溶液(200mL)に、4−(2’,3’,4’,6’−テトラ−O−アセチル−β−D−グルコピラノシルオキシ)−2,3,5,6−テトラフルオロベンズアルデヒド[2](209mg,0.4mmol)およびサルコシン(53mg,0.6mmol)を加え、Dean−Starkトラップを用いて水を除去しながら、8時間加熱還流した。
反応液を減圧濃縮して得られた褐色固体(515mg)を、シリカゲルカラムクロマトグラフィーに付した。二硫化炭素溶出分より未反応のC60(85mg,30%)を回収後、次にトルエン−酢酸エチル(5:1(v/v))溶出分より褐色固体[226mg,44%(63%)]を得た。さらに褐色固体をベンゼン(20mL)で加熱溶解した後、放冷下にヘキサン(30mL)を加えて再沈殿し、褐色固体[5][200mg,39%(56%)]を得た。得られた生成物の分析結果を以下に示す。
Under a nitrogen stream, 4- (2 ′, 3 ′, 4 ′, 6′-tetra-O-acetyl-β-D-glucopyra) was added to a dry p-xylene solution (200 mL) of C60 (288 mg, 0.4 mmol). Nosyloxy) -2,3,5,6-tetrafluorobenzaldehyde [2] (209 mg, 0.4 mmol) and sarcosine (53 mg, 0.6 mmol) are added and water is removed using a Dean-Stark trap And refluxed for 8 hours.
The brown solid (515 mg) obtained by concentrating the reaction solution under reduced pressure was subjected to silica gel column chromatography. Unreacted C60 (85 mg, 30%) was recovered from the carbon disulfide eluate, and then a brown solid [226 mg, 44% (63%) from the eluate of toluene-ethyl acetate (5: 1 (v / v)) ] Was obtained. Further, the brown solid was dissolved by heating with benzene (20 mL), and then hexane (30 mL) was added under cooling and reprecipitated to obtain a brown solid [5] [200 mg, 39% (56%)]. The analysis result of the obtained product is shown below.
Brown Solid, mp.>300℃.
Relative ratio of diastereomers determined by 1H NMR:1/1.
IR (KBr) 2950, 2778 (CH), 1754 (C=O), 1493 (C=C),
1220, 1036 (O-C=O), 526 cm-1 (C60).
1H NMR (400 MHz, CDCl3) δ 2.03 (6H, s, CH3), 2.05 (1.5H, s, CH3),
2.06 (1.5H, s, CH3), 2.08 (3H, s, CH3), 2.88 (3H, s, N-CH3),
3.78 (0.5H, ddd, J = 2.3, 5.0, 9.6 Hz, 5”-H),
3.79 (0.5H, ddd, J = 2.3, 5.0, 9.6 Hz, 5”-H),
4.11 (1H, dd, J = 2.3, 12.4 Hz, 6”-H), 4.20 (0.5H, J = 9.6 Hz, 5-H),
4.21 (0.5H, J = 9.6 Hz, 5-H), 4.27 (0.5H, dd, J = 5.0, 12.4 Hz, 6”-H),
4.28 (0.5H, dd, J = 5.0, 12.4 Hz, 6”-H),
5.03 (1H, d, J = 9.6 Hz, 5-H), 5.17-5.33 (4H, m, 1”, 2”, 3”, 4”-H),
5.46 (1H, s, 2-H).
13C NMR (100.5 MHz, CDCl3) δ 20.57, 20.62 (CH3×4),
40.31 (N-CH3×2), 61.42, 61.47 (6'-C), 67.96 (4'-C×2),
69.39 (3 or 4-C×2, disappeared by DEPT 135), 69.71 (5-C×2),
71.25 (2'-C×2), 72.34 (3' or 5'-C×2), 72.42 (3' or 5'-C×2),
74.97, 75.03 (2-C), 75.74 (3 or 4-C×2, disappeared by DEPT 135),
101.51 (1”-C×2), 111.65 (1'-C×2, disappeared by DEPT 135),
134.00 (4'-C×2, disappeared by DEPT 135),
135.53, 135.55, 135.82 (2C), 136.52, 136.54, 137.90, 139.52 (2C), 140.11 (2C),
140.15, 140.16 (3C), 140.25 (2C), 141.59 (2C), 141.62 (2C), 141.67 (3C),
141.69(3C), 141.84 (2C), 141.86 (2C), 141.93 (3C), 142.06 (4C), 142.13 (4C),
142.16 (3C), 142.20 (2C), 142.58 (5C), 142.68 (2C), 143.01 (2C), 143.08 (2C),
144.26 (2C), 144.39 (3C), 144.41 (2C), 144.69 (3C), 145.15 (3C), 145.21 (4C),
145.27 (3C), 145.33 (4C), 145.37 (2C), 145.43 (3C), 145.52 (3C), 145.59 (4C),
145.66 (2C), 145.97 (4C), 146.06 (3C), 146.10 (3C), 146.18 (3C), 146.28 (2C),
146.34 (2C), 147.31, 147.35 (2C), 151.13 (2C), 152.28, 152.30, 153.20 (2C),
153.22, 155.42 (2C) (C60, 2', 3', 5', 6'-C, disappeared by DEPT 135),
169.19 (2C), 169.26 (2C), 170.11 (2C), 170.45 (2C)
(CH3 CO, disappeared by DEPT 135).
MALDI-TOF-MS (Pos., Dithranol) m/z 1272 ([M+H]+).
UV-Vis (CHCl3) λmax nm (log ε) 430 (3.30), 310 (4.46), 256 (4.97).
HPLC (ODS, CHCl3, flow rate 1ml / min) retention time 2.28 min.
Brown Solid, mp.> 300 ° C.
Relative ratio of diastereomers determined by 1 H NMR: 1/1.
IR (KBr) 2950, 2778 (CH), 1754 (C = O), 1493 (C = C),
1220, 1036 (OC = O), 526 cm -1 (C 60 ).
1 H NMR (400 MHz, CDCl 3 ) δ 2.03 (6H, s, CH 3 ), 2.05 (1.5H, s, CH 3 ),
2.06 (1.5H, s, CH 3 ), 2.08 (3H, s, CH 3 ), 2.88 (3H, s, N-CH 3 ),
3.78 (0.5H, ddd, J = 2.3, 5.0, 9.6 Hz, 5 ”-H),
3.79 (0.5H, ddd, J = 2.3, 5.0, 9.6 Hz, 5 ”-H),
4.11 (1H, dd, J = 2.3, 12.4 Hz, 6 ”-H), 4.20 (0.5H, J = 9.6 Hz, 5-H),
4.21 (0.5H, J = 9.6 Hz, 5-H), 4.27 (0.5H, dd, J = 5.0, 12.4 Hz, 6 ”-H),
4.28 (0.5H, dd, J = 5.0, 12.4 Hz, 6 ”-H),
5.03 (1H, d, J = 9.6 Hz, 5-H), 5.17-5.33 (4H, m, 1 ”, 2”, 3 ”, 4” -H),
5.46 (1H, s, 2-H).
13 C NMR (100.5 MHz, CDCl 3 ) δ 20.57, 20.62 (CH 3 × 4),
40.31 (N-CH 3 × 2), 61.42, 61.47 (6'-C), 67.96 (4'-C × 2),
69.39 (3 or 4-C × 2, disappeared by DEPT 135), 69.71 (5-C × 2),
71.25 (2'-C × 2), 72.34 (3 'or 5'-C × 2), 72.42 (3' or 5'-C × 2),
74.97, 75.03 (2-C), 75.74 (3 or 4-C × 2, disappeared by DEPT 135),
101.51 (1 ”-C × 2), 111.65 (1'-C × 2, disappeared by DEPT 135),
134.00 (4'-C × 2, disappeared by DEPT 135),
135.53, 135.55, 135.82 (2C), 136.52, 136.54, 137.90, 139.52 (2C), 140.11 (2C),
140.15, 140.16 (3C), 140.25 (2C), 141.59 (2C), 141.62 (2C), 141.67 (3C),
141.69 (3C), 141.84 (2C), 141.86 (2C), 141.93 (3C), 142.06 (4C), 142.13 (4C),
142.16 (3C), 142.20 (2C), 142.58 (5C), 142.68 (2C), 143.01 (2C), 143.08 (2C),
144.26 (2C), 144.39 (3C), 144.41 (2C), 144.69 (3C), 145.15 (3C), 145.21 (4C),
145.27 (3C), 145.33 (4C), 145.37 (2C), 145.43 (3C), 145.52 (3C), 145.59 (4C),
145.66 (2C), 145.97 (4C), 146.06 (3C), 146.10 (3C), 146.18 (3C), 146.28 (2C),
146.34 (2C), 147.31, 147.35 (2C), 151.13 (2C), 152.28, 152.30, 153.20 (2C),
153.22, 155.42 (2C) (C 60 , 2 ', 3', 5 ', 6'-C, disappeared by DEPT 135),
169.19 (2C), 169.26 (2C), 170.11 (2C), 170.45 (2C)
(CH 3 C O, disappeared by DEPT 135).
MALDI-TOF-MS (Pos., Dithranol) m / z 1272 ([M + H] + ).
UV-Vis (CHCl 3 ) λ max nm (log ε) 430 (3.30), 310 (4.46), 256 (4.97).
HPLC (ODS, CHCl 3 , flow rate 1ml / min) retention time 2.28 min.
[比較例1]2−[p−(2”,3”,4”,6”−テトラ−O−アセチル−β−D−グルコピラノシルオキシ)フェニル]フレロピロリジン[7]の合成
窒素気流下、C60(288mg,0.4mmol)の乾燥p−キシレン溶液(200mL)に、4−(2’,3’,4’,6’−テトラ−O−アセチル−β−D−グルコピラノシルオキシ)ベンズアルデヒド[3](181mg,0.4mmol)およびサルコシン(36mg,0.4mmol)を加え、Dean−Starkトラップを用いて水を除去しながら、8時間加熱還流した。
反応液を減圧濃縮して得られた黒褐色固体(533mg)を、シリカゲルカラムクロマトグラフィーに付した。二硫化炭素溶出分よりC60(135mg,47%)を回収後、ベンゼン−酢酸エチル(5:1(v/v))溶出分より黒褐色固体[216mg,45%(85%)]を得た。さらに黒褐色固体をベンゼン(4mL)で加熱溶解した後、放冷下にエタノール(20mL)を加えて再沈殿して黒褐色固体[7][158mg,33%(76%)]を得た。得られた生成物の分析結果を以下に示す。
Under a nitrogen stream, 4- (2 ′, 3 ′, 4 ′, 6′-tetra-O-acetyl-β-D-glucopyra) was added to a dry p-xylene solution (200 mL) of C60 (288 mg, 0.4 mmol). Nosyloxy) benzaldehyde [3] (181 mg, 0.4 mmol) and sarcosine (36 mg, 0.4 mmol) were added, and the mixture was heated to reflux for 8 hours while removing water using a Dean-Stark trap.
A black-brown solid (533 mg) obtained by concentrating the reaction solution under reduced pressure was subjected to silica gel column chromatography. C60 (135 mg, 47%) was recovered from the carbon disulfide eluate, and a black-brown solid [216 mg, 45% (85%)] was obtained from the eluate of benzene-ethyl acetate (5: 1 (v / v)). Further, the black brown solid was heated and dissolved with benzene (4 mL), and then ethanol (20 mL) was added under cooling and reprecipitation to obtain a black brown solid [7] [158 mg, 33% (76%)]. The analysis result of the obtained product is shown below.
Brown solid, mp.> 300℃.
Relative ratio of diastereomers determined by 13C NMR:1/1.
IR (KBr) 2950, 2810, 2784 (CH), 1758 (C=O),
1228, 1040 (O-C=O), 526 cm-1 (C60).
1H NMR [(400 MHz, CDCl3 - CS2 (2:1)] δ 1.99, 2.015, 2.023, 2.04 (each 3H, s, CH3),
2.76 (3H, s, N-CH3), 3.80-3.86 (1.0H, m, 5”-H),
4.12 (1H, dd, J = 2.3, 11.9 Hz, 6”-H), 4.24 (1H, d, J = 9.6 Hz, 5-H),
4.24-4.27 (1H, m, 6”-H), 4.88 (1H, s, 2-H), 4.96 (1H, d, J = 9.6 Hz, 5-H),
5.06-5.15 (2H, m, 2”, 4”-H), 5.18-5.28 (2H, m, 1”, 3”-H),
7.01 (2H, d, J = 8.7 Hz, 3', 5'-H), 7.70 (2H, br s, 2', 6'-H).
13C NMR [(100.5 MHz, CDCl3 - CS2 (2:1)] δ 20.39, 20.42, 20.48, 20.55 (CH3×2),
39.90 (N-CH3×2), 61.78 (6”-C×2), 68.09 (4”-C×2),
68.82 (3 or 4-C×2, disappeared by DEPT 135),
69.90 (5-C×2), 71.02 (2”-C×2), 72.00 (3”-C×2), 72.60 (5”-C×2),
77.23 (3 or 4-C×2, disappeared by DEPT 135), 82.92 (2-C×2),
98.66, 98.74 (1”-C), 116.89 (3', 5'-C×2), 130.42 (2', 6'-C×2),
131.69 (2C), 131.73 (2C), 135.57 (2C), 135.73 (2C), 136.33 (2C),
136.79 (2C), 139.50 (2C), 139.82 (2C), 140.07 (2C), 140.10 (2C),
141.43 (2C), 141.57 (2C), 141.71 (2C), 141.79 (2C), 141.86 (2C),
141.92 (2C), 141.94 (2C), 142.01 (2C), 142.04 (2C), 142.12 (4C),
142.47 (4C), 142.51 (2C), 142.58 (2C), 142.90 (2C), 143.04 (2C),
144.23 (2C), 144.28 (2C), 144.46 (2C), 144.58 (2C), 145.03 (2C),
145.11 (4C), 145.15 (2C), 145.19 (2C), 145.24 (2C), 145.27 (2C),
145.38 (4C), 145.45 (2C), 145.60 (2C), 145.81 (2C), 145.99 (2C),
146.02 (2C), 146.05 (4C), 146.09 (2C), 146.17 (2C), 146.19 (2C),
146.28 (2C), 146.47 (2C), 147.17 (4C), 153.00 (2C), 153.18 (2C),
153.76 (2C), 156.03 (2C), 156.60 (2C),
156.64 (2C), (C60, 1', 4'-C, disappeared by DEPT 135),
168.81 (2C), 168.96 (2C), 169.79 (2C),
170.08 (2C) (CH3 CO, disappeared by DEPT 135).
FAB-MS (m-NBA) m/z 1200 ([M+H]+), 720 (C60).
MALDI-TOF-MS (Pos., Dithranol) m/z 1200 ([M+H]+), 1222 ([M+Na]+),
1239 ([M+K]+), 480 ([M-C60]+).
UV-Vis (CHCl3) λmax nm (log ε) 431 (3.58), 308 (4.59), 256 (5.09).
HPLC (ODS, CHCl3, flow rate 1 ml/min) retention time 2.62 min.
HPLC (Diol, CH3CN, flow rate 1 ml/min) retention time 8.28 min.
Anal. Calcd for C83H29O10N : C, 83.07 ; H, 2.44 ; N, 1.17%.
Found : C, 82.26 ; H, 2.90 ; N, 1.25%.
Brown solid, mp.> 300 ° C.
Relative ratio of diastereomers determined by 13 C NMR: 1/1.
IR (KBr) 2950, 2810, 2784 (CH), 1758 (C = O),
1228, 1040 (OC = O), 526 cm -1 (C 60 ).
1 H NMR [(400 MHz, CDCl 3 -CS 2 (2: 1)] δ 1.99, 2.015, 2.023, 2.04 (each 3H, s, CH 3 ),
2.76 (3H, s, N-CH 3 ), 3.80-3.86 (1.0H, m, 5 ”-H),
4.12 (1H, dd, J = 2.3, 11.9 Hz, 6``-H), 4.24 (1H, d, J = 9.6 Hz, 5-H),
4.24-4.27 (1H, m, 6 ”-H), 4.88 (1H, s, 2-H), 4.96 (1H, d, J = 9.6 Hz, 5-H),
5.06-5.15 (2H, m, 2 ”, 4” -H), 5.18-5.28 (2H, m, 1 ”, 3” -H),
7.01 (2H, d, J = 8.7 Hz, 3 ', 5'-H), 7.70 (2H, br s, 2', 6'-H).
13 C NMR [(100.5 MHz, CDCl 3 -CS 2 (2: 1)] δ 20.39, 20.42, 20.48, 20.55 (CH 3 × 2),
39.90 (N-CH 3 × 2), 61.78 (6 ”-C × 2), 68.09 (4” -C × 2),
68.82 (3 or 4-C × 2, disappeared by DEPT 135),
69.90 (5-C × 2), 71.02 (2 ”-C × 2), 72.00 (3” -C × 2), 72.60 (5 ”-C × 2),
77.23 (3 or 4-C × 2, disappeared by DEPT 135), 82.92 (2-C × 2),
98.66, 98.74 (1 ”-C), 116.89 (3 ', 5'-C × 2), 130.42 (2', 6'-C × 2),
131.69 (2C), 131.73 (2C), 135.57 (2C), 135.73 (2C), 136.33 (2C),
136.79 (2C), 139.50 (2C), 139.82 (2C), 140.07 (2C), 140.10 (2C),
141.43 (2C), 141.57 (2C), 141.71 (2C), 141.79 (2C), 141.86 (2C),
141.92 (2C), 141.94 (2C), 142.01 (2C), 142.04 (2C), 142.12 (4C),
142.47 (4C), 142.51 (2C), 142.58 (2C), 142.90 (2C), 143.04 (2C),
144.23 (2C), 144.28 (2C), 144.46 (2C), 144.58 (2C), 145.03 (2C),
145.11 (4C), 145.15 (2C), 145.19 (2C), 145.24 (2C), 145.27 (2C),
145.38 (4C), 145.45 (2C), 145.60 (2C), 145.81 (2C), 145.99 (2C),
146.02 (2C), 146.05 (4C), 146.09 (2C), 146.17 (2C), 146.19 (2C),
146.28 (2C), 146.47 (2C), 147.17 (4C), 153.00 (2C), 153.18 (2C),
153.76 (2C), 156.03 (2C), 156.60 (2C),
156.64 (2C), (C 60 , 1 ', 4'-C, disappeared by DEPT 135),
168.81 (2C), 168.96 (2C), 169.79 (2C),
170.08 (2C) (CH 3 C O, disappeared by DEPT 135).
FAB-MS (m-NBA) m / z 1200 ([M + H] + ), 720 (C 60 ).
MALDI-TOF-MS (Pos., Dithranol) m / z 1200 ([M + H] + ), 1222 ([M + Na] + ),
1239 ([M + K] + ), 480 ([MC 60 ] + ).
UV-Vis (CHCl 3 ) λ max nm (log ε) 431 (3.58), 308 (4.59), 256 (5.09).
HPLC (ODS, CHCl 3 , flow rate 1 ml / min) retention time 2.62 min.
HPLC (Diol, CH 3 CN, flow rate 1 ml / min) retention time 8.28 min.
Anal. Calcd for C 83 H 29 O 10 N: C, 83.07; H, 2.44; N, 1.17%.
Found: C, 82.26; H, 2.90; N, 1.25%.
[実施例2]
レジオレギュラーポリ(3−ヘキシルチオフェン)(メルク社製、製品名:lisicon(登録商標)SP−001)20mgおよび化合物[5]10mgを、クロロベンゼン1mLが入ったサンプル瓶の中に加え、60℃のホットプレート上で15時間撹拌して溶液Aを得た。
正極となるITO透明導電層を2mm×25mmのストライプ状にパターニングした25mm×25mmのガラス基板を30分間UV/オゾン処理した後に、基板上に正孔輸送層となるPEDOT:PSS水溶液(H.C.Starck社製、製品名:Clevios P VP.AI 4083)をスピンコート法により30nmの厚さに成膜した。ホットプレートにより150℃で30分間加熱乾燥した後、不活性ガスにより置換されたグローブボックス中で上記の溶液AをPEDOT:PSS層上に滴下し、スピンコート法により膜厚90nmの有機半導体層を形成した。
その後、有機半導体層が形成された基板と陰極用マスクを真空蒸着装置内に設置して、装置内の真空度が1×10-3Pa以下になるまで再び排気し、抵抗加熱法によって、負極となるアルミニウム層を100nmの厚さに蒸着した。
以上のようにして、ストライプ状のITO層とアルミニウム層とが交差する部分の面積が2mm×2mmである光起電力素子を作製した。
得られた光起電力素子の光電変換効率は、ソーラーシミュレータ(分光計器(株)製、OTENTOSUN−III、AM1.5Gフィルター、放射強度:100mW/cm2)を用いて一定の光を照射し、発生する電流と電圧を測定して求めた。結果を表1に示す。
[Example 2]
20 mg of regioregular poly (3-hexylthiophene) (manufactured by Merck, product name: risicon (registered trademark) SP-001) and 10 mg of compound [5] were added to a sample bottle containing 1 mL of chlorobenzene. The solution A was obtained by stirring on a hot plate for 15 hours.
A 25 mm × 25 mm glass substrate obtained by patterning an ITO transparent conductive layer serving as a positive electrode into a 2 mm × 25 mm stripe pattern was subjected to UV / ozone treatment for 30 minutes, and then a PEDOT: PSS aqueous solution (HC) serving as a hole transport layer on the substrate. A product made by Starck, product name: Clevios P VP.AI 4083) was formed to a thickness of 30 nm by spin coating. After heating and drying at 150 ° C. for 30 minutes by a hot plate, the above solution A is dropped on the PEDOT: PSS layer in a glove box substituted with an inert gas, and an organic semiconductor layer having a thickness of 90 nm is formed by spin coating. Formed.
Thereafter, the substrate on which the organic semiconductor layer is formed and the cathode mask are placed in a vacuum deposition apparatus, and the vacuum is again exhausted until the degree of vacuum in the apparatus becomes 1 × 10 −3 Pa or less, and the negative electrode is formed by resistance heating. An aluminum layer was deposited to a thickness of 100 nm.
As described above, a photovoltaic device having an area where the stripe-shaped ITO layer and the aluminum layer intersect each other was 2 mm × 2 mm was produced.
The photoelectric conversion efficiency of the obtained photovoltaic device was irradiated with constant light using a solar simulator (manufactured by Spectrometer Co., Ltd., OTENTOUN-III, AM1.5G filter, radiation intensity: 100 mW / cm 2 ). It was determined by measuring the generated current and voltage. The results are shown in Table 1.
[比較例2]
化合物[5]の代わりに化合物[7]を用いた以外は、実施例2と同様にして光起電力素子を作製し、その特性を測定した。結果を表1に併せて示す。
[Comparative Example 2]
A photovoltaic device was prepared in the same manner as in Example 2 except that the compound [7] was used instead of the compound [5], and the characteristics thereof were measured. The results are also shown in Table 1.
Claims (7)
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CN105924471A (en) * | 2016-05-03 | 2016-09-07 | 南京邮电大学 | Open-loop fullerene interface modification material, and preparation method and application thereof |
CN109232559B (en) * | 2018-10-08 | 2021-02-02 | 河南师范大学 | Synthesis method of [60] fullerene dihydrocarboline derivative |
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